im Published by: AARYUSH EDUCATION. 8-3/2, Ground Floor, DLF, Ankur Vihar ‘Ghaziabad (U.P.) Branch : 570/140, Bhartiya Colony, New Mandi, Muzaffarnagar (U.P.) Mob. No.-09650813715 09312466953 09457640709 website : wwwaaryusheducation.com iM © Author i First Edition : 2014 Design by : 2 Prakash Graphics Hi] to partot his book may be reproduced in rial sytem or taste, in any form or by fany means electronics, mechanical photocopying, rearing ar without pemission ofthe ‘Auterpubishers Pn 2 co To the memory of my motheree! pleasure to introduce this book. The content given in the book will be invaluable to teaching and learning concept of Organometallic & Bioinorganic Chemistry. also feel pleasure that tis book is written by my colleague, We (myself, Ajai Kumar and Meenu Srivastava) normally share ‘and discuss the fundamentals of inorganic chemistry including Organometallic & Bioinorganic Chemistry when we ae in laboratory, staff room or the teacher's room. ‘The questions, objective and subjective have the levels of various competition exams lke ITTJAM, CSIR-UGC (JRE/NET), GATE, Se, BAR, _TIFR, DRDO, ONGC, NTPC, NBRC etc. The fundamentals of Organometallic ‘& Bioinorganic Chemistry are written according tothe need ofthe students. {wish thatthis book may give away of sure success, Dr. Ram Sharan ‘Associate Professor (Deptt. of Chemisty) Hindu College, University of Delhi, Delhi In this book I have attempted to highlight the concepts Organometallic & Bioinorganic Chemistry relevane to students of undergraduate and postgraduate levels of all Indian universities. { have ‘written this book ina readable and easily understandable way. Numerous cexamplesare provided throughout the tex. hope that this book wall be very helpful for che aspicants of all competitive exams related to chemistry ike ITTJAM, CSIR-UGC (NET/IRF), GATE, TIFR, BARG, IISc, DRDO, ONGC, NTPCetc. Thave incorporated large number of objective questions asked in the past competitive exams to know the level of question paper for future competitive examinations. Thavetaken particular care to ensure thatthe textis ree of errs. ‘Thiseditionis successfully produced with the help of Mr. Prakash Arora. 1 express my sincere thanks to my daugghters-Apeksha and Aradhya, iy son-Aaryush and my wife-Mrs. Archana and my other family members, Without the help of my wife Mrs. Archana, writing of this book would only be dream, notrealit. 1 thankeo itz Gulam Nabi Yatoo and Mr. Vikas Yadav Kosta for heir most ‘valuable support and suggestions. {thank to Dr. Meenu Srivastava, Dr. Sudarshan, Mt Kuldeep Garg, Dt. Raghvi Katt, Mz. Gobidn Goyat and Mr Vipin Khoker for their constructive suggestions. Ifa Jeamer found any error in the text, please send your constructive “criitsm ard suggestions to. update the book time to time. The eiticism will be gratefillyreceived and acknowledge. teal —Ajai Kumar 21-June-2014 ajailecthe@rediffmall.comOrganometallic & Bioinorganic Chemistry ‘An Introduction to Organbitietlic Compounds ‘Meial Carbonyis ‘Cluster Compounds “Reactions ‘of Organometallic Compounds Alkyl, Carbene, Carbyne, Alkene, Alkyne, Ally! and Buta-1,3-dierie' Complexes: Cyclic Polyene Complexes: Catalysis Coupling Reactions Bioinorganic Chemistryi | | An Introduction to Organometallic Compounds ‘An organometalic compound is define as one that cintins alent one direct mesbatbon bond. Thisexcides some catbon compounds which ar cosiered tobe inorganic uch a abides, 6, Ca and cynies eg, NacN. The exon conning groupe may te carbon alae, aromatic, ey ot heterojli,Te vaso ids tht ae attached to meta in organometalc compounds are sunmaizedin Table 1. ‘There are some complexes which do not contain ary M--C bonds but are considered tobe the members of erganomealc compounds For ramp Wikinson catalyst R(PPh),Cl which sased for tydrogenaton of alkenes and alles. There is no metalatbon bond. However, itis an ergenometalie compound. Ducingextalye eof hyogeaton of lees a tage comes when alkene is atached othe metal and fonts metaarbon bond, Due to this eason it a member of trganometaie compounds. According leting journals of organonetalc compound, the bondlg interaction sonic or covaten, old or deloealied between aleastone carbon atom of an organi group or molec and a man gp, tension, lnchanide or actnide metal stom, Exeepinaly binty metal carbons ike NICD), ae considered as organometalic compounds even though CO ian inorganic amp, Sm orga dervatves of the metals sch teon, lion, germanium arsenic and ele re considered eo be organometalc compounds. Organomet compounds straddle both inorganit and organi chemist. The fis organomazalic eompound ofan grou cements was encod oxide which has repulsive smell and saton igi. ay at an or ((CHs),A8},0 Hy Dineliyasions ggperte (Cacodyl one)Oraanometic snd Binnie Chemisty ‘This compound was orginally synthesized by heating arsenic trioxide with potassium acetate. £05 + ACH,COOK —+{(CH3),Ae],0+2K,003 +200), Dicacodyl is alo considered one of the earliest organometallic compounds ever discovered. It ‘was investigated by Edward Frankland and Robert Bunsen, I¢ was orginally made from arsenic distilled with potassium acetate any at, ee or (Gilg) Ase 4 any at, a Tetameshyldiarsane ieacody ‘The first organometallic compound ofthe transition metals was Zeise's salt, K[Pt(CaH,)Cls} co ™ ai eises salt Unlike convensional transition metal complexes, the central metal atom in an organometallic . ‘compounds is often in alow oxidation state (Le, -1, 0 ar +1 or Sometime + 2). On the basis of periodic table, organometallic compounds can be classified into main group, transition metal and lanthanideactinide organometallic compounds. Main Group Organometallic Compounds Na"CsHZ, n-BuLi, B(CH,CH)s, Lig(CHs)4,R,PDE kyl or aryl group, X = CBr, 1, Ala(CHy)o te ‘Transition Metal Organometallic Compounds : Examples, Q P . @ < r ocw-Ni— ,Rh(PPh),Clete Q We Examples ‘Aa Induction to Orsnemeac Coiponds Lanthanide/actinide organometallic compounds : Example Uranocene Applications of Organometallic Compounds (2) Organometallic Compounds as Reagents : Some organometlie compounds especialy the alkali and alkaline earth metal compounds such as n-BuLi, sBuli, Bai, Grignard reagent (RMgX), Gilman's reagent (R,Cul) etc are used as reagents. (2) Organometallic Compounds as Catalysts : The organometalic compounds are being routinely used as catalysts forthe sythesis of organic compounds. Some well kowm organomezallic homogeneous catalysts are given in Table 1.1: ‘Table 1.1 Homogeneous Catalysts —— {Rh(CO),1,) ‘Methanol carbonylation (Ir(CO) 12) ‘Methanol carbonylation av] Sh Olefin metathesis PCys (Second generation catalyst, heterocyclic carbene)ee (Orgasonitalic nd Biiorpaic Chemisty ‘Vitamin By, Gnown as roenryme 62) isthe only known organometallic compound in nature. It incorporates cobalt into a corrn ring and has been found to have many catalytic properties Organometallic Compounds as Drugs : ‘The frst organometallic compound found for anticancer activity was Cp2TiCla (Fig. 1.1(8)). An another important organometallic compo i ferroquine (FQ) [Fig 1.1(0)] which is used as antimalarial drug, © Fig, 1.1 Structure ofa) Gpe TiC (8) Forroguine {9} Organometallic compounds as additives : Organometallic compounds have find applications as bulk additives for modifying the existing properties of eompouncs. Rrrocene is readily soluble in liquid fuels, ar stable, non-toxic and usually thermally sable. Ferrocene i, therefore, added to liquid fuel to reduce carbonaceous partcilete mater like soo emitted by diesel engines. The carbonaceous paciculaes are health hazard. Tetraethyllead [Fig 12(b)] was Used as antiknocking agent in the gasoline. TEL helps the gasoline to bur slowly and smoothly and preveats ‘knocking. Combustion of TEL along with gasoline forms paricles of Pb and PbO which are very hharmful. for health. Now, therefore methyleyclopentadienylmanganesetrcarbony] (MMT) [Fig 1.2(€)] is used in place of TEL. as ant-knocking agent. ~~ «2S Fe Pb: 9. /— Ne aR oc eo NAL ® @ © @ ‘An Intoducion o Onanonetalc Compounds 18 ewas found that MMT is harmless fr automobiles. Bistributyltnoxide (TET) Fig. 1.2 (is an anti-foulant. tis used for coating outside of ships. Organic Ligands and Nomenclature According to IUEAC recommendation in the formulas of organometallic compounds metal is ‘writen ist owed by formally anionic ligand in alphabatcl over, the neural igands are then sted in alphabascal order based on heir chemical symbol A number of unsstursted gegenicigands such as all, cRlopentadient ethylene, benzene ec. can interact with metal in more than one rode. Hapticity A single organic igand may interact with a cena! meta atom using one or moce ofits atoms simultaneously. The number of atoms ina ligand atached to the metal atom is denoted bythe pref 1 (Che Greek eter eta) followed by a superscript indicating the numberof ligand atoms tached 0 the metal atom. Thisis alld haptic, Most ligands aah through one tom ony, therefore, they recalled as monchapto (a). Cyclopentadienyl ligand, CgH5 of Cp for example cam azack metal tom through one thre of five catbon atoms. Therefore, it may act as mono (yt (q?> oF ppentahapo (n° Higand (Fig. 1.3). Om nip @ Fig. 13 The tem hapo comes fro the Greek word haptein meaning to fasten. Therefore, pemtahapto + moans fastened ve placed ‘The hay of vais ligands is shown below : (a)n!-monohapto ligands) : MR (where R= Clty, — GH, —CH,,— Cyl ete) 9 ll MCR W MoCmsae An nts ‘Orsinometlic Compounds wacd” (ot- Norbomadiene where COT = gclooctatetaene i MiSr Orasnomatalic nd Bsinoganic Chenisty “The ligand which can change its haptic is called a luxonil ligand thapticty ofa ligand is not given, then the ligand has to be assume ints highest haptcity. eg, Cp on, allyl on’. ‘he IUPAC name of some compounds ae given below = @ a fk bis(eyelopentadieny) iron(i) & @ ao Ie vistonl'bpettondnaexiea of, IN. @) cr (benzene) tricarbony| chromium we? 4], co © ighoon Electron Rule The main group element such as lead uses its four valence electrons for the formation of four Dongs and asa result a stable compound such as PEt, is obtained. In such compounds, the total ‘sumer of valence electrons becomes equal 98, :¢, these compounds obey octet rule, On the other hand PLE, contains only si valence ekerons and therefore doesnot obey octet rule and is unstable However there are some complexes which do not obey the octet role and are unstable In general organometallic compounds of warsitan metas ate formed with metals that are inlow oxidation states (-1, 0 and +1). According o Swi effective atomic number (EAN) rule, the EAN ‘of metals equal tothe sum of electrons on metal plus the electrons donated by the liginds and EAN isequal tothe atomic number of next noble gs, i, equal 46 (Kr), 54 (Ke) of 86 (fn) ‘An alterate and more general rule isthe 18-leeuon rule, According to this rule, in an organometallic compounds and other complexes the sum of valence shel electrons of transition ‘etal ormetal ion and electrons donate by the ligands is equal to 18, It provides a closed and stable valence shell configuration (n ~3)d"ns%npS, In tacsiton mets, che electrons of (h~I)d and ns clectrons are considered tobe valence electrons. The complexes which obey the FAN or 18lectron ral are considered tobe stable. The EAN and 1S-leeron rules ae similar. The 18- Na"{V(OO))" ‘The complex which contains 19 or 20-electrons is strong reducing agent. Forexample,CoCp2, a 19 electron complex, is eal oidied tothe 18-ectron cation cK ps Cocp; —> (Cpx0o)" +e° Similarly, Nigp2 i a 20e” complex and is eaiy oxidized to 18e~ species NiCp™ Nicp2 —> (Nicpal® +28 eliwedciato rocco Some examples electron counting ae given in Table 1.3. Table 13 i ‘Hieerron Counting No] Compound | Oxidation State Method | Neutral Atom Method 6 Te 1. | taco), me | we te 22108 5x2=10e $6 Sx2e1Oe | §c0 7 * we 7 Fe fe 2 |P-coti nak ca Fa 7 se -csHts)Fe(CO)2ct | Fe oe Fe : 3. | (9? Cots) Fe(Co) os eae ee Jeo" 4e |200 4e | or ae |a ee ee" . te 4. | ammo, Mat ce | Me X aoe | 5 oe ee" Be ze | Mo ber ge") alts Se 5. be | We Gatls Seo ° ae | KO) le Be ~ Ie oer Mom oe oa es . a Gslls aes Not) a Ko") 3676) Oranomtalli a Bioinorganic Chemie Ru Be _— 2h, ae : acts a (ez Objective Questions Charge Te Ne Tee" 1, The complex that does not obey 18 electon rule is creas (@) (Gn? ~C3H,RUCCCONPAS)) ‘ mace aac ©) {WCCO}, ite )(CNCMedg] lee (©) [IrCly (PPh3 )2(AsPh)) (@ [050)Br,(PMe5)0NMe. 2. Among the following, che unstable carbonyl species is ' (@) Mn(C0),c1 (©) IMn(CO)s- (© (Mn(CO),)" (@Mn(C0)s 3, In which one ofthe following complexes isthe formal oxidation state and coordination number of Co are=1 and 4 respectively? (@) Cox(CO)s (B) RCO(CO}, i (©) Na{Co4(CO},.} Ed) Na{Co(CO},] t 4, Identiy the 18 specie inthe ist below (@) Ni(H,O)e (b) Fe(CO)s ©) (n'CcHs) Ru @ VCO), ‘5. The oxidation state of molybdenum in ((n?-tropylium) Mo(Co),]"is {a) +2 &) +1 } @o @-t i 6. The cote formulcon for ea (ydopentadieny!)sianiam(V) complexis | (@) (Ma -C3H)4) ©) fH! -C3H1)41 i (©) (TiC? - CHS TS CsHs)s] © [Tien -CsHs)2(0'-CsHs)n] 7 Asnong the complexes () (Cle)Ce i WMn{CO)s} HD UCH,CO)R(CO}LT and - | (iv) CpPe (CO), (CH), the 18-electron rule is not followed in : | (a) Gill) only (b) Gi) and (iti) ' () (i) and (iv) (@ Gi) only 8. Oxidation number of Fe in[Fe(NO)(CN)s] is @1 2 3 @0 9. Oxidation number of Coin Co(NO) (CO); is | @1 2 (3 @aw ooo) Y (¥) [n° -CsHs) Rh(CHs) (PPh3),]" L 118 = Organometallic and Bioinorganic Chemistry 1419 10. The organometallic compound W(C3H),(CO); follows the 18-electron rule. The 19, The hapticity of nitrosyl in(Mo(y ally); (q? ally) gNOI is s){COz fe 18-lecton The haptic in Mo(a all) (q? ally!) .NOlis hhapticities of che two cyelopentadienyl groups are : @1 “we | (@) Sands @ Sands 3 @o | (© 3and3 (@ Land | 111. Which one of the following molecules does not obey the 18-electron rule? (@) Mn(Co},)* (b) Fe(CO)s, ba (© [ex(co) 5] (@ IMa(Co),Cl,]* La 2@ 38 40 50 6@ 2 : 12, The hapiiy of pcohepn-.35-wiene in (CH e(OO)s i: 80 80 2H 2H 2H BH we | 5 w4 KO 6 O Oe BH 9 w ‘ 6 (7 | 418, The complex which obey the 18-electron rule i _ | (@) Fe(0O), 0) NiO} PPIs) te ae A is | (© x00, (@) crtC3Hs), sf 5/__ Subjective Questions : 14, To satisly the 18-clectron rule in the complex (cycloheptatriene, Mo(CO.)), the hapticity ofthe coordinated glohepttrene ligand must be : : @6 ws 1, Show that che meal centres in the following complexes obey the 18-leetron rule: | | 4 (2 (@ Rh CUED ala? -Cotl,) PPh a)2 | 15. 44 ee sae of ein he comple Op Fe(COhla is Gi) (n° -CsHs) Ie’ -CyH,) (PPh) 1 a) + O+ 2 ° | fo 1 Gi) (? - CFs) 2RAG-C), Rh (q°-CoH5) 2 rl PT 16 nent (Em, | te: PPhy 2. Compute the coordination number, oxidation numberof metal, VEC and give the name of \ (@) 18erule and stable the following species. alo select the species which obey the 18-eletron rule: (©) 16e" rule and unstable {@) Cp(CO) Inr-CO}, Re(CO)Cp (0) [Fe(CHeIICH)I” (9 1% lead email ans (0 Ti(n’-Cyach (@) [epFe(COMPPDS XCFIBRL ° erste (€) Op} ZC © LewNOKCN)sI* 17. The complex that o ul i ic) cone eae (@ [Feqoxey,F (8) 6-0). ©) {ey ~Ca.),00) { Ma(No),(CO) @ (COMPRA; CUNO | (© fMo(C0},(€H1,0005) 9 Cp COW-NO}s © [eterhs)s(2)2I" @ les -CHS)7) (m) Np(Cp)sMe (n) (y*-c01) Fe(CO)s 118. Identify the complex which does not obey the 18 electron rule : (0) [(m? ~C3Hs)a(1-CDRb};—_ (Rh—Rh single bond) (@) Fe(H.0),1" 8. Fallowing the 18-electton rule determine the unknown quantity in the following © RRu(n® -CoHedn® ~CHa)) , anon pF(COs (© Na{Co(CO},(FPhs)] @ pinccoy,)" ()[CpMx(C0),}, _(4nMn = Mn double bond)(© MaglFe(CO),)] @ [CpW(CO},}: © IcpM (CO); } (WW single bond) (single M—M bond, M is 4 transition metal) 4. A metal complex having methyl substituted Cp and CO ligand with the formula FeCgHi,03. The complex is highly soluble in polar solvent and obey 18-clection the ofthe complex. Determine the structure ofthe complex. 5. Define organometalic compounds. Which of the following are organometallic compounds ? © CHa MgB Gi) TOE, ©) ° ~Colig aCe 6, (a) What is meant by the term “Heptiity”? Explain with suitable examples. (© Whathapsicities are possible forthe interaction ofeach ofthe following ligands with a single d-block metal atoms ? (0 Coz, (i) butadiene, (i) cyelobutadiene, (iv) cyelopentadienyi, (¥) Cele, (i cyelooctatetraene. 7. (@) Give the valence electron count inthe following @OMn(s-C3H (CO)4) Gi) EHCo(CO}«1 GiD Fe(@-Cslt5) 9) (Mtn¢oo).ct (b) Predict whether the following obey E.A.N. rule and explain : @OMa(Co)s(CH)]" 9 (Co(a-CHs}(CO)s] Gi CO, G(VCO).F 8. (@) Using the 18-electron rule, indicate the probable numberof, mand the 3d metal (M1) inthe followings = Want ~C4H4,XCO),] GUGn® ~C Hg) ,CH(CO) Gi (9? ~ C3H453)M (CH14)0) Go) RAC? ~C HH 5XCO) a] )Ru (CO), 2 (©) Wirt the formulae of tree organometatc compounds having muticentred bonding. (iD (Cztts}azn (iv) Zeiee's salt ooo An Sones Metal Carbonyls carbon monoxide is undoubtedly one ofthe most important and most widey studied ligand i ‘organometalc chemistry. Almost al! ofthe ransitfon metals form metal carbonyls (the complexes containing only CO as ligands) and these homoleptic carbonyls are useful precursors for other ‘organomezalic compounds. Though carbon monoxide isnot considered a very Strong Lewis base, yet stforms strong bonds tothe metals in their complexes. In most ofthe metal carbonyls the metas are always in low oxidation states, most often in an oxidation state of zero but sometimes -1 or +1 and these carbonyls are often quite stable with respect to dissociation, substitution or oxidation. CO may bone to a single metal or it may act as a bridge between two or more mesa. The number of CO ligands coordinate tothe metal i generally in accordance with the 16-letron rue. The 18-electron rule is followed by almost 99% of metal carbonyls Classification of Metal Carhonyls (a) Classification on the Basis of Ligands : Metal carbonyls can be classified into two categories (0 Homolepticcasbonyl complexes (i Heteroleptc carbonyl complexes () Homoleptic Carbonyl Complexes The complexe in which a metal isbound to only CO ligands are knowin as homoleptic carbonyl complexes. For example, Ni(OO)4, Cx{CO)s, Fe(CO)s, {604(C0)s, Sn(CO)o,Fes(CO) ze (CO) g eteGi) Heteroleptic Carbonyl Complexes : The complexes in which metals bout! 19 CO as ‘wel as other ligands such as PR), PP, PF, NO, RNC, PF ete. For example, Ni(CO}s(2Ph3), Mo(CO)s(PF:)s,Cr(00}, (NO), ete 2) Classification on the Basis of Number of Metal Atoms and the Structures of Metal Carbonyts : (@ Mononuclear Metal Carbonyls These carbenyls contain only one metallic atom and these carbonyls donot contain any bridging CO ligand Forexample, Ni(CO)4,Cr(CO)«, Fe(CO)s et. i Potynuclear Metal Carbonyls : Polynuclear carbonyls contain two or more metal atoms. These are cassifed as (@) Homonuclear Metal Carbonyls : These contain metal etoms of only one element, For example, Fes(CO)», Mls(CO), CoO), Fes(COra, (CO), Rha (CO)z, r4(COVay ee () Heteronuclear Metal Carbonyls + These carbonyls contain metals of diferent cements. For example, MnCo(CO).. ‘The polynuclear metal carbonyls are also classified as (@) Non-bridged metal carbonyls and (©) Bridged metal carbonyls, () Nom-bridged Metal Carbonyis : These carbonyis contain terminal CO ligands and MM bonds. For example, Co4(CO)g (in solution), Mns(O),Ir(COrs et. {by Bridged Metal Carbonyls : These carbonyl contain bridged as well as terminal CO ligands and MM bonds. For example, Fea(CO)s,Coz(OO)s (in sold state), Fea(CO)a et Bonding in Metal Carbonyis (is considered to bea good c-donor as well asa-acceptor ligand, This property of CO and the other n-acceptor ligands such as CN", NO, CH, etc. can be explained by the MO diagram of CO igure. 2.1). When energy difference between 2s and 2p-orbials is small there will be mixing of s and p, orbitals. Since the energy difference between 2sand 2p orbitals for carbon is small, therefore, the 2sand 2p, orbitals on carbon mix to produce wo sp, mixed atomic orbitals. The higher energy c—o = @ Fig, 22 : (2) One bonding MO (6) One antibonding MO _ Singh fled sp, and p,aritals on each atom forma and a r-bond respectively. This eaves the orbital empey on carbon and the doubly ied p, orbital on oxygen (Fig. 2.3). The p., orbital on oxygen donates its pair of electrons to the empty p, orbital of carbon to form a dative bond or coordinate Singly occupied ‘peobital 6 ~w ca Eko \ SG Doubly occupied Vacant spgorbital py orbital Doubly occupied p, orbital bond (Fig. 2.3(b). This dative bond is also x-bond. This dative bond leads to aC—O* polarization in CO molecule which is almost exactly canceled by an opposite polarization * C—O" caused by the higher electronegativity of oxygen, Due 1 high elerranegativty of oxygen the x-bonding electrons are localized on oxygen and cause C*—O" polarization. ‘The molecular orbitals.energy level diagram (Figure, 2.1) shows that the HOMO has a 6 syrametry and the HOMO is localized on carbon, nt on oxygen because the effective nuclear charge or electronegatvity of carbon is less than that of oxygen. The HOMO of CO ligand donaces its lone pair of electtons to the empty orbital of suitable symmetry on the metal (eg., an spedz hybrid orbital) to form a M—CO o-bond (Figure. 24), OND + csv] — wD c= D on M~c=0 Carbon monoxide has two LUMO x orbitals which are also localized on carbon. These orbitals have cotrect symmetry to overlap with non-bonding metal dsorbitals that have symmetry such a thet (dy dy OF d,,)orbitalsin ocrahedral complex. A metal atom having electronsin a habia of suitable symmetry can donate eleetron density tothe LUMO x* of CO (Fig 2.5). The minteraction leads tothe delocalization of eleerons from filled orbital of suitable symmetry onthe metal atom {nto the empty x" orbitals onthe CO ligands. Because the electron density is lowing from the metal orbitals on to the x orbitals on ligands, this donation is known as rback donation or back bonding and che CO ligand i sald c be a strong x-acceptor (oF n-acid). The a-donor and x-acceptor interaction are shown in Figure. 2. Oe) Ge A Con Compound | veo tin em") rico), 1780 (vCOeI" 1860 [cx(CO)54 2000 [Min(CO),* 2100 {Fe(COygl* 2200 For cationie carbonyl complexes such as (Fe(CO)s]* the C—O stretching frequency is higher ‘than that in CO itself. Due to high positive charge on meta, the sity of metal to back donation of electrons is almost diminished. The HOMO of CO, 2 «orbital wich is slightly antibonding with respect to the C~O bond, donates its electron pair to metal. Therefore, population of HOMO and results in the strengthening of C~0 bond. Alternatively, in free CO, the electrons are polarized towards the more electronegative oxygen, he electron density in the x-orbitals is greater near tothe oxygen atom than tothe carbon atom. A ‘tansiton metal cation atracts the bonding electrons and, therefore, reduces che polarization inthe C0 bond there isa decrease in the wm 625 Less polarization of ¢~0 bond Due tothe reduction in the polarization of C—O bond, the electrons inthe cationic carbonyl complexes are more equally shared betvieen carbon and oxygen, and as result C—O bond becomes Stronger. Hence C—O stretching frequency is high in cationic carbonyl complexes. (2) Number of CO Ligands : As the number of CO ligands attached to a metal increases, the formal negative charge on metal increases, Therefore, che extent of back donation increases and fhence C—O stretching frequency decreases as shown Table 2.2, Organometallic and Bicinorganic Chemistry ; Table 22 ‘Compound veo Gin em") ‘Ni(CO), Ciadf Fe(CQ); 2034 00g = 1981 (3) Presence of Other Ligand on Metal : Carbonyl frequencies are also useful in CSe > CS > CO > PF > C=sNR > PCls > As(OR)y > PCOR)s > PRs > RC *), it wl N Sore triple bonded ligands which are isoelectronic with OO can also he arranged in order of -acceptar abilities. c=240 ‘Ornonitali-end Bisinorganic Chemisty ‘Therwo charged ligands CN" and NO* ofthis series difer substantially from other members and ae not always good analogs. The electron rich CN” isnot only a poor x-aoeptor but also a good ‘-donor and, therefore, forms many complexes with metal atoms in higher oxidation states. tthe ther end ofthis series, NO" is very strongly electron withdrawn. forms linearly inked MNO complees in which i is considered to be NO". in suc cases NO is considered as the cv electron donor NO* on the ionic model and asa three eletron dona onthe covalent model (Figure. 2.21 and 2.22), When NO takes an additional electron to form NO", the MNO links bent. n such complexes NOs considered as the two eleetron donor on the ionic model and one electron donor on covalent model (Figure 2.21 and 2.22) ‘The substituted phosphene ligands show the following order of basicity (Le, donor ability): hy > PAry > PCOR)s > PCOA) > PA, Where R= ali and Ar = ary The order ofx-aeceptor strength ofthese ligands is PRs PCl > PB > Pls It isto be noted that in phosphine PX, (where X= H,F, Cl, Br, I, Me, OMe, OAr) vacant 3d orbitals of Pas well as o* orbitals of PX act as x-acceptors but the vacant Storbtals play only a rminor role “The effect of other ligands present on Vg is shown in Table. 2.3. Table23 Complex veo in em) Ni(CO), coed Ni(CO)9(PF) an NuCoys(PCOPh) 1 2085 Ni(CO)sP Mes 2064 ‘On moving down the series in Table 2.3, the o-donor ability ofthe phosphine ligands increases and he x-acceptor ability decreases, PF; is the strongest x acceptor and the weakest donor (due to the presence of highly electronegative Suorines) As a result, nickel in Ni(CO), (PFs) carries the lowest electron density and, therefore, it has the lowest ability to donate electron density to x* orbital of the CO ligands, Therefore, there is less reduction in bond order of free CO. Consequently, the OD ligands in Ni(CO);(PF,) have shorter and stronger C—© bonds and therefore veo is larger than the lower complexes in Table 2.3. ‘nthe other hand, PMe isthe strongest a-donor and weakest x-acceptor. Asa result the nickel in Ni(CO),PMes cartes the greatest elecon density and it has greatest ability to donate electron density tothe x orbital ofthe CO ligands. Consequenty, tke O ligands in Ni(CO3 (Mes) havethe largest and weakest C—O bonds and hence, lowest C0 stretching frequency. However veg in Ni(CO), is highest because CO ligands are strongest x-acceptors in this series. Some examples of C—O stretching frequencies of te substituted facial carbonyl complexes of ‘molybdenum are shoven in Table 2‘Meal Carbs 2413 22, ‘Organometlc and Bsnorgic Chemisy Bonding Modes of CO eee The cao iandmay bono unsonmetisin an end-on ain through cto tm ae several ways. tsmay bond as a termina ligand asin simple carbonyl complexes such as Ce(CO)g, in Seats seo eee). Mihich it ac a2.a two eleazon donor. The veo for these complexes is usually in the range of Mo(CO);(PF)s 2090, 2055 12120-2850 em"! F carbonyl ligand may aso bridge two or more metals. (In this ase, the oo is in the range of Mo(CO),(PCls)s 2040, 1990 aa ‘Mo(CO)3{P(OPh)}, ‘Mo(GO) ;{P(OMe)s]s ‘Mo(CO)s¢Phs)5, i 1984, 1835 Mo(CO)s(Py), 1888, 1746 Mo(CO)3(PMes), | Mo(CO),(NMey)s 1045, 1954 If aligand (L) trans to aCO ligands a and x-donor, it will increase electron density on metal ‘which in turn increases metal to CO back bonding, Consequently, it decreases the C—O bond order and inereases the M—C bond order. Thus voy decreases and MC stretching frequency increases. If ‘we compare cs- and trans-isomers of PX(CO)LCI:] the C0 stretching frequency of trans. isomer is lower than that of cis-somer. ay yc L c=o 14 i L7 Na av" Na rans cs is 00s well as x-donor ‘where L = 6-donor = py, NHs, NMes Order of a donor ability is: NMes > NH > Py Order of ve_o Py > Nis > NMes. Nature of Lewis Acid other than a Metal The Lewis acid (like BH, AICI) other chan a metal can not form x back bonding. In ease of adduct HB CO, there is no xback bonding and only pure o-bonding occurs to BH. Sinee HOMO 1 CO isslightly antibonding in character, bond order of CO increases. Thus, CO stretching frequency is raised. 143 emt 165 Veo for free 00 Voo for HBO, 1860-1600 cm"). When the carbonyl ligand bridges two metals, the vo isin the range of 1860-1750 cm carbonyl that bridges two mea represented bythe prefix. (and for convenient by the prefixu) and donates one electron to each metal. An example of a carbonyl complexes with w-CO bridging is Con(CO)g. 5 ‘When the carbonyl ligand bridges three metals the vco lies inthe range of 1730-1600 em”. A carbonyl that bridges three metals is represented by the prefixy®. These most often occur in cluster compounds such as Rhg(CO). : “The terminal and bridgining modes of bonding and their C—O stretching frequencies are shown in Table 25. Freeco* 21a Terminal M—CO 2120-1850 *symmeticy”—CO 1860-1750 ° x, wo a symmetricy’—0O 1730-1600 ° &, ZN MM _| * Asymmetric w? ~and y.?-C0 are also known.* 244 ~ Organometallic and Bioinorganic Chemistry ‘When CO ligand bridges two metals, both metals contribute electron density ino x* orbitals of CO resting in the lower bond order of bridging CO than for terminal CO ligands. Therefore, C—O ‘bond becomes larger and weaker and hence the Veo for doubly bridging CO is much more lower than for terminal CO ligands. For example, vco for bridging and terminal CO ligands in Fes(CO)s (igure 2.8) are 1829 en“ and 2082, 2019 em respectively Yoo = 2082, 2019 en Fig. 28 When CO ligand bridges three metals, three metals contribute electron density into x* orbital of (CO and further decreases the bond order of CO and, therefore, C—O bond length ofa triply bridging (CO further increases and becomes weaker. Hence the veg is still lower than in doubly bridging CO. ‘he decreasing order of ven is: ‘Terminal 00 > bridging CO > bridging CO q o i 1 5 ¢ M u7 \M ‘Terminal 1? bridging 1 bridging Asymmetrical bridging CO is also known : Semibridging, c /x asymmetric bridging and ‘socarbony bridging. In the semibridging carbon, the M-—CO—M bond is asymmetric rather than syrumetrc. The semibridging carbonyls are considered to be part way between terminal and bridging carbonyls Figure 29) 245 Fig..29. Ing / nbridging carbonyl, 00 acts as a four or six electron donor and CO ligand donates its as ‘well as n-eleetrons tothe two metals (Figure 2.10) 4 we “oN, Ph iy ° oo. | A, [00 Sta - Min’ oc% | Bysco Phe PPhy SO Fig, 2.10 Isocarbonyl bridging occurs via the oxygen atom of a coordinated CO electron deficient early ‘transition metals such as titanium (Figure 2.11), but itis very rare. -216 Oe ameitillad Bcnorani Chemisty (X-ray Diffraction Iniee CO, the C—O bond lengths 112.8 pm. In eta carbonyls theC—0 bond becomes longer and weaker than tha of free CO. This is due to x-back bonding. The C-O bond distance values in metal carbonyls for terminal and u?-CO age 115 and 120 pn respecvey ‘Number and intensity of Infrared Bands Infrared spectroscopy can be used to determine the structure of carbonyl complexes of transition metals. Amolecule is infrared active if a stretching mode resuks ina change ina dipole moment. For example, in an octahedral complex, M(CO),, a symmetrical stretch of each C—O bond gives no overall change in dipole, therefore, this stretching mode is ne sen i de infrared spectrum ofthe compound, However for a compound all other possible stretching modes have to be considered. The symmetry ofthe molecule and group theory are used to calculate the expected number of infrared active stretching modes for a molecule. The number and inteniy of infrared scretching bands of ‘CO depend mainly on the loal symmetry about the metal which she carbonyls ace attached. The symmetry ofthe other ligands and their influence on the rue molecular symmetry is usually not important The calculations of the number of bands are beyond the seope of this book. The number of (C—O stretching bands for various geometries are given in Table 2.6. Ithas been observed that more. symmetric is the molecule, the fewer willbe the numberof infrared bands expected, For example, Cr(0), is an octahedral complex with the poine group Ob. Table 2.6 shows that ‘one strecching mode ofthis compound is infrared active and, therefore, only one band is observed in its infrared spectrum, oe x ee? !Nco Fig.212 the symmetry point group of the molecule drops, the number of carbonyl stretching bands will increase (to limit of one per CO ligand in very low symmetry molecu} one CO ligand ofCr(CO), is substicted by a halide Figure 2.12), the overall molecules still ‘octahedral bathe shape made by the MC isa square pramid witha point group Cay. Table 2.6 shows that ther are three infrared active modes and thre infrared bands are observed in is infrared spectum. the fourfold aray of CO ligands is inthe same plane asthe metal atom, two bands wl be observed ‘Mel Carbon s a 2or3 nowt eeu (the four old array Ci Cay | of CO Figands les in oc | Noo the same place a i ‘the metal atom two band wil be | observed.) 2 wns | acy 7 i De 1 of Neo M(CO), Le ten a , oN Oi te ane co oy [Nema are nearly oc! » L collinear, only three om bands will be . cose) : oy st : ui : 2 viN " oof IN MCO)sts aon sc : ONS the trans CO oy | ands are nearly oc Ni eats am ely will be observed)Onanomalli ad Bioinorganic Chemisty z 5 7 Pana (| arama Sette | lat | Maher oft M@CO)s aca f° M—co cs 2 a a aac ail L 2or3 onl (the three fold a Cw | array of Co ligands ocd! is nearly planar, ©o only two bands wil be observed. M(CO}4L Cov 4 | exstaniat | oc uo Das 1 oc“! M(CO}sha cgenorit | CN | Mt cs 3 oc | M(CO), ing M % 1 ol M(CO)sL e he cv 2 “1S. oc co ° 249 lithe CO ligands are not related to an inversion centre ora threefold or higher axis of symmetry, a molecule with C9 figands will show nCO IR bands. For example, cis isomer of M(CO)2Cl, gives bent arrangement (Figure 2.13) of M—CO bands and willhave two bands in its IR spectrum because both the symmetric [Figure 2.13(a)] and antisymmetric (Figure 2.13(6) stretches cause the change indipole moment andl ate infrared active. 3 S Ne. L Ne. L Restart SUC < ar ys Resultant 6 sae) o Fig. 2.18 (a) Syrmetic stretch () Asymmetic stretch of cis (COL 2 ‘Thetans isomer of M(CO) Ls gives linear arrangement of CO bonds and ony one inated bond is observed because the symmetric stretch does not cause change in dipole moment {Figure 2.14(@)]. Only unsyramesic strech causes the change in dipole Figure 2.14()} Zo 9 LA 7 Resultant ero LS Resuttant uc M Woe yo “ @ © w Fig. 214 (a) Symmetie stretch (0) Unsyrmeti stretch in transMICO)aL2 Although the number of infrared active bands can be predicted by the symmetry and point roups, fewer bands may some times be observed. In some cases bands may overlap and can not be distinguished; alternatively, one or more bands may be of very low intensity and not readily observed. If isomers are present in a sample, then it may be dificult to determine which infrared absorption bands belong to Which compound. "Now let us consider the (n° ~Cp)Fe(CO),] comple. Inthe solid state, this compound exists as trans isomer (Figure 2.15).220 ‘The trans isomer exhibits only one high fequency infrared band for terminal CO and a single band for bridging CO ligands, becawe the two bridging CO ligands are nearly collinear. This Indicates that two infrared bands are observed for the trans isomer although both are split owing to intermolecular coupling. In aqueous solution it exists as cis isomer. The cis isomer (Figure 2.16) exhibits two high frequency bands for terminal CO and one lower frequency band for bridging CO ligands. - BAS = SX es a V7 / é ig.2.16; ‘The intensity of infrared bands depends roughly on the magnicude of the change in dipole ‘moment. The asymmetric vibraions have more intense absorptions whereas the more symmetric vibrations have lesser intensity, (Le, extinction coefficient) Synthesis of Metal Catbonyis 2) By direct interaction of finely divided metal with carbon moxoxide : This method is usually used to synthesize the carbonyls N(CO),,Fe(CO)s,Co(CD)g only. is.400- 222100), [Ni(CO), is toxig,colouriess, mp-I7G, bp 43°C. Purification of Ni by the Mond provess is based on the decomposition of Ni(CO),. srg at0 Fer sco Fe(CO)s Fe(CO) is an orange and toxic solid, mp -20°C, bp 103°C. 200+ 8c9 PSE" Co (CO)g (2) Reductive carbonylation : Thic method is most widely used forthe synthesis of binary carbonyls of most of the transition metals, The reducing agents such as Na, Al, Za, tialkyl aluminium, Grignard reagent orn some cases H are used in the reaction of a metal halide or acetate or other salt along with earbon monoxide. chy + A+ 600 MEE, excOY5 + Ay Metal Carbonvls 5 eee 3 221 Vl, + 4va+ 600 PEM, watdigtyme)=}*{V(CO).T” + 3NaCt HPO. VECO cine ese prone (7) Tach, + 6KC Ht, E2AEEMS (KCAS-Chown- 8); [TUCO)aI™ + 4KCL+ Ce In this reaction potassium and naphihelene react to give the naphthalide radical anion, a powerful reducing agent capable of stabilizing reactive intermediate by coordination tothe metal prior to CO coordination. Modis + SNa +600 PH »Mo(CO), + Sal 200005 + 2H, +800 PPP 5c0,(CO)_ + 200, + 21,0 2Mn(OAe), + 1060 + AlBty = +¥4n3(COn + ALCOAC)s aain(OAg «aa +1000 MEMES nny CO)p + 4NACOAE) ‘smu(acae)s #4) Hg +1200 -aperpas? Rus (COia + SMeG(O)CH,C(O)Me in the case of reduetion of metal oxides, carbon monoxide itself acts as a reducing agent and converts itself into 00>, 2c00 +1000 — 22+ Co4(60)4 +2003 260 9(00)4 > Cog (CO)y2 +400 010, +2400 ME, (#12002 FeO +1900 ==", aRe(C0); +3002 Fe(CO)s +208” ——> [HFe(CO),]" 43Mn02 Fe,(CO),2 +3Mn0 +308" Re,0, +1700 7" Rey(CO)9 +7002222 Organometallic snd Bsinorgnic Cheaistry (8) Higher carbonyls can be synthesised by thermal or photochemical reaction of lower carbonyls 30s(CO}; —*4055{CO)i2 +360 2Fe(CO), "> Fep(CO)9 + CO 3Fe(00}; —*-+Fes(CO). +360 200; (CO), "50, (CO), +460 Properties and Reactions of Metal Carbonyls ‘The mononuclear carbonyls of nickel, Ni(CO), and iron family Fe(CO),, Ru(CO), and Os(CO)s are liquids at room temperature and pressure but other carbonyls ate solids, All ofthe mononticleat carbonyls are colourless or faintly coloured wihezeas the polynuclear eatbonyls are coloured. The {intensity of polynuclear carbonyls increases with increase in number of metal atoms, For example, Fe(CO) is colourless liquid, Fey(CO), is golden yellow solid and Bes(CO)y isa very datk green solid. The colours ofthe polynuclear earbonyl arise from electronic transitions between orbitals that are largely localized on the metal framework. The mononuclear carbonyl are volte. The bigh ‘volatility and toxicity of Ni(CO), requires not to inhaled or allowed to couch the skin. Reactions of Metal Cazbonyls ‘The variety of reactions of various carbonyls isso large that only the principal reactions are ‘mentioned here: (Q) Substitution Reactions ‘The metal carbonyls undergo substitution reactions by ether dissociative or associative ‘mechanism depending upon whether these obey 18 electron rule or not. The complexes which obey 18 electron rule undergo substitation reactions by dissociative mechanism because the alternative, associative activation, requires the formation ofan energetically unfavourable 20-lectron activated ‘complex. The complexes which contain 16 or 17 valence electrons undergo substitution reactions by ‘associative mechanism and its rate is faster than the dissociative reactions of metal carbonyls which ‘obey 18 electron rule. CO ligands can be substituted by other ligands either thermally or photochemically, Complete removal of all CO ligands either thermally or photochemically is rarely posible. The incoming ligands are generally weaker x acids than CO and back bonding to the remaining CO ligands increases with each sucessive removal of CO ligand and increases the M--CO bond strength. Meu Carboy _ 223 Dissociative Substitution General mechanism of disocatve reactions is given below 04 : MACOS LM og MY a ‘The first step is the slow dissociation of a CO ligand. This step is rae determining and independent ofthe concentration of incoming ligand Y. The rate law for this reaction is Rate Ky {Complex} +2) In some case, the back reaction, K., becomes importaat and the intenmediat LyM partitions between the forward and backward reactions. The rate of reation is affected by increasing the concentration of ligand Y because X now competes with K.y. The rate of reaction (1) is: se Aube {Complex} (¥) Rare (CO]+ KH) ae {the concentration of €O equation (3) is negligible, the equation (3) reduces to equation (2). In the dissociative mechanism, an intermediate of reduced coordination number ot more probably a solvated intermediate suchas (Cr(CO); (THE formed. This intermediate then combine with the incoming ligand. (CO), + THF —s1M(CO),CTH)} +60 {{(CO)5(THF) + PRe—o{¥(CO),(PR3)]+ THF where = Cr, Mo, W Since tetrahydrofuran (THF) i only @ 6 donor ligand, there is no ack bonding between metal and THF. inorder to minimize electron densty-on metal, it donates its extra electron to CO by back bonding. This makes M-CO bond strong and M—-TH® bond breaks. When PR approaches to metal, it replaces wealy bound THP and gets sabitted resulting i the formation of singe produced ‘The lgands ike Lewis bases, olefins and arenes can thermally be substituted on mca earbonys. ‘Weald coordinating ligand, ie, more labile ligands such as CHyCN, THF, CHCl norbora diene (BD), eyloocaterrene (COT) and cyelooctadiene (COD) facilitate removal of CO by stabilizing the coordinaively unsaturated intermediates before they ae themselves replaced, e{CO); $22.» Fe(CO)s (COD) 2+ Fe(CO}s (PCI)224 iS Oftanonitlc ind Bioinorganic Chemistry ‘Cr(CO)5(PPhis)5 HCO), Fa Cre y(Mecn), eT 7p o oc” | oo aN \ oF jentione " Note MeCN aways replaces 300. oc“ | co co G rh oem LS, Sey am oc! oc | Ny Neve colt cy, $y ¥ x00, Sty NL 5 CINp oo oO. nie Me cx0n,+ ‘nh oo oc JN bXco (CO)g + BtgN* Be” 22°, Br" [Cr(CO), BAT” +O Maul Carbo oi ae 225 ye 0 oc F,¥ c1(00), 5 > Ne FO" ocd INe 6 cov ‘he Me aa ¥ = ene) 2280 ldimetst pe phorphoo)etame | Me Me c Mico), 2. oe Zens pen en ae (C0), BE Where M=Cr,Mo efCO) Bry Subsequent substitutions by the incoming ligands like phosphines, PR, always occur cs to the Initial ligand. Tis is because the substitution of any ligand that is a better © donor but a poorer x ‘Acceptor than CO wil lead roan increase in the back bonding between mecal and che CO tigand trans te the incoming ligand. The substitution reaction rarely proceeds further than fac- M(CO)s15 because the electron density on the metal would be to great.225 Oreonaic and Binorznis Cheniy ‘The facial isomer [Figure 2.17 ()] in which the incoming PR ligands occupy a triangular face of the octahedron is preferred tothe meridional isomer [igure 2.17 ()] in which the ligands occupy a meridian. This i because COs have a higher tans effect than that of phosphines, Therefor, substation continues until there are no COs trans toa CO. co 0 - Oey Ht Oca Pt ony ft J1Nco 2 octNco acd 2 get oc4 1 co oc | Sco oc IN oc | Nt \ Fig. 2.17 (a) ue DA. oc. byt K oc Neo Fe 2170) Figs 2.1% ‘The rate of CO substitution in si-evordinate metal carbonyl, M(CO)g often decreases as more strongly basic ligands like phosphines and phosphites replace CO. With bully phosphine ligands, further substcution may be thermodynamicaly unfavourable because of the ligand rowding, When + phosphine ligand (a strong « -donor and a poorer x acceptor ligand ie, @ net donor ligand) replaces a CO ligand ((e., a x-acceptor ligand) electron density inereases on the metal and the remaining CO ligands bind more tightly and, therefore, reduce the rate of CO. dissociative substitution. The donor ability ofthe phosphines and phosphites follow the order PR; FH (Fe(CO)s]° + Fe(CO)4L Metal Cabos Dissociation ofa ligand is accelerated for bulky ligands with increased cone angle. For example, the complex Ni(PR;)4 with cone angle 118" is slightly dissociated whereas the complex [ENiEPC Buds} ] with cone angle 182° s highly dissociated. The ligand P(* Bu) sso bulky thatthe 14 electron complex PHP Bu)3) 2] can be isolated. Let us discuss the substitution reactions of NI(OO), Ni(CO), 4 ANiCCO)sL] —E->NECO)2tg "+ NiCCONLy E> Nib g ‘Where L groups are phosphines or phosphites ‘On moving forward tothe reaction, theate of reaction wil decrease. The two ligands are readily replaced to form Ni(CO);Lz but the last rw are much less reactive. It can be explained in terms of theirbeing only two strong x bonds Between Niand CO ligands and these ate largely localized on the remaining two CO ligands and, therefore, produce trong Ni—C bond. Also, since phosphines such as Rs actas strong ¢-donor and weak x-acceptor, its responsible to form strong Ni—C bond which is tobe broken during the reaction. ‘Some dissociative substitution reactions are shown below Iry(CO)y2 + 2PPhj;—> Irg(CO (PPh) +200 e(C0), 47H? + ACO), (PPhis) "A? + Fe{CO)(PPh)2 Ni(CO), +2PR; ——+ Ni(CO)_(PR)2 + 260 ‘W(CO), + 3PR; ——>W(0O), (PR,)3+300 Gr{CO)g + 2NO —+ G(00); (NO), +300 ‘Two NO ligands always replace 3C0 ligands Some dissociative substitution reactions are accelerated by using amine and im-chloroperorybenzoic acid (m-CPBA). The m-CPBA oxidize the amine into its oxide o Me Me, mom, MN. Mew 22% we Si—o- Me” Me “The amine oxide attacks the carbon of OO ligand of ly MCO to form the Ly M(NMe,).Metal Carbon 229 2-28 Ea oe ~~ Organometalli‘and Bioinorganic Chemistry Associative Substitution Inassciativeubstkon eats, the ncomig ligand fist dds tothe mea omplxt form Eel - 40 a Me ‘an intermediate. This is slow and rate determining step. In the next step, the dissociation of one of the OMe WTS ye SBR HMI Me orginal igands occurs rapidly. “SMe aco) ty pL ‘The complex L,M(NMes) then reacts with the incoming ligand such as PRs to form 2 single product. 2 T.M@iMe,) 785 L,M(PR3) Complexes of 4d-series transition metals react much more faster than those of the 3d: and ‘Sdseries transition metals homologs. This is one of the reasons why Ru, Rlh and Pd are much more Widely used as most ative catalyst than Os, Ir and Pt Photochemical substitution of CO usually leads in the formation of monosubstituted product because photochemical excitation of a tactal carbonyl with a coordination sphere of mixed substituents causes the dissociation ofthe ligand whichis che most Isbile (c.e., most weakly banded) inthe ground state. If the ligands of neal same ligand strength are used, one can replace al the CO ligands. The labile igands are THE, MeCN, alkenes et. W(CO), + PPh —*-W(CO),(PPh3) + CO W(CO)g + THF—Y>W(C0) 5 THF) 2» W(CO)5 (PPh) Fe(co), estate ogy) Buchan, onlO] Photochemical reactions of some substituted carbonyl cause the change in hapicy. by (mes BE Cuno, ® Q-o0, amd & co(CO), a ow ‘y ‘The rate of substitution wil be given bythe rate equation Rate =k (Complex) (V] ‘This mechanism js often adopted by an unsaturated 16 electron complexes because the intermediate is 18-clectron species and, therefore, provide a lower energy route than the 14-lecton, wermediate that would be formed in dissociative substitution. Ror example, associative substirutions on square planar 16 electron complex with PR; is shown below PMePh2 oc, Pe, oc, Merb, , Saad Sah Phamep “cL ce, ay’ PhzMep “ | Sa PhzMep% PMe; 7 N oo eth PhaMep“—PMes (dd electron complexes (17 or 19 °) react faster than even electron analogs, ‘V(CO), + PPis —_+V(CO)g (PPhs) > V(CO)s (PPhs) V(CO)g reacts 10" times faster than Cx(CO)e. Some 13 electron complexes also undergo associative substitutions. For example, if nas or allyl ligands are present which can change from a 3- to 1-eleetron donor mode. Coden = =O — + ayOds Ma—Hy,— +1 (00s MS N=0 290 neo 186 tao oo se Leen ‘The binuclear complexes with metal:metal bonds undergo M—M bond homolysis to form cleciconically unsaturated radicals which then undergo associative substitutions230 Organic Bsinorganic Cheney (603(00},—"» 200(C0), » CD(CO}, + Co(CO}sL, —+G03 (CO), The photochemical substiution of CO in Mag(CO)yo by PPhy proceeds via 17 electron Jncermediate Mn(CO)s. Mn(CO)j9 + Phy —+ Mig(CO)9(PPhs)+CO ‘The steric crowding between ligands accelerate dissociative substitutions and decrease the rate of associative substcution. ‘The Interchange Mechanisms (I) ‘Ichas been observed that 20 electron intermediates are unlikely Buta 20 electron transition state seems tn be possible, An intermediate is a species which has to survive as an independent entity. Unlike an intermediate, a transition state has a much shorter lifetime which is comparable to a ‘molecular vibration (about 10°! =) ie,, a transition state is an unstable entry and 20 electron ‘ansition states ate common in interchange mechanisms, In interchange reactions, the leaving and incoming ligands bind simultaneously in one step forming. transition state, The leaving and incoming ligands bind more weakly than they vould bein a more stable 18 electron incermediate LgM—X+ YY My. xp lM ‘The interchange mechanism is further divided into wo following categories : (1) Inverchange dissociative (La) (2) Imerchange associative (I,) (1) Interchange Dissociative (I) “The MY bond begins to form before the MX bond is fully broken but the MX bond breaks preferentially and the inerchange is more close to dissociative than to an associative. The evidence for an fg mechanisms that certain strong nucleophiles at high concentration with group 6 carbonyls show a second order rate expression. Cx(CO}g “Ms fxecone (Pes) > (ECOVsPMA (2) Interchange Associative (I,) ‘The M—-X bond begins to break before the M—Y bond is fully formed but the MY bond forms preferentially and the interchange is closer to an associative. Experimentally, it is not easy to distinguish an, from associative mechanism because there is n0 evidence for , mechanism. ‘Meal Carbon 231 Carbonylate Ions “The reduction of metal earbonyls gives anionic complexes which are cle carbonylate ions Ccarbonyate ions usually obey the 18 electron rule. The species that form carbonlate ions most really are odd-lecon species particularly 17-electron species and dimes. ‘They are often electronically and structurally related to neutral carbonyl complexes. For example, [Cx(CO)4I*, [fn(CO),]°", [Fe(CO}.]* and {Co(CO).]" are isoelectronic and Jsostracural with NiO), Similaly [Fe,(CO)q]™ i isoelectronic and isosuuccral with Co=(CO)s and [C'3(CO),*isieleesoni and isostructral with Mng(CO}y “The carbonate ns ae thermally stele but in contrast to most neutral meta earooyl highly The metal carbonylat fons behave as nucleophiles and are succeptible to atackbyelectrophiles. They can be oxidized or futher reduced and, therefore, they are used in the synthess of carbonyl derivatives Synthesis of Carbonylate Ions (2) By Reduation : common method of synthesis of carbonylae fons is the reduction of neutral metal carbonyls with strong reducing agents such alkali meals, alkali metal hye, NaBH, LifHBEX3} o{00)g+2iLHBEE3} + 21ifCo(00)4) +28 + Hs May(CD)o + 2KH Py 2K0tn(CO)s +H NaepFe(O),] \ 8 oc “co | V(CO)_-+Na —> Na* + (V(CO)gI” Fe(CO}s +2Na—* 2Na* + Fe(CO)E (CO) SE ane +fextco}el™ +0 My(CO)jo +2Na —™ 2Na" +21M(CO)5] ‘where M = Mn, Te, Re.Organomet and Bicinoranic Chey 60;(CO), + 2Na—BE 20a’ + 21Co(COT Ms(CO) + 6ne—™ where M = Fe, Ru, Os Ey GNa* +3(M(CO),]* ‘Mg(CO),2 +12Na—™ 5 12Na* + 4(M(CO)3]” ‘where M = Go, Rh Ie Re,(CO)yo + 2LITHBELs]~™" 5 21i(Re(CO),)}+ ets +H, r(C0)g SHG, NaglCr, (COD) +200 ‘The reduction of metal carbons with common reducing agents such as alka metas leads the formation of mono or danionic carbonyls. But reduction with more stronger reducing agent such as Navlig, NH, NAMPA, LYNaphthalene or alkali meta/erown ether, they are Further reduced to form super reduced carbonates with the formal oxidation state ofthe meta slow as 4 Na{V(CO)g}+3Na—H8" as V(CO)s] +4 NaxC.O2 Na(hin(CO)s]+3Na—!0824y NagfMin(CO),]+3 Na,C02 K(Co(CO)41+3K 2K (Co(CO)3}+3 KC02 vow, +1 Na Nalte(CO)¢1+3Na—!ME4-y Nar (CO)a} +3 NAO, @) By Nucleophilie Attack : The carbonyate ions can also be prepared by the reaction of ‘metal carbonyls with strong bases. These reactions involve the reduction of metal by CO already resent in the metal carbonyls Fe(C0)s + NaOH —z>NallHFe(CO),] 8 5Na (Fe(CO)4] Fe(CO); + 4NaOH ——+Naz{Fe(00),] +Nas005 +240 peconr SL [Fe(C0),)* | +0 | 1,0 tFe(00),* ‘Metal Carboy 233 Nag{Fe(CO)4) or [Re(CO)4]* sealed Gollman’s reagent. Gx(CO)g + 40H” ——+[Cr(CO)s]* +00F +H,0 Fe, (CO)y + 40H” —n{Feg(CO)s]* +COF +2H,0 (8) By Disproportionation : The binuclear complexes with metal-metal bonds can undergo Alsproportionatio inthe presence of non x acceptor ligands such as NH, py, dppe leading to a carbonyl anions. For example, Hing (00)0 +3NHs =p {in(20),(NH)3]* + 18in(C0)5)" Inthis rection electron transfer takes place ftom a 19e Mn(CO);(NHs)s intermediate toa 17e~ [Mn(CO)s fragmento give che disproportionation product (2) 3Mnz©O)yy +12Py "> 2p Mn Py)<)* + 41Ma(CO).T +1000 (3) Mg (CO)yp +2dppe —> {Mn (CO) s(dppedeI* + Mn(CO),]” +3.00 where dope = PhaFCH,CHPPh (4) Co4{00)g + 6NH, +> {COCNH )g]{C(CO)4} (6) 3Ni(CO), +3Phen —> [Ni(Phen)]INiz(CO),] +600 (© Cog(CO)g +5 RNC —+ [Co(CNA) s]E.Co(CO}_}+ 400 In each ofthese cases, the disproportionation produces a positive metal ion and a metal in ‘negative oxidation state. The CO ligands bound tothe softer metal species, the anion; che nitrogen. ‘donor ligands (hard bases) bound to the harder metal species, the cation. Properties of Carbonylate Ions Casbonylate ions belave as nucleophiles and these are basic in nature. Te basicity increases on descending te group because on descending the group, electrons become less tightly bound and the carbonylate ions donate electrons realy. [Mn(CO}<}” < (Te(CO)s}” < [Re(CO)sI Increasing order of basic character rey | 8]. & oe | ooHigher the negative charge on the earbonytate ion, more willbe its basicity besides CO other -acceptor ligands like PR, N2, NO ete, are present, then they will withdraw some ofthe electron density from metal and decrease the eletron density on metal and thus will decrease basicity ofthe carbonylate ion. Ifelectron donating ligands like NH, ANH, py, Cp, RsP ete. are present, then they wil inrease ‘the basicity ofthe carbonylate ion by donating electron tothe mera. For example @ @ W. W oO 1 Neo oc” | co co co Reactions and Synthetic Applications of Carbonylate Ions ‘Nucleophilic Substitutions : As nudeophlescarbonsiate ions attack readily onthe posive centre of the organic halogen compounds to give alkyl, aryl or acyl complexes. Alternatively these reactions may be viewed as electrophilic attack on the metal (M{Go)s)° +Mel —+ Mem(CO)s +1" 9 (9 {i I [M(Co)s + R-C—X —4] R—C—M (CO), | 4x oe (Ni(CO)_" —*s te" — aly C0) + Be a \ Ue? -alyb41C0),1+60 (ico), 252 (ate,simccoys) +c- where M = Mn, Te, Re [60(00),]" 8 iP+—Co(CO}, +” Br~ RO : Ee ef + thatco).)” —stancoysn +685 alkyl complexes ean also be prepared by this method, cls [Feq(C0)4}* + CHa —+000), fe — Fe (Coy, +2 ‘Metal Carbonyls ° 235, ‘Nucelophilc attack is also observed on meals. {in(CO)5)° +Min(OO);Be-—+¥in-(CO)j9 + Br™ ‘ng(CO)jo can be used in synthesis of metal carbonyl halides and metal carbonyl hydrides. (0C)s Mn+ Mn(CO)} —> 2[¥in (CO) X] xix Br 1B {Re(CO)s]” + Min(CO) Be —+(0C)s Re—Mn(CO) +Br™ HgS0. + 2IMn(CO)<]” —(0)s Mulig Mn(CO}s +502 (PhsP) Nicla+ 21C0(00),” —+(0C)_ CONiCo(CO), +201" PhSnCl, + 3{C0(CO),]” —+ PaSn{Co(CO)4], + 3 2PhgP AuCl+{Fe(CO),]* —>(PhgPAu), Fe(CO), +2C1 Collman's reagent Nag{Fe(CO),] have found numerous synthetic applications. {e(CO)_]* +RXK—IRFe(CO), +X", R= allyl group ‘When [RFe(CO),]” reacts with CO of PhP, insertion of CO which is already coordinated 0 metal between metal and allyl group occurs to give corresponding acyl complexes. ° tRee(Conar +00 Hs [R-CFelCODg When [RFe(CO),J° reacts with CO, alkyl group migrates from M to CO which is already coordinated to metal and create a vacaney and that vacancy has been occupied by the incoming ligand. This phenomenon is called migratory insertion. Migratory insertion occurs in the presence of CO or PhP give corresponding acyl complexes‘Oreanonsflic nd Bcinoric Chemisty [RFe(C0)4)° 62> [, 4 seo L ! XS oo Various synthetic applications of Collman's reagent are given below : CHO nage (COT ong Ae ORO © scoot ata J ° [R-C—Fe(C0),)” BE» RoR’ ° i nda Hof yroe coon RCDOR’ Carbonate ions are highly reactive and are able o reduce 003. IM(CO).1* +260, ——+ (C0), +COF Where Ms cr, Mo . Metal Carbony) Hydrides : Carbonyt aydhides are hydrogen deviates of carbonyl complexes. These are conjugate acid of erbonylae ions Synthesia : (@) By Acidification of Carbonylate fons : [04(C0),1" + Hy0* ——> (CO), + H:0 Where M = Min, Te, Re [60(CO),]" +0" —> Heo(C0), +40 {etCo).]* 90 fH Fe{CO),]” Es H,Fe(O0}, ‘Metal Cabo CCarbonylate ions can also be protonated with acids that are even weaker than water. {cx(Co)5]* + MeOH —> [Her(CO) 5” +Me (erénjqh> BOE, [onset deeo,| ‘When cusercarbonyis are protonated, a hydride ligands encapsulated by framework of metal atoms to form interstitial hydrogen. [€06(C0)g]* + HY ——>{HCO_(CO),s1 [Neutral carbonyl complexes are protonated by strong acids to give cationic hydrides. Fe(C0); (PPh), +H ——+[HFA{CO)3(0Phs)}° (2) By Reduction of Carbony{ Complexes with Hydride Donors : Fe(Co)s > tHFe(CO),]" +60 Mechanism : al O°. (OC), Fe: € “gO REC noe {HFe(C0),} +00. Hs Aan foamy complex Hydroxide fon can also serve asthe source of hydrogen. Joong, I ‘Aaliyah complex > [HFe(Co),1" +00; (che hydrogen supplier reagents NaBH or OH” in these reactions are used im excess, the lone spss wil Ye formed. The interes [oowrg ] aod Na foo, [ umd sn i28 rsanonetalc and Bisinorganic Chemisty eliminating CO and CO, respectively. When these reactions are attempted with Cr(CO)., abridging ‘carbonyl hydride is obtained instead ofthe(HCx(CO),]- LY (€0)s 6 ° am fona-ed’ | ster a OC) sCr— HCC), Fet(C0), —™* 5,Fe(C0), (8) By Direct Addition of Hydrogen to Carbonyl Complex : (0¢)5 Mn Mn(oo)s + > 2HMn(C0) 5 Hon (00), Co--co(C0, + + 2Hc0(0), Hin ‘These reactions are known as oxidative deavage of MM bond, Usually the reaction of hydrogen with transcion metal carbonyl complexes gives monohydride complexes. But reacts with coordinatvely unsaturated metal centres of dof Sseries transition 1metals ofthe Fe, Co and Ni groups o give a complex with two coordinated H atoms, k H PhP, PhP : Sut ae, PP Poe dH oc 7 "pens a7} ‘pen, a7t SpPhs “eat mh rc) © In this reaction the oxidation state of Ir increases from +1 and +3 since H is more RH+ [XFe(CO),7 where X =CL, Br a 9 9 tl R—C—Cl +H1CH(C0);7> —s RCH #chcr(CO)s- ‘Meal carbonyl hydrides are highly reactive and most reactions involve the insertion of another species into the M—H bond. Some typical reactions of metal carbonyl hycrides are given below: (CO), M+H—+ (00), M—CH, —Cit, Ht He= CH,2-40 Onsanonitalic and Biinorgaic Chemisty , eo cn we v r—cSe_r "erion of ge (CO))MH +CHHaN, —+(C0),MCH +z “™ _ c (COMA + dyin —, cone Pane | (eo). “Metal aly! give insersion reaction with CO. Insertion of CO occurs between M—CH bond to sive metal acs : 9 i] (00) M—cH, +40 —(00),M@—C—cHy (0C), MH +002 — (00), MCO;15 on as x CO.M Hoc eg © ( Lo (00), M—H +S, —+ (00), MCS 3H sh ck 4M H—100,m-C€ ‘Meal Carbeols a 2a Bonding Mode of Hydrogen in Hydride Complexes Tn multinuclear hydride comperes Aydrogen can be bonded as shown in Figure 2.18 J 4 Fe(C0),X2 +60 where X = Br “Metal-metal bond in polynuclear carbonyls are often cleaved when these substances are treated with halogens (0C}s MnMin(CO); —+ 2NIn(CO)5x xLx where X = CL Br, As the halogen atom s attached to metal, there is loss in electron density on metal. Consequently ‘the CO stretching frequency of ptoduet Mn(CO);X becomes sigr” cantly higher than Ma3(COjo ‘The reaction of CO with some metal halides results inthe srmation of metal carbonyl halide completes dicey 2MCI, +20 —“+IM(CO}Cla}s ‘The structure of fM{CO}CL} cla 60 NaN 007 Ka ay where M = Pd or Pt Metal Cabo 243, —— oc. 00 2aRhCly +400 Nand” Send’ b+ RKC Rh oc” Sa” Sco Irradiation of metal hexacarbonyls in the presence of halogens gives seven coordinate dimeric complexes which are halogen bridged (Figute. 2.20) 2M(CO), + Xp—"> [MICO}4X], + 400 were: Mo,W, X= CL, Bf «0 ad © oc71 Xx71 Sco © & Fig. 2.20 Structure of M(CO),X]2 The taogen gs can be broken by eating the dimes with trong gad such as pin IMin(CO) 4,1. + 4Py ——+ 2Mn(CO),(Py)1+ 200 ionic carbonyl has ae obtained when macarons are ested within aes, M(CO)g + BtgN*X~ —> BtyN*[M(CO).X1" + 00 ‘where M = Cr, Mo, W. Mng(CO}o + 2BtgN* A” —s (Et4N }pLMnq(CO)s Xa] + 200 X co ¥ co | 1A oc Mi —— Mico 7 /\ occ oC Co P,P, Cu, Ag and Au do not form stable binasy carbonyls but give stable carbonyl halides. ‘The metal carbonyl halides are useful compounds in tha the halogen is often easily replaced by other funetional groupe in substiution reactions.(004m + te oc” | “ee IM \co ew °° (00)gMn—Co(C0), feo nna, “ORS Mixed M—M bond Ronis ©, y. 0 in(CO})* Alc, Oca HA EA F700 MMNCOTA = Me orp) ANSTAh oc Nx Nc (0 -6p) Fe(CorgCl+ Narop” —BE> fin? ~cp)FetcO),6n' ~CpD Metal Nitrosyis Free NO molecule has one more electron than CO and this unpaired electron resides ian antibonding x* molecular orbital and is easily moved to give NO” asin NO"BF; and NO" PF salts. [NO™ is isoeleeronie with CO. When an electon is removed form x*of NO the bond order increases from 25 to 3. Because NO* is nitrosyl ion, the compound containing both NO and CO ae called n=0 @ Fig,221,(a) Linear structure (0) Bent structure of MNO unit on the basis of covalent model Symon. Sumo +m; d md econ easter om Ml, 1oN0 Fig. 222 =0 > ait=o Fig, 2.23, ‘The formal oxidation state ofthe metal is calculated by considering linear NO as NO* and a bent 'NOasNO~. When linear NOis converted to bent NO, oxidation state of metal increases by two units, On covalent model, @ linear NO is a 3e~ donor ligand. In this case there is no need of ‘chybridization on N atom of NO because the metal hs a singly occpied da xbital to overlap with ‘ingly occupied x* orbital of NO to form an MN r bond and N donates its lne pair of electrons to the empry do orbital of metal to form a c bond. tn bent NO, N has to be rehybridize to put thisne I era Srgunetlc end Bioinorganic Chest @ 29? hybe ining stl inorder to bind. One ofthe sp?-hybrid nd. One of wv rid orbital pointing towards the met sectsan in an sp? hybrid orb aie dhat causes the nicrasyt group tO be bent. cet estar coco Ussaly 21 aM Satan or ir 188 RMD racecar ns ae "emt i es Sg a te LN bond lengths in (CiRu(PhP)(lin— anf tenn cee ds me vis respectively as expect® is i e224) ‘are 173.8 pm and 185.9 pm! For ine ponds aay ceivronasamer encores a a aha | pPhs OSC aa ; 1 compen ig. 2.24 Suse of ORUPPRGn-NOW Ber) NP , rosopy.The neared sing infeed POSS pu met cba comple nso ea wei ee se fe, NO A SO ae m tively, Polynucieat nitrosyls are also Saat So cpr Seen ee AN : 1 | @ QBLre - BL | a, af ye d i Fig. 2.25, 4 thing esuencis ve dag fread ND ligonds orth due Fg, 225) vyo ermina = 1672.0" 384109 cridsing) Some nitrosyl complexes are known where the linear and bent forms are in equilibrium, For example, Col Alaflin-NO) =" CoL-AL (bent - NOI 18 ,con) "we conn In dhis case vyo (linear) ® 1750 crm“! and vyp(bent) = 1650 cm". The difference between equencies of 40 (linear) and vo (bent) issmall and, therefore, these structural types overlap. Thus the vyo frequencies are not reliable to characerize the linear and bent structure, Since NO* is stronger -scceptor than CO ligand, ill cause to increase the C—O stretching frequency. NO can, replace CO from some metal carbonyls to form carbonyl nicosyls, Two linear NO ligands replace thee COs, since in electron counting terms, 3CO = 2NO, ‘Coa{CO}g +2NO 9260160} NO+200, Feg(C0)y +4NO ——>2Fe(CO),(NO), +500 Ma3(CO)y5 + 2NO ——»28(C0}4(NO) + 260 Depending upon the conditions, eis posble to replace all ofthe COs in metal carbonyls CxCO)g + 4NO "4 Ce Cin-NO, ‘The first ben nicosl ligand found ina derivative of Vask's complex Fig, 2.26). I(PPhg)a( CO) Ch NOT BEY —> fe(PPLs} (COX bent-NO}.CAT” BE ute “suse Fig, 2.25 Sruare pyramidal stu of Ph) (00)(bant-NO}OH" When [Co(diars},(lin-NO)|** [Figure 2.27(a)] reacts with thiocyanate ion SCN {Co(diars) (NNCS)(bene - NO)" {Figure 2.27 (b)] complex ion is formed [Co dias) lin - NO)]** + SCN- —»fCoCdiars)_(NCS) (bene - NO)” cae” amit The Co! (iars)(lin- NO} obeys 18 eleeton rule. The reaction ofthis complex ion with SCN (two electron donor) will not give a 20 linear gitosyl complex because it violates the 18e rule n this rexesion an electron pair s shifted (roma malenular ital of largely metal character ta ‘an orbital of nitrogen. As a result 32" lin-NO changes tole bent-NO leaving a coordination site for accepting a par of electrons.‘Craanowtallic and Bisinorenic Cheiy 248 7 6 et | is BS aiars \ | a= Cpe ") @ ia. 2.27, Suture of (0) Cotdareata: NOP ando) Go(iars) bent: NONNCSY. Fluxionality cles neg vibra abou i gaat ose atoms of any molec co No mec iy, une an ont angie ae not Bd he Denes eas and ending) of atoms, There are many molecules in whicl ae aeeat Caexing ad bemnd) of oe peel ox on change as hw St ae ire found in an enormous variecy ‘of compounds suc 0 ca serangeens a owe lie ae si tbe sehen non genome compounds io st nomenualent, the molecules are calle eutomels 298 the format cher ‘equivalent, the motectles a more conformations are Fe ec cal tonal Fos sw) oes see ea iran compe on he tesa 4a a == asnong th Eve cis i tered ove tare angen >t Os uni ds a eb ipdsan oes ideo muh meee es ens om Se tan Pe ny nie eae a ero TSP geome. All th four basal ligands in sahare PYRE nal fecaacel le zt ‘This square pyramidal geometry ‘being less stable, quickly rever oes ey bee ial ligands now become equatorial ey fernaor = se sane a “nr geste (5, sure TE Tp hich were ain TBP Vcore snarl 2.28(0)] 7 a #, u Be NN et — v-u ue IN @ Fig.228, The fluxional molecules give fever NMR resonances than would be predicted from ther static geometries, Thisis due othe reason tha the ligands concerned exchanging places more rapidly than the NMR time scale(~ 10”? ~10"s) For example Fe(CO), gives only one catbon resonance t 25. Bucits IR specu (a technique withthe much faster ime eale~ 10" than the ligands exchange) inglcates a trigonal bipyramidal geometry with two types of carbon ligands (0 axial and tnee equatorial), NMR spectroscopy is used to identify the stefochemical nonvgid and fon in molecules because the energy of acvation forboth proceses(Ruxionsiy and NHR) isin the range 0f 25-100 8 no Four coordinate complexes which ae considerably rigid undergo square planar-tetchedral inwerconversion in the anstion metal complexes For example, square planar NPR), Xa oAvers to fetrahedral geometry with activation energy of about 45 kJ mol"! and at rate of ~10°s" at room temperature. ‘The process of fluxionaity Yecomes slower at Yow temperatures and faster at higher eenperatures. Atsuficiently low temperature (perhaps if the molecule isin solid state) the rate of exchange of ligands may slow sufcienty that each ligand remains in position during the absorption ‘of the ragiqwave and the axial and equatorial ligands show distinct NMR peaks and che static spectrum is obtained, this is called she low temperature lit. As the temperature inereases, the tO sharp peaks broaden. Ifthe temperaure ‘of the sample increases continuously, the broadening increases untill the two peaks coalesce. On further increasing the temperature, the single peak ‘becomes narrower. This is due to the reason thatthe rate of exchange of ligands betwoen sil and ‘equatorial positions is too rapid 10 allow separate radiowave absorption by distinc axial and equatorial ligands (Le, rate of exchange of ligands is much faste than the NMR time scale) and the fully averaged specirusn is obteined. This ie called high temperarare limit. The change in NMR spectrum on varying the temperature is shown in Fig. 2.29. mnie Ct SELES | |High temperature limit Coalescence ‘Temperature Boardening of peaks Fig. 2.29 Fluxionility in Cyclic Polyene Complexes : ‘one ofthe mos remarkable features of many clic polyene complers ta sehen noni. For exangl, oom temperature, the ro eyopentadieny) AEE nS Pony alae to each ote. Tis type of Cusionalty is alle interal RAT a So etn st font that observed when a conjuane oi lens NET ae eae am by some but nt al of carbon atoms. This Eso Boats ae ott cordtaton number, A conjgated fle polyene lean opens, sample, si -learon aromatic compound i anion sine Ds 8 9 SA Seimstied ony on Bve cabon atoms Ic gives only one "H and one 6 HA peak 2 a7 aerate ean bad id ock metal fons intwo common mae. reap Sie ner er hon atoms donating three x-letton pais. In this mde of bonding Ha aoe ey peakat any temperate. The chemical hits are diferee fom SET ream eon Te Cay on can loin to metal ions throegh on caiban sin mS y tne pairfleroos: The compound, for example, etn! ~CsHs) ees hes vane aoe trey ratio2 21 atsuficietly Iw teperautes, Bu a high emperans O09 a errs enon i Groomsmen Cas ring at high temperature. This & Known as ring whizzing ‘Two eyopentadenie, CH ligands may bind w retain in all the five carbon atoms and one trough only one carbon atom wo diferent modes : One with 251 An example is Fe(n! -Cslls)n® ~CsHts)(00)2 in which one Gp rng binds enough one carbon atom and the other binds through all the five carbon atoms (Fig. 2.30). This structure is based on 18 electron rule and TR spectroscopy. Fig. 2.90, Structure of Flu! 1) de wound ae cen‘Onanonstalic nd Bicinogani Chenisoy te ! Te 1. The order of CO bond strengths in the following metal hexacarbonyls is likely tobe (a) V(COY; (Mo(CO)s(PCOPH);)5] > {Mo(CO)(PMe3)31 > [Mo(00), (PCI, )3} (©) PMoCO}5 PCls)5] > [Mo(CO);(NMe551 > IMo(CO), (P¢OPh) a )a} > EMo(CO)s(PMes)3] (© [Mo(Co}5(PC1s)5] > [Mo(CO);(PCOPh))s] > IMo(CO}5 PME )2] > [Mo(CO)3 (Mes) (@) {Mo(CO) (PMe ss] > IMofC0)3 Mes )31> IMfo(CO)(PCla)3] > [Mo(CO)3(PCOPH)s 3} 5. In the transPtClsL (00) complex, the OO stretching frequency for L = NH, pyridine, Nie decreases in the order (@) Pyridine > NH > NMe, (@) NH > Pyridine > NMes (©) NMes >NHy > Pyridine > “(@) Pin > NMe5 > NEY, 6. Reaction fFe(CO); with OH leads to'complexA which on oxidation with MnO gives. ‘Compounds A and B respectively are : (@) [HFe(CO)4]” and Fes(COh2 ——_(b) We(CO)(OH]” and Fea(COy (© e(CO),}* and Mng(CO\y _—_—(@) HFeXCO), and FeO 7. On reducing Fe 5 (CO), with an exces of sodium, a casbonylate ion is Formed, The ion is isoelectronic with: @) Din(CO)5] ©) IN),) © Dancco)51" (@ (VCO). “The infra-red stretching frequency Veo ofP-S follows the order @MnCOE CO WH BHCO SIVCO! Metal Carbonyl 10. uu. 12. 13. 14. 15. 16. (@)P>R>S>Q ()Q>S>P>R @S>P>R>Q (@R>Q>P>8 ). Which ofthe following compounds will show the highest C—O stretching frequency in the IR spectum ? [Fe(CO)s}, (Fe(CO),Brp], (Fe(CO),}*, [Fe(CO), (PPhs 1] (@) {Fe(CO),(PPh)] ©) fFe(CO),]™ (© fFe(CO),B1] @ FetC0)s] ‘The value of M—C stretching frequencies of (i) [V(CO),}”, (i) {Cr(CO)]and [Mn(CO),]* follow the tend (@) Gi) > @ > Gi) ©) Gi) > Gi) > @ © @> Gi) > Gid Gin > > 0 Solid Co (C0), shows infrared CO stetching bands at 1857, 1886, 2001, 2031, 2044, 2059, 2071 and 2112em™. WhenCo .(C3}g is dissolved in hexane, the carbonyl bands at 1857 and 1886cm™ disappear. These changes in the infrared spectrum in hexane are due (@) toss of terminal CO (0) structural change of Co (CO) involving conversion of terminal CO to bridging CO {© dissociation of Co3(CO0), t0Co(CO), (@) structural changes of Co (CO), iavoving conversion of bridging CO to terminal CO In linear nitrosyl NO acts as /an: (@) one electron donor (©) two electron donor (©) three electron donor @) four electron donor Which one ofthe following s most easly reduced ? (@) VCO, (©) CxO), (0 Fe(CO)s @NiCO), The oxidation states of manganese in NaMn(CO)s, B:Mn(CO)s and Mn3(COhy respectively are @1,-10 11,0 01. @r01 ‘The stretching frequency of NO in a 16 electron complex having the following empirical formula [Ir(NO)CICPPhs }2(CO)]" is expected to be (a) 1850cm™ (©) 1950em™ The final product inthe reaction {Mn(CO)¢]* +MeLi—> is (@ fMn(CO}, Me (© f04n(C0),] © 1650cm* (@ 2050em* () IMn(Co)sMe] (@ [MecoyMn(CO)5}264 ‘Oreanometalic nd Bivioranie Chnisty 17. im the complex, Nin? ~Cp)a(CO)a} the IR stretching frequency appears at 1857 em (strong) and 1897.an (weal). The valence electron count and the nature ofthe M—CO bond respectively are : (a) 16e", bridging (0) 17¢", bridging (©) 18e", terminal (@) 18e°, bridging 18. In metal carbonyl complexes, as more electron density moves from the metal orbitals to the CO m* orbital the CO stretching frequency (a) increases (6) decreases (© remains same (@ disappears 19. The correct order ofthe 00 stretching vibrational feaency i (@ [Ti(CO)g}* > IV(CODeI > CO> {Cr(CO)4] (B)ICr(CO}g} > CO > [VECO] > [THECO) 5] (0.60 > [V(CO)g]” > [THCO)g]* > ECr(CO).) (€) CO > [Cx{CO)g] > (MCO)g}” > [TCO g}* 2. The values of CO stetching frequencies of (1) Ni(CO),, (2) Ni(CO},(PMes) and (8) Ni(CO),(PMes). follow the tend @1>2>3 @)3>2>1 (© 1>3>2 (@2>3>1 21. CO bortd order slowest in (@) Uneoordinated CO () 60 bonded to one metal (6) CO bridging wo metas (€) CO bridging tare meats 22. Amongst the following, the metal that does not form homoleptic polynuclear metal carbonyl is : @ Mn ) Fe ©cr @Co 23. Complexes of general formula, fac ~[Mo(CO); (Phosphiné)s} have the C—O stretching frequency bands as given belwo, Phosphines : PE (A), PCls(B), P(DPh2(C), PMes(D) Veo, em? 2090); 20404); 197 7K; 1945(W) ‘The correct combination ofthe phosphine and the stretching frequency is: @A=i,8=i,C=ii,D=iv Metal Carbone 265 @ ina axon” \co co 24, For the molecule Consider the following statements about its room temperature spectral data: ‘A. SHENMR has singlets a 5.48 and 3.18 ppm B"H NMR has multiplet at §.48 and a singlet a¢3.18 ppm Ras CO stretching bands at 1950 and 1860 cm". D. IRhas only one CO stetching band at 1900 cm". “The correct pir of statements is (a) Aandc (b) Band (© AandD (d) Band DB EGS 2aCIis L@ 20 20 40 5 6a 27% 60 2 BO HO BO Bo we BO 6O MO BH BHO we We 20 2) @ A. Subjective Questions 1L, Whats synergistic effet. How does it relate to metal carbonyl bonding ? 2. Explain the following I (a) Decreasing order of vgn forthe following complexes is [Ni(CO), > Ni(CO)5{P(OMe)s] > Ni(CO).{P(OMe}y}2 > NiCCO}{PCOMe)s}s : () Decreasing order of basicity of the following carbonylate ions [Fe(CO},}* >[V(CO)«I" > [Mn(CO)s}° > (CofC. (© Decreasing order of basi ofthe following complenes: {€0(00),(PME,) > Co(CO)s(PPhs) >Co(CO)s{PCOPH)s] >CoCCO)s(PF,)(2) In infrared spectra of VCO), and Cr(CO)¢ Veo Hs obtained at 1850 cm"? and and 1980 ce respectively and vy is obtained at 460 cm and 440 cm” respectively. (€) Decreasing order of stretching frequencies of NO (yg inthe following complexes [Fe(CM)5(NO}™, vy =1939 mn"? > [Mn(CN) (NON, vyo =1725 emt >{CHEGN)(NON*, v9 =1515 an (8, The vanadium-carbon bond distance is longer in V(CO)¢ than in V(CO)41” (@) CN", CO and PMes act as o donors as well as acceptor. (i) V(CO), is easily reduced to V(CO),]- @ {€o(00}s(PPh al” has only single carbonyl stretching frequency. Match the compounds with the corresponding CO stretching bands in the following tables o Compounds co Cin em) eCNHi,)4(CO)s 1900 CXC), 2060 Ni(COD. 1980 o Compounds Yeo (in emt) NCO). 1790 co 1890 FCO} 2143 (COV 2060 Which ofthe following will be most table ? Explain. Fe(CO)g, Fe(CO)s, Fe(NO}s, Fe(CO)2(NO)s, Fe(CO}s¢NO)2 When Mo(C0), reacts with an excess of CHSCN, a pale yellow product A is formed. When compound A is refluxed with benzene, the pale yellow product Bis formed which has the ‘molecular formula Cytig0gMo and shows a sharp singlet at 6=5.5 ppm in the "H NMR spectrum, When compound A is refluxed with eyclooctatetraene in hexane, compound Cis {ormed which has the molecular Formula CyyH,0 Mo. Identify the compound A, B and C. Predict the produces from each ofthe following reactions (2) Feg(00)y +NO —+ (0) Ming(CO}e + NO —> (© C(C0),+NO —> Nickel carbonyl, N(CO), reacts with eyeldpeniadiené to give ar - (@) @ CxO), +CHeN — (© Mag(COyy +f; —> (9 x00), +g —> @ Ni(CO), +P —> (8) Ning(CO)p +81» —> (@ Fe(CO}5 +Cslly —> @) Rey(CO)9+Na/ 1g —> € Cx(COY, +6yMef © Vico), +NO — (2) Mo(00), +PhyP—CH,—PPhy —> (©) Fe(00), +08, = ch —> (0) Re(CO)s) + Mel —> ‘The compound (CsH1s)_Fe(CO) shows two peaks of equal area in the "HINMIR spectrum but lower temperatures it show four resonances of relative intensity S:2 2:1. Explain - Which metal carbonyl should be more basic toward a proton? Explain. (@) [Fe{CO)4)* or Co(C0).1 ) (Mn(CODgT ortRe(CO)sT™ diamagnetic compound of formula NiC\oH,. The "HNMR spectrum of this compound at room temperature shows four Aiferent types of hydrogen, integration give relative areas of 5: 4:2: 1 with the mot intense peak inthe aromatic rings. Suggest the structure of NiCjoH;s that Is consistent with the NMR. spectrum. ). The compound Mo(CO}, reacts with LiPh followed by strong carbocation reagent, (CH,050,CF, to give a product ‘A’: Draw the structure of product ‘A’. (CO), is monomer but the analogous cobalt compound is dimer. Explain, () Ni(CO) is tetrahedra Explain. (© Draw the structures ofthe following compounds © FelCO}s, (i) CHCO)g, Ki) Ni(CO)4, Civ) Ru(CO)s2-68 ‘Onanosicalic and Bioinorganic Chenisy 12, (a) Fe(GO)s is known while Fe{CO). is not. Give eason. comme acc (6) Why are M—CO complexes are referred to as x-acid ligand complexes 7 ts aan electron 13. Using the molecular orbital diagram of carbon monoxide, explain why donor and acceptor through carbon and not through oxygen, 114, The CO stretching wave numbers in the TR spectra of certain metal carbonyl species are as, follows: [Mn(CO),I" 2090.m"*, C4(CO)g 2000 em, {V{CO}gI” 1860 em", [11(CO),)* 1750 em’ The vale for COX) is 2143 om", Discuss Cluster Compounds 15, TheV—Chond lengthsin V(CO}, and{V(CO)<)” are 200 pm andl 193 pm respectively. Explain. 16, (a) Giving reasons arrange the following in order of @ Shortest C—O bond tength (COs, (C0(CO} 41° Fe( COD) 4 Lowest C—O stretching frequency tr ataceeaaae se ‘Compound in which several metal bound together diecly(e, dough M—Mbonds) ‘ompound in which several metal atoms are bound together directly (Le. through M—M bonds) el Sam de ne ee ee ‘are call metal cluster compounds, The metal atoms in cuter compounds tend to agglomerate fo. form the maximum number of M--M bonds in such a way that the ML. fragments should be sufficiently sterically unhindered to approach to within M~M bonding distance ofeach other. The non structures of the clusters resemble the close-packed structre of the elemental metals themselves. ‘This i due to the reason thatthe clusters contain unsaturated L4M fragments. The unsaturated 16-lecton fragment Os(CO), is unstable and fonm a stable triangular luster Osa(CO)2 which obeys 18-electron rule, Similarly, the 1S-electon fragment Rh(CO)s forms tetrahedral cluster Rhe(COhi2 which also obeys 18-electron rule. The tendency fo form M—M bond itereases on descending the group in the periodic table. ‘The stable transition meal cfusters canbe divided into: (i crginometalf duster i) inorganic clusters ‘The most extensive clas of organometallic clusters belongs to metal carbonyls because M(CO), fragments are suficienty unhindered to approach to within metal-metal bonding distance of each other. In these clusters the metals are in low oxidation states (ie,,-1, 0, +1, +2). In inorganic clusters such as Re,ClZ", Mo,CI$, the metals have higher oxidation states. There are also some naked metal clusters ofthe postranition elements such as Sad ‘Metal Carbonyl Clusters ‘The metal carbonyl clusters are classified into two categories (1) Low nucleacgy carbonyl clusters (2) High nuclearity carbonyl clusters.33 32 ‘Organometallic and Bioorganic Cheaity ‘Chaser Compounds (2) Low Nuclearity Carbonyl Clusters (NGC) : The first metal carbonyl cluster having (MM bond is Mng(CO);9. The low nuclearity carbonyl clusters contain metal atoms <4. Calculation of number of M—M bonds using 18/16-clectron rule in LNCC : The procedure for calculation of M-—M bonds ina compound involves the following steps const) (sotto Step 1: Calculate tual valence electons (TVE) on central metal inthe compound (say itis A) ‘which sequal tothe numberof valence cleronsofthe metal pls the numberof electron rom each {1 ~CO},C04(60)5 ligand and the charge ‘Step I: Substract A from n>19(Wwheren sthe number metal atoms inthe compound) say its (3) 70,(C0)91 Bie, = 8x2620 9294 Benxl8-A a Step The ae este tt nie -M nds. Theaheo gether number of MAC bonds = 1 of electrons per metal «Total mumber of 14 216 then there wil be 0 MM bond _ Number of MM bonds per metal = 1 14 17, then there wil be one MM bond per meal. 0°02 Pt £ co Sr re eer DIL 114-15, chen there wi be tree MM bonds per met ‘A214 then there wil be four M—M bonds pr met 2-CO);Fex(CO)e ‘This procedure can not be applied for HNCC. Calculation of M—M bonds in some multinuclear complex is illustrated below (4) Fes(CO),2 + (1) M,(CO),9 + Where M = Mn, Te, Re. Aw3x 84122248 A= 2x742410=34 Ba3x18-48=6 2 g Total number of M—M bonds ». Total number of M—M bonds = 1 22 4-816 5. Number of Fe—Fe bonds per Fe atom = 2 4 meu a One MM bond pet cae 2).603(C0)4 + NY oc, JR 00 NIN A=2x 942x834 OK co B=2x 18-3: oc” Xcfheo ty Total number of MM bonds = 1 (a2 -C0),Fey(COh (One M-—M bond per meta. Bib titea ‘Orginial and Biinongaic Christy (5) M,(CON2 + 9+ 12x ‘otal number of M—M bonds = [Number of Co—Co bonds per Co atom = 3 co oc. 00 on / Te 700 ANT AN oN Zbpe° aN oc’ ‘co Gy -CO}sC04(CO)g [At high temperature all weakly bridging M—CO bonds are broken. Therefore, all CO ligands ‘become terminal point, (©) Mz(CO), = Where RusOs A=2x849x Ba2e18-3422 Buz. ‘Total number of M—M bonds Number of MM bonds per metal = 1 2 eo oe] ANI 00 a oc Sco co | (7) Ms(CO)2 = ‘Chater Compounds : 35 a.8. fotal number of M—M bon« Bs Total numberof MM bonds = 3 ata «Number of MM bonds pet metal =2 oe co M eo ol Z co oc’ | Ico oo (8) Ir4(CO)y2 Anax941 B= 4418-60 Bli2_6 Total number of Ir—tr bonds 272 4 [Number of rir bonds per Ir atom co oc. foe0 oc /|\ 20 oc je Zoo oc \ | 7 Sco ik “K od feo ‘The 16 electron rule is of great importance for predicting the number of metal-metal bonds, but it does not play any role to distinguish the bridging and terminal CO ligands inasmuch a5 the electron countis the same fr ether mode of bonding. The factors causing the CO ligands o bridge or not bridge are the steric factors. (CO), does not dimerize as it would become seven coordinate and increase in steric hindrance. In Mns(CO)o, if bridging oceus, there wil be increase in coordination ‘number beyond six and therefore it wil be destabilize. ‘An interesting feature of the structure of binary carbonyl complexes of transition metals is that the ability of CO ligands to bridge transition metals decreases on descending the group in periodic table. For example, in eg (OO)y there are three bridging CO ligands but in Ru(CO)p and Os,(CO)y there is ony single bridging CO ligand. Ths is not due to steric hindrance but tis due tothe reason thatthe orbitals of bridging CO ligands are less able to interact effectively with transition metals as the siz ofthe metals increases. As the M--M bond length inereases (Co < Rh <0), the M—C bond Tength increases ot/and the M—C—M bond angle opens up. Rither of these changes would |36 (9) EFe (CO)a(u2 -6O)]* + ‘Total number of Fe—Febonds “Onenocalic and Bioorganic Chessy destabilize the compound. For this reason Fes (CO) [or Fes (12 ~CO);(0D)a} and Co4 (CO) [or Cog(uz ~CO}(CO)y}are bridged and Ru(CO)2, sy(CO)r2 and re(CO) i are unbidged [Number of Fe—Re bonds per Fe atom = 3 os oJ (10) RegHy(CO),s + oc” (Seo AwAx7+491242=28+ 4424256 Ba 4e18-56 2.-56=16 [Number of Re—Rebonds per Re atom ‘Total number of Re—Rebonds = 8 ‘This compound requires eight Re—Re bonds rather than the six usually found in tetrahedral arrangement of four metal atoms. The expected distortions for a structure (Fig, 31) with two localized Re =Re bonds are not found and the extra Ke—Re bonds are considered tobe delocalized cover the metal framework so that the each Re—Re bond becomes shorter. VAN D e Figs ‘Therefore, the expected structure for Re cluster (Fig. 3.1) would contain two localized Re—Re ‘bonds This structure shows thatthe Wo Re Re bonds will be shorter and two Re—Re bonds will be Caster Compounds : a7 longer, Butt structure detremination shows that all the four Re—Re bonds ace shorter and equal. ‘Therefor, ithas been considered that the two extra bonds are delocalized over metal cluster. In this structure each H is found to bey ~H face bridging (Fig. 3.2). This structure is eabane ike. “The two electrons of one M—H bond are donated to two another metals, n ths structure, the delocalized Re~Re bonds are included in the 5 ~ bridging. Therefore, this compound six Re—Re bonds (tree Re—Re bonds per Re atom) and four bridging js-H bonds. In this model, delocalized ‘M-M bonds are included in the py-H bridges. ‘The trinuclear carbonyl clusters which obey 18-electron rule, have TVE = 48. But in this compound TVE = 46, {eit lacks 2-electron from TEC of 48. Therefor, it may be considered that this compound contains anOs—= Osdouble bond because the TVE fora system with four MM bonds in a three metal atoms cluster is 46. By having one Os=0s double bond, each Os atom obey the 18-eletron rule, Due tothe presence of Os— Os double bond, like C=C double bond, it behaves as an unsaturated duster and is much more reactive than Os3(CO);z- Fg. 3.3 shows that ane edge ofthe (sy triangle is shorter than the other and is bridged by two H-atom,38 ~Oressontlic and Biinogarie Chemistry For square planar complexes : ‘Step I: Determine TVE (say itis A) Step: B=nx16-A Step UH: 3 =Total number of M—M bonds A216, NoM-—M bond inthe complex 15, one MM bond per metal 14, Two M—M bonds per metal Some examples illustrating the calculation of number of M—M bonds in square planar complexes obeying 16-electron rule are Ln? = ethylene), Rh(q- CDI Ao 4x 242%942x3=84 1846=32 Be2x16-32=0 BL Bo A32, Cietie ‘Therefore, number oftoal M—M bonds and numberof MM bonds per metals ero Aa Ny voNaewTy Lin? =ectylene), Rh(u- He 41842=28 ‘Total Number of M— Mbonds = 2 Number of M—Mbonds per metal = eS CNS ToDetermine the Unknown Quantity Using 12 Flectron Rule GENIN, CW — Wigton’) DSe 2x60 20-36 aac aras 3 ‘Chaser Compounds lin'-CsH45)Mn1CO}, Ja (An— Mn double bond ) 2454247444 40= 36 28 4x =36 oc Ma —M oa SS ‘oo Noo ‘To Determine the Expected Charge on the Complex Ions Using 18-Electron Rule {Co(Co):1* 943x 24x18 1S+x=18 x=18-15=3 ‘Therefore, charge on the complexion is = -3 [(00),Ni—0o(C0).)* 342410427 9+3%244=36 ors 2 S436 1=36-33-3 ‘Therefore, charge on the complexion = —3 Un = CsHts)sNig(y—CO}I (three Ni-Ni bonds) 15+30+2x243%24x054 4 Ss 54-55: 1543044464 554 Therefore, charge on the complex ion = +1 3930 " Srpnamealc and Bisiorgnic Chey ‘To Identify the Transition Metals in a Complex Using 18-Electron Rule (LG -CyHlg) M(CO)sTa_ (Misfistrow transition metal and one M— Msingleboad) Gi) IM GS Colle) (CO)sla _ (Misthe second row transition metal and one M—= Mbend) 2M + 442% 644x2=36 2M= 36-24 12 M=6 ‘Therefore, metal is MO(4d*5s" Gi) [M (2 ~CgH1s) (CO)s] (Mis 3 series transition metal) 8 Mi 345% 8-1 Therefore, metals V(3d*4s") __ ee "HIGH NUCLEARITY CARBONYL CLUSTERS (HNCC) High nuclearity carbonyl clusters have metal atoms > 5, each forming atleast one MM bond “The firs HINCC was discovered to be Rhe(CO)ys- Electron Counting in Carbony! Clusters “The rules that are applied to LNCC for valence electron count and calculation of number of M—M bonds do not always follow for HNCC. Many carbonyl clusters have structures and are electron deficient similar to higher boranes B,H?-. Therefore, the approach used to describe the bonding, “structure and electron count for higher boranes can be used for carbonyl clusters and other clusters. ‘Wade gave the method for electron counting in HINCC. The structure ofthe cluster i decided purely by the number of cluster electrons (cle skeletal electrons), not by any other factor, Chaser Compounds _ ot leis general feature ofcloso-ByH2 anions that there are no B—H—Bor BH group nd each Hf bond i normal 2e bond requiring one electon from B and one electron fom H. As boron stats with three electrons, ithas two electrons let to conuibue to the cluster and these electron aie regarded as skeletal or framework elecrons. Thus, BHF anions have 2n + 2skeletal electrons (the 2melectons from nBatoms an the 2elecvons from the anionic charge) In borane clusters, each BH ‘nit as an sp orbital that points diecly towards the centre of the cluster and the other two py and orbitals that pont along the surface ofthe cuter, ‘The nB atoms have dn atomic orbital which are always distributed as follows ‘in the n(8—H,) bonding orbital, (n+1) in luster bonding molecular orbitals, (2n—1) in non-bonding and antibonding cstr molecular orbitals 1nBH, cluster, there aren +1 csterbonding molecular orbitals and 2 electrons contributed tym BH uns, two adtional electrons are required fo ByH” ion, This i che season wy the Bg ions are more stable than BH isl. ‘Since the shape of the cluster depends only on the number of skeletal electrons, it is possible (conceptually to remove a vertex group, BH, fom the duster leaving rwo skeletal elecuoas thatthe vertex BH, group was contributing. This is possible only if BH™ is removed instead of a BH, unit leaving one vertex ofthe cluster empty. 1f BH unit is removed from BH then BsHE” ion is obtained. This wil have the same polyhedral structure because the electron count has no changed dut one vertex is now unoccupied. The neural BsHy borane ean be obtained by adding the appropriate number of protons (four protons inthis case, this doesnt alte the nuber of eleczons in the system because protons (H") ate the zero electron species. Hence all the bonding molecular cnbitals ae jus filed The protons bridge the faces of polyhedron which inclide the missing vertex. In general, the number of skeletal electron pairs a By” will be equal to 3(2n +s) and the number twee 00 [an 9-1) ‘The boranes ar clasifed as: dos, nid, arachno, hypho end klado boranes. ‘The branes in which each comericrapedbyB atoms recalled dosoboranes. These havethe formula, The number of vericesand skeletal electron pars re respectively nand (n+. This indicates thatthe vertices ina cso borane willbe one ss than the numberof skeletal electron pairs Ione B atom sremoved froma vertex ofacloso struc, a ido (Latin: nest it) strata wl result The no boranes have the formula ByHS" of BH, . The number of vertices willbe (n —Dof an ncomered polyhedron and the numberof aletal electron pais f(r + 2) IF ewo vertex B atoms ae removed, an arachno (Grek : spider's web lke) borane wil rs, ‘With two vertices missing, the srucure is even more open than inthe nido struecre.Arachno boranes have the formula BH oF BH, The numberof vertices wil be (n 2) fan ncomered polyhedron andthe number of skeletal electron pits i (a+ 3)342 Organon and Bisinorgic Chniny ‘The fypho (Gres : net he) borane have the formula ByHf oF By Tey have (x3) vertices leaving three vertices unocuped af an mcomered poljtedron and the number f sla etecron pairs is (n+). ‘The klado (Greek: branche) oranes have the formula By Hot By Tey have (n~8) verces leaving four verces unoccupied of an n comered pobhedron. The umber of stele elecron pairs is(n +5, “The method for alcuation of skeletal electron psi calledthe Wade rule Wade his sugested hat BH unica be replaced by a transon metal equivalent that donare ‘the same number of skeletal electrons. Wade has created the (CO), unit as analogous to BH unit, ‘Transition metal with nie valence orbitals (one thee pand five dort have fie more orbitals than boron which hs only four valence orbitals (one «and three p orbital). When thse five exra oils ae fled asa consequence of boning within the skelwon (or famevort) and with surounding ligands the numberof electron count increases by 10 electron er skeletal stom, For cxample, when we replace all the BH units in closo BH with Os(C0)s groups, the species (Os{COM is obtained and therein increase in electron count fom 261086 {Che transition metal MisOs, the nine orbitals in Os(CO) are assigned as follows: three orbitals are filed by electron pais donated by three CO ligands, three more orbitals are fled with six electrons out ofthe eight elecrons of Os, these electrons are used for back boning to CO ligands, ‘The two electrons are ff inthe remaining three metal orbitals, These wo electrons are avalable for skeletal bonding similar to a BH unit. ‘The structures ofthe HNCC canbe determined by skeletal or famework electron counts with the help of Wade's cle. 1, Calculate toa eleston count (TEC), 2, Add to TEC the valenee electrons for interstitial atom, for exaanpl, {fr f, 4 for C,$ for, 5 for P ants0 00 3, Each metal atom utilizes 12 electrons and each CO ligand utilizes 2 electrons imespective of its bonding, terminal or bridged for non-skeletal bonding. 4. Calculate polyhedra electron count (PEC) + PEC=TEC~nx12 where nis the number of metal atoms Pec 5. Caleulate PEC & 2 rs super claso hyper claso closo sido arachno hnypho lado Cluster Compounds 343) The alee aaron cunts comesponingovros suc sens sin and transition metal clusters are summarized in Table 3.1. soe Table 3.1 oe eanes Structure Type = lake LTR [tectrom Pairs ss ned Evel vane 2 co sido ans m4? Mats nea arachao ane nis tne nea yp ans na Mas 8 ata ‘Some examples of HNCC illustrating thee structure type ate given below : 1. Rhg(CO),g, here n= 6 Tec x 9416 8614x642 (14n+2) 4 86 -6x1; Bap e641 oe: PE wl 07 643 (041) Therefore, Rig(OO)c ita eloso metal cluster. 2. Oss (COhs TEC 5x 844+15%2=74=14x 5+ 4140+ 4) PEC=74-5x12= 14 PEC If. aa ‘Therefore, O8sC(CO)s is a nido metal duster, 3. Nis (Oy; +2 (n+2) TWO= Sxt0412x2+2= FEC = 76-$12= 16 Pac _16 22 ‘Therefore, Nis (CO); is an arachno metal cluster. 4. Cos(COg THC 6x 94 16x 2= 5442 PEC = 86~6%12~ 14 = 14x 54 6(140 +6) +3043) 14x 6+ 2(04n+ 2)Organomalc and Bisinonznic Chemisty PEC 17-641 (n+) 22 ‘Therefore, Cag(CO)ig Isa eloso metal cluster. 5. Rul (COir TEC= 6x844417x2 2484 4434= PEC = 86-6«12= 14 PEC 147 641 (n41) aed (n+) he alc) lon che 6. mes NCO ; = 4045+ 28+1=74 14x6+2(14042) 14x5+4(40+4) PEC=74-Sx12= 14 f PEC M47 5420042) : 272 ‘Therefore, Rus N(CO)iy is nido metal cluster. : ESS : INORGANIC METAL CLUSTERS Binuclear Clusters Containing M—M multiple Bonds “The most widely stded binuclear species are{Re, Xe)” ions, (where Xs F, Ch Br NCS, CHa te), The [RejCg}™ ion was the frst inorganic compound containing a metal-metal quadruple ‘bond, tis isostructural with Mo3Cl3]*” 1, HsPO, or PRCOGL in the presence of X ions. ne0; gio, al™ Inlowerhalid clusters the metal oxidation state are usually +2, +3 oF +4 the Re—Re distance (224 pm) is extremely short compared with an average ial and 248 pm in ReCly. Re—Cl bonds may either show that the Cl atoms are In{Re, Xe] fons, ‘Re—Re bond distance of 275 pm in rhenium met have eclipsed or staggered conformation, But the structural analysis has cetipsed rather than staggered (Fig. 3.4. Res X¢l~ ions can be prepared by reuetion of ReO3 with + Chanter Compounds a dat alipsed form a Staggered form Fig. 3.4 ‘Both ofthese features can be regnized de to qudruple MM bons. Ech rhenium atom is bonded tofourchorne toms that re almost in a square planar ary. Ted fbi ofthe two reals are wed for bonding to CI" ligands. The Re—Cl bonds are formed iy using dp-hybrid exbialson bah meals using» ori. This leaves ourobtad., dd addy td the four electrons on each Re™ ion (4*). The metal d. and orbitals may hybridize to form two dp hybrid orbitals :one orbital directed towards the ther henium tom anda seco rita directed in ¢he oppose direction The former hybrid orbital overlaps with the sinlaron he second Re atom to form a Re—Re-bond (Fig. 3.5] whereas the second orbital fons a non boding orbital ‘hed, and, orbitals of each metal atom overlap to form to x -onds Figure 3.5) and ©] ins and ye plans respectively Finally, sideways overlap of dy orbital ofthe two metals form a bond. The formation ofthe Sond causes the ecipeed conformation because overap of the dy bits is possible ony inthis geometry (Fig. 3.5(0)] Ifthe chlorine atoms are staggered thet dy bias wil ikewis be staggered which resus zero overlap (Fig. 3.50] iQ, RD ORD —+ ORDO RO @ A,2 @,2 AAD 5 PS TS OD ® ea oe Aa Dd dey - TO FD PO's346 Organon and Bioinorganic Chemisty oQ,/ aw gia q Sa it ct i 4 oe Ae. Sea SKS i a Fig 35 (a) Formation of o-bond by the oveapeing ofp, hybrid obals on each Re atom, {0} Formation ofa -bond by overap of bias on each Re atom, () Formation of another s-bond by overlap of dole on each Re ams) Famatn fans by Norah fy 5 sotiaisin-eoipeed confoaaton and a Ze ova sdagored contortion. ‘The binuclear metal clusters with quadruple bond ate possible only when each meta has d* consiguaton. A qualitative molecular orbital diagram forthe formation of M_-M bonds is shown in Fig. 36. “The Re—Cl bonds are regarded as coordnaicbondsbetweenRe™ ionsand the ligands. The eight d electrons from two Re™ ions (fur eleetons from each Re™ jon) oocupy ao -bonding,:vo xx-bonding and one 6 -bonding molecular orbitals to fom the quadruple bond. Therefore, the lecronie configuration in (ReaCls]™ ion (ig, 3.6) willbe o?x*6%, Which indicates how many clectons ate present in each bonding molecular orbital. The complex is therefore, diamagnetic. Fin. 26, (Che Compounds = = a7 The species {RezC1g]™ [Fig. 3.6 (b)] and{Mo,C1,]* are isostructural. In both the eases the CL atoms are eclipsed and both have considerably shorer M—M bond distance (Re-—Re = 224 pm, ‘Mo—Mo = 214 pm) than in the metals themselves (Re—Re = 275 pm, Mo—Mo = 273 pm) this is ‘due tothe formation of MM. quadruple bond. ‘The strength of bonds follows the order : o> x>& The &-bond isthe weakest bond but itis strong enough to maintain (Re; Xe]* in the eclipsed conformation. This 6 bond strength is comparable to that ofa hydrogen bond. The Re=Re bond energy is ~ 85 kcal/mol, of which ~6 kcal/mol is assigned to the S bond. Both Sand 6+ molecular orbits are almost non-bonding. If electron is added to 6° or removed from Soria, there wil be no too much loss instability. The compounds, for example, which occupied 8* omit are Res, PMezPh)41 [ResCl«(PMe,PH)41°, {hRe,Cl,(PMe;Ph) «]* . These compounds are stable and have been synthesized, Some examples of cluster compounds are given below : MeqCl,(PMezPh),]: let the oxidation state of Re x 2x-44020 2x. x42 Re > 4a® Therefore number of electrons on two Re ions =10, Electronic configuration in this compounds iso? x* 8? 5° Bond order = (Ns -Nq) 58-2 =30 ‘Allelectons ate paired, therefor, itis diamagnetic. -€RexCt,(PMiePh),]" et the oxidation sates of two Re atoms are x and y. a ‘Therefore, number of d-electrons om Re* andi cine fons =5+4=9 Electronic configuration in this cluster ion is watsTe = 348) ‘Organoaalic and Bisinarganie Chemisty Bonu order=3(8-1) =35 There is one unpaired electron, therefore, itis paramagnetic {ReyCl,(PMezPh),]* + ‘et the oxidation states of two Re atoms are xand y, xt y-Ab0=42 Number of electrons on two Re fons = 8 Electronic configuration in this chustrion is ox*8?, Bond oder «850.4 All electrons ate paired, therefore, itis diamagnetic, ‘The compounds, for example, which have les than full acupation of the S-bonding orita are: [Moa (HPO )4]*,M02(S04)4]*,lMon($04}4]™ and (Mo, (SO, ),)*. These compounds are also stable and have been synthesized. [M0,(8P0,),]* : {et the oxidation states of Mo atoms are x and y xty-822 xty 26 xedy =33 Mo™ 4a ‘Number of electrons in two M™ fons = 6 Electronic configuration in this duster ion ie: a%s* Since all eletrons are paired, therefor, his cluster ion is diamagnetic. [M0280 4), xty-t2-2 xryns6 xet3y28 (Chster Compounds 3 348 Mo™ -> 4d? ‘Number of valence electrons on two Mo™ ions = 6 Electronic configuration inthis cluster ion is: o* Bond order =950-30 Since all electrons are paired, therefore, this cluster ion is diamagnetic, [M0 ($0 4)4]** = Mo* —+ ai, Mo™ —» 4d? ‘Number of valence electrons on Mo® and Mo” ions Blectronie configuration in this duster ion is: 0x8? Bond order =259=35 Since there is one unpaired electron, therefor, this ion is paramagnetic, [m102(804),1* = ‘Number of valence electrons on two Mo™ io lectronie configuration inthis cluster ion is: o*x*6* Since all electrons are paired, sherefore, dis ion is diamaguecic ‘The energy difference between Sand 8 orbitals li inthe visible region ofthe electromagnetic radiations. Therefore, most of the complexes with quadruple bond are of intense colour. For example, (Re,Cle]® and (MozCly]* are royal blue and dark yellow respectively. The colour of compounds containing M—M guadnuple bonds is due to 8-3 erasition.320 = ‘Ormond Bric Chewy ‘The compound (IMz(OR)g}, where M = Mo, W) has an M—M triple bond and an electronic configuration er. n these compons good overlap is posible in ee tapered geometry 2 the 4, orbital isn parscipating in bonding. Ro. OR ROM = M—OR Roy (NOR Ifthe two metals have n electrons in d-orbitals, chen no metal etal bond is formed. tn general ifeach metal has 1, 2,3 and 4 electrons in orbitals then single, double, tiple and quadruple bonds are formed respectively and if each metal has 5, 6 or 7 electrons in orbitals then tiple, double and single bond are formed respectively. To form a M—M bond of bond order n, the number of electrons being shared berween two metas should be equal to or greater than n because it needs a ‘minimum of w electrons, Binuclear Compounds Containing Quintuple Bond ‘A quintuple bond in chemistry is aa unusual typeof chemical bond reported by Philip Power etal, {in 2005 for an ari substituted dichromium compound. (Figure 3.7). Fig. 37, The bulky aryl group (2, 6 {2,6-dilsopropyDpheny?) phenyl} stabilizes the chromium dimer hhaving low coordination number. This ved colour compound is stable upto 200°C. Each of the ‘chromium atoms has six electrons. One ofthe electrons ofeach chromium atom used for bonding ‘with substituted an group. The remaining ten electrons ofthe two chromium atoms ae distributed in molecalar orbitals wit the electronic configuration o?n'5* (Fig. 38). ‘Chast Compovnds 321 (0) Fig-8.8 Molecular ort dagram foc metst metal auinturle bond The § - orbitals are highest occupied molecular orbitals (HOMO) and 6* are the lowest unoccupied molecular orbitals (LUMO). Bond order acconfing to this MO diagram is(10-0)/2= 5. 1 2009, a dimolybdenum compound with quintuple bond and two diimdo bridging igands has been synthesised (ig. 39) ‘The Isolobal Analogy ‘The isolobal analogy was developed by Roald Hoffmann in 1982. According to Hoffmann two fragments are islotal if the number, symametry properties, approximate energy and shape oftheir frontier molecular orbitals and the numberof electrons in em ae similar not identical bt similar. Some ofthe reactions of che metal carbonyls are parallel with main group non-metals and compounds. For example, chlorine atom and methyl (CHS) free radial both have 7valene electrons, one shor of ane gas configuration. Three ofp? orbitals of cazbon are involved in the formation of ‘0- bonds withthe hydrogens. The fourth sp® orbitals singly occupied and has higher energy than the ‘bonding ones. The M(OO); fragment has 17 valence electrons, ane short ofthe 18-lecton. The ‘bonding berween Min and CO ligands in this fragment may be considered to involve the iv of dsp? hybrid orbitals of Mn, The sixth hybrid oxbeais singly occupied and has higher energy than the five322 Dram ond Biinoreai Chemisty « bonding orbitals. Hoffmann points out that any fragment witha singly occupied orbital ofa ype fsa fee radical and may be able to form structures similar to those found fr methyl radical. Halogen ‘atom and methy radical exhibit chemical similarities with 17-clectron organometallic fragments like ‘MnCOs. (Fable 3.2) Table 3.2 Properties of CH, C1and n(CO), fragment IMR COD ‘sta dimer. Ma(COxp i, ch 2. | Reduced tw anion tmncooy” CHR, Cr (asin AMC 3. | conjgaetase ofan acd. | n(CO),}eonjusme base of | C5 conjugate base of CHy and nis conju base of CL 4. | combine with one another | RMa(COs. Raa, nico cht “Therefore, these three fragments are isoloba or electronically equivalent with each other tis to ‘be noted chat if two fragments are oth isolobal with a third, they are also isolobel with each other. ‘The isolobal analogy is expressed by a double headed twirly arrow («—g—¥) City q+ Min(CO)s, CH PCL, Cle—g 41D) 5, Chis p92 p> MN(OO)s, ‘The to fragments say CH, and Mn(CO)s are not isoelectronic because Ma(CO), has more clecronthanGH, but the orbital by which the two fragments frm bonds other fragments are the same in symmetry and occupancy. Me—Me FelC, HS Gelectron _16-leeton fragment fragment ‘A1Seelectron fragment such as Ir(CO), i isolobal with a S-lecron CH fragment and with group 15 elements such as phosphorus, Each ofthese is three electron shor of a closed shell and each has three vacant sites and form tetrahedral structures. Hep Pg F105 Clg OP ttn Cluster Compounds a 3-23 Structures of, and tr(CO)4 are shown in Fig. 3.10, co or AINE WANG = VP XD? @ wo Fig, 8.10 Structure of: Pt )e( Cds Correlation between transition metal fragments and main group fragments according to electron counts given in Table 3.3. ‘Table 33 Correlation between Transition Metal and Main Group Element Fragments sno “vansiion Metal ‘Main Grou Hlomeut/Pragments 1 1" eo 2 v 7 2 6 6 4 1s s s. 1 4 ‘The fragments of polyhedra with same number of valence electrons and with same or different coordination numbers are also isolobal with one another. For example, 17-electron fragments ‘Mn(0O); and Go(CO), of an octahedron and trigonal bipyramid respectively are isolobal ©0 co © |7 oca | OC—MACD gr OD I oc4 | oc* ¢o © Some examples of isolobal fragments of polyhedra with same number of electrons and different coordination numbers are given in Table 3.4324 To worl and Bisinoranic Chis Table a4 ‘Valence’ Electrons of (eae Fragments, PM, My My My Mg ” ay dy at dM My 16 = Pilg Mg tly My 3s ‘The two electron donor ligands are treated sine to CO. For example, CH, 5? MA(CO), Mn(PRy)s yPOMNCs)* <—$ 9 Mn(CNR)s ‘7-electron fragment 17-electron fragment n* -CsHs and 1° ~CgH are treated to occupy three coordination sites and to be $ and G-ectron donors. Fo example, (8 =CHg)Fe(CO)2 yn ~C gH) Ma(OO), ya Fe(CO)s]" MN(CO)s (7-etecron fragments) (a ~CsHs)Min (CO), ¢g—+(n* ~CeHg) Cr(00)2 gy AIMn (CO)s]” —g—PCr(CO)s (a6-lectron fragments) Some examples of transition metal fragments which are isolobal with main group fragments are sven in Table 3.5 ‘Table 3.5 Some Isolobal Fragments of Transition Metals and Main Group Elements og a eee é CO nico Feo, 7 [oy, | FeO ‘(Mn(CO},]" tFe(CO})" CrlOO}s, Co(CO}; Ni(CO), retcoy Neon Fe(CO)s ‘Co(CO), ‘CpOs(00) Cpcr(co), Cr{(CO), Nico, cpFe(CO), (cao, on coco ‘CpMn(CO},_ Co{CO},, ae cH cH veo ons om ar P § Since a 6-electron CH fragment is isolobal with 16-electron Fe(CO), fragment. The two CH, fragments combine together to form stable CH =CH, whereas the dimer of Fe(CO), isnot nearly as ‘Clee: Comprands 335 stable, Also, both CH, and Fe(CO), form three membered cyclic structures, clopropane and Fes(CO), respectively. Cylopropane is a trimer of Ci, fragments but Fes (CO); has two briging 0 ligands (Fg. 3.11) and therefore, is not a perfect timer. Osj(CO)ia is Isoelectronic with Fe,(CO)a and is perfect trimer formed by combination of three Os(CO}, fragments which are ibolobal with Fe(CO), and CH. ey co Hc— cH, oT 0 of [co eh, Der ee or oc oc br\, Lo? °E\P/t0% oc” INo5° 007 Nog ¢o) co @ © © Fig, 311, Structure o a) cycooropane (6) Fes(COh2 (2) Oss(COhe Similarly Co(CO)s, Rh(CO)s, (CO), CR and P fragments are isolobal with each other. The 15.eectron fragment I(CO), forms Ir (CO) thachasa tetrahedral symmetry Pand CR fragments also form tetrahedral symmetries of Py and (CR), respectively. The Co(CO), and Rh(CO) fragments form isoelectronic Co4(CO)yz and Rh (CO), complexes respectively and they have nearly tetrahedral array of Co and Rh atoms but have tree bridging CO ligands (Fig. 3.12). fone or more (Co(CO) fragments of Co, (CO), axe replaced by CR fagment (Pig 3.12), the vetrahedral structures ‘now, do not have bridging CO ligands. Ths i similar to the replacement of P atoms in the P, tetrahedron by Co(CO), fragments co hed ee ‘afb, ag co oN“ oc ‘co co3.26 (Oreanometalc and Bivinorgnic Chemiey Chster Compounds Isolobal analogy in boranes and earbonyl clusters can be determined using electron counts and geometries ofthe clusters. Superhyper closo boranes (B,H,)* with (n 1) skeletal electrom pairs are isclobal with the “0. spt coo cont ae For Example : O5e(CO)23 OF [Os4(CO)a4]” TEC=8x8 + 2342-6444 PEC 110-84 12=110-9 EC 14 2 8-1 (1-1) superhyper oso [Betty + Number of skeletal electron pais (8x2-2) 14 22 =1 (n=) super byper oso Os4(CO) sg [055 (CO) ae] MBH)” ‘Therefore, Simi, hypercioso borane BH, ae isolobal with hypercoso (polyhedron with one face metal capped, coso boranes are isolobal with closo (Le, regular polyhedron like tbp, oh, nido ‘oranes are isolobal with nido Ce, polyhedron with one vertex unoccupied, arachno boranes are ibolobal with arachno(.,polyheron with vo vertices unoccupied) and hyphoboranesaretlabal with hypho (ie, polyhedron with thre vertices unoccupied) metal clusters. A wansitian metal cluster and a borane are isolbaliboh have same numberof vertices. Some examples ae given below 2) 05,(C0), Tao 6x 8410.2-40696-04 Pica e4- 61284-72012 12 22 2) ypercloso: Bette: aber shel ato pis S22 Aopen These, CO) ye (2) [0s6(CO)61* + TEC=6* 8+ 18x2+2=48+36+2=86 327, PEC = 86-631: 4 86-72 =7=641 (+1) 4 loso (regular octahedron) (Botle)® (regular ocahedron) (6x2+2)_14 2 ‘Therefore, [05,(CO)s]* ¢5 918 Ha) Number of skelca elec pairs (n+ Veloso (3)(05,(CO);5]* = (sits? Numer of stl elesue puis 5°22 6 (n+ (a0 Therefore, {0%s(00),) p18) (4) Fe,C(CO),s = Tene BAe 190 2=904-44 25 FEC = 62-4x12062-48=14 Pace Dorie? 44) Arachno (BH Number of see elecwon p= 22+ 6 Marina ara Ha7(n+4) arachno Therefore, (8) FesC(CO)is + Felis 3918, TEC=5x 84 4415x2= 40444 30-74328 ‘Onzanometalic and Bisinoganic Chemistry Cluster Compounds 329 [e5(CO),sI*: (7LOpNIT = TEC Sx 84 15x2+4= 4043044074 PEC =74-Sx12=14 PEC 14-7 (n+2) nido Seay oT (n+2) ‘therefore, FesC(CO)ys goles (CO}ss]* —gUBsHsI (){HCO6(CO)sT + £69 415x241 =145449041=86 96-612 =86-72=14 (n+) doso [oog(CO)s1* aC =6« 9415 2+2=54+ 304 GFes(CO)s]* = TEC=6x 84 18%2+2=48+96+2 PEC =86-6%12=14 PEC 2 14 oso ar(ned a (lta): 6x26 oma Therefore, [HCog(CO)g]” [BsHgI Zintl Tons “The ionic dusters of main group elements are caled Zin! ions Since these ions have no igand, {hse are alo known as nacked cisters. Some examples of Zn ions are: PL, Suf SbF, Sn, Ge, Bit, Sn, BP, Te, SOP ee intl ions are lo classified into caso, nido,arachno and hypho dusters. «tee n+2 (close) TEC 4n+4_(nido) Tuc= 4n+6 (erachno) ‘TEC= 4n+8 (hypho) ‘where n =number of metal atoms in the Zintl ion. Examples: (1) PE, TVE = 5x 44.2= 22(4n + 2) . ie - Because =§; the total electron count = 4n +2. Therefore, Fby has eos structure. (snd, TE Because n 44 4= 40 the total electron count = 4 n + 4, Therefore, So$> fas aido structure, (Bit, TVE=5*5-3= 22, ‘Therefor, Bi¥’ is adloso. (80, VE=4x5+2= 22= an 46 ‘Therefore, Sb# is arachno. ned330 Ree ‘Oreanadalic and Bininorgnic Chemisty Cater Compounds at Synthesis of Carbonyl Clusters : (1) By pyrolysis of mono di- and trinuclear carbonyls Af Objective Questions 3Ru(CO), > RUs(CO) +360 - ‘2Fe(CO)s; —+Fer(CO)s +00 1, Intense band at 15000 cm“ in the the UV-visible spectrum of [Bu4N]2 Re ,Cls is due to sere, 500mm cD i i : BR (COn2 2Rlhg(CO)s + 400 the wanstion: ~~ (2) By nucleophile atack ofa carbonyl anion @ rom 5% ! [Dn(CO)s}" + BrRe(CO)s ——+ (OC), Mn—Re(0O)s Os>m @ x3 i O%s(CO),2 + {C0(CO)_]° ——> [C005(CO)x)" + 300 2 Teunbe of mea meal tds in (OP i Rus (CO)y2 +{Fe(CO),]” ——> [FeRuy(CO)j2]* +300 ais ha ‘8. The bond order of the metal-metal bonds in {ResCly]™,[ReCls(P(C2Hs)s )2) and [esq PCzH15)Pha)4] respectively are (@) 44nd 3 (0) 3,4and 4 : (© 42and3 (@) 23 and 4 i 4. Among the following, the correct statement is @) CHisisolobal to Co(CO)s (©) Gis isisolobal toNi(CO)2 (© CHlisisolobal to Fe(CO), (@) GH, is isolobal to Mn(CO), 5. The correct statement regarding the terminal/bridging CO groups in solid Co (COs and ry(COha is (@) both have equal number of bridging CO groups (©) numberof bridging CO groups in Co 4(CO) is 4 (© the mumber of terminal CO groups in Co (CO), is 8 (@) the number of bridging CO groups in iy (CO is zer0 a a 6. Which of te following metal fragments, d? ML, is solobal with CH? @d-Ms am, © @-My @d>-Mig ‘Among the following clusters : A=[€4)Co6(CO);sI", B = [(H)2056(CO)],C = (64),035(CO)s) His encapsulated in 7 (@) Aonly () Bonly (©) Band Conly (@) Aand Bonly 8. Thecorrect statement regarding the terminal/bridging CO groups in solid Co (COja and. Ity(CO)a is (@) both have equal number of bridging CO groups (b) number of bridging CO groups in Co. (CO), is 4332 10. 12. 13. 14. 16. 16. ”. 18, Organometallic pd Biinareanie Chemistry (©) the number of terminal CO groups in Co (O)a is 8 (@) the number of bridging CO group in Ir (CO)y i zero ‘The cluster having arachno type structre i (2) [055(CO) 0) 1053(COha} © Bry(COra] (@ Rhg(COs} Inthe luster{Co 5 (CH)(CO)sJobeying rue, the number of metal-metal bonds andthe bridging ligands respectively are (a) Sand 1 cH (6) Oand 3 CO (© 3and1.co (@ 6and 1. cH ‘According to polyhedral electron count rule, the structure of Rhg (CO) is @) doso (0) nido (6) arachno @ hypho Total number of M—M bonds in the given camplexes Fes(CO)2, Co.4(CO}z and {m°CpMo(CO)s]> are respectively = 345 03,42 © 43,2 3,63 The bond order ofthe metal-metal bnd inthe dimeric complexiRe jl, (PMePH)4]* is: (@ 40 35 © 30 @2s ‘The cluster Rh (CO)s, O55C(CO)s and [eq (CO}z}™ has structure respectively : (a) closo, nido, arachno () nido, closo, arachno (© closo, arachno, nido (@ arackino, loso, nido ‘The value of x in Fe, (CO), + @s ws @w --. - @2 Predict the number of Fe—Fe bonds in fq ~CsHs)Fe(CO)}, molecules using the 18, electron rule : (@) one () a0 © three @ four Considering the quadrupolar nature of M~M bond in [Re Clg], the M—M bond order in ReCl,(PMe ;Ph)<]" and Re Cl,(PMe;Ph)«] respectively are (@ 30and 3.0 (0) 3.0and 3.5 (© 35 and3.5 (@35 and 3.0 {[Co(CO)4}is isolobal with (2) Cy Oo cHs © cy ou (Clases Compounds 333 19. ‘The compound which hes four metal-metal bonds is + (@) Fex(CO)y (©) Coa(CO) © Rec @ Rus (COh2 20. The molecular orbital configuration of the Re—Re bond in [Re sClg]* is = @) 02x57" (0) 07n'5%57 (© 07x62? @ o?n'5* 21, Metal-metal quadruple bonds are well-known for he metal: @ Ni 0) Co Ore @re 22, The total number of metal-metal bonds in Rus (CO and Go (CO) respectively ie: (@ Band 6 (©) 4and5 (© weroand 4 (@3and4 23, The number of MM bonds inry(CO) are ©@) four ©) six © eight @ zex0 24, The number of metal-metal bonds in the dimers (CpFe(CO}(NO)]_ and [CpMo(CO),}. respectively ate : (@) two and two (©) one and ewo (6) two and three (@ zer0 and one 1® 2@ 30 £@ &@ 68 70 ®© %9 BO KO Bo Bo we BO BE moO MH BO MH mw 20 BO 2m @oe Copa aay mi Subjective Questions 2. fRexlg}* adopts an eclipsed conformation whereas Res(CO)oadopts a staggered conformation in the solid state, Explain 2, Calculate total number of M—M bonds and number of M—M bonds per metal in the flowing species ung 1-lecron rl. Aso draw the stucures of eth specie : ad @ tO ©) Fes(Oha Reactions of Organometallic,.-=:: (©) (CpMo(Co),}, (@) [is -CO)Fe., (Co), - j Ge tacpNOWH, (0 Rus(CO PAs a Compounds QM 3. Predict the M—M bond order for the following species: (@) (00) 4Ce(u-PPh,)sCr(CO)4] (©) (C004 Mn(u-PPhg),Cr(00)4} 4. Calculate the total valence electron counts ofthe following clusters. Also classify them as close, nido, arachno and hypho: @ Beli ©) [Cog (COnse}* Oxidative Addition ee eee Oxidative addition reactions are among the most important reactions in organometallic COR COs chemistry. An Oxidative adition reason involves 5. Classify the following species as closo, nido, arachno or hypho: 1. The addition of a molecule X—Y with cleavage of X-Y single bond toa coordinatvely (@) Balls (CoCp)2 (©) Ball FFe(CO)s}2 unsaturated compound ia «relive iow oxidation sate, (© Poy @ sat 2, Formal oxidation of metal by two units and atthe seme time increase in metal coordination ©) Re CiCO)_I* OfFe.N(CO)a)” rumber by 2. ooo 5 ~ © ‘Adaitibi of a multiply bonded spesies with reduction in the bond otder to forme metlacyele is also an oniatve addition reaction ‘Addition of @ CH bond in an ortho-metallation step is also an oxidative ation reaction. H Wy uM mR 4 Ph >2 ‘Organica we Boiorc Chiy Reacts of Onsmmeli Compounds a The ingot fea of ona dation reacons are a |L, The metal should be in low oxidation state (0, +1 or sometimes +2), Le, there should be NiQPEL), + a) 7, an) non boulng electron density on metal i 2. The complex must have two vacant sites, ie, the complex must be coordinatively Pet, unsaturated, : a {T the numberof ligands that can be xecommodated within the coordination sphere of met Thera of oxidative addon reaction ister in coordinately unstated complexes ite Aibeman feds arcane corinne of meta square planar complenes whereas the rate of oxidative addition reaction is slow in Sep bip reerrn par coordinaively saturated completes lie octahedral complexes, An octahedral complex may CpcuPMes)a + Met [cpcobte (PMes)a)"F undergo oxidative additian if it loses ligands during the coutse of the reaction making the ‘The 18-electron complex such as [Fe(CO),}* has only four tigands but addition of X—Y site availble for interaction, would require the use of snuboediag molecular orbitals which is energetically not 3. The at of ordative addition reaction decreases with increase inoxdation state of metal favourable and increases on descending the group in pesiodc table Fe? Got Ni! Mechanisms for Oxidative Addition Reactions tue ht ue Increasing order of rate of oxidative additon elas He ms Depending upon the nature of XY, oxidative addition reactions may undergo bythe following mechanisms: Decreasing order of rae of oxidative addition (1) Concerted Reaction : If ¥V is non-polar such as My, O; then it undergoes oxidative 4, Mos commonly the metal inthe complexes in their lov oxidation states havea or !? ‘udition reaction through concerted or three centred transition state. Concerted oxidative addition configuration. For example {ir(PPh.,)2(CO)CI), d°[P4C@Ph}41, d*,[Ni(PCOEs) 4), action tan associative reaction in which the incoming ligand XY fistbinds sac complex and 5. The metal must have stable higher oxidation state separated by 2 units because during then undergoes XY bood breaking resulting in stong back donation of ve elesuns from the oxidative addition oxidation state of metal increases by 2 nis, ‘metal nto the antibonding molecular orbital of. 6. In gener iis seen that during oxidative addition square planar complex converts ino ocxahedral complex and 2 16 electron complex changes to I&-leczon comples. x 2 7. The complexes with metals of oxidation state higher than +2 rarely give oxidscive addition LM+X—¥ —> bam] — Mg reactions Y 8. The complexes wih cms in tht highest oniacon sae do wot give oxidative addition The second step really involves the oxidation of metal because co electons are formally reas Forgrample Ct {Mn’*, Ta® can not undergo oxidative addition to gives Cr*™, transferred to ¢ antibonding of XY. Some examples of concerted reaction of Vaska's complexes ia and Ta’ respectively ae: 9. Complexes with d? metals do noc undergo oxidative addition. {@ Oxidative adon of on Vash’ complex 10, An cleawen rch edonor ligand coordinated tothe metal incesses the cae of oxidative addition reaction whereas 4 x -acceptor ligend decreases the rate of oxidative addition - a HH H vt reaction PhyP—ie—PPhy +H, —— PhxP—le— PPh, + PhP ir ‘LL. In general steric hindrance decreases the rate of oxidative addition reaction. a 4 "at PPh 12. ‘The complexes with 18-electrons can not undergo oxidative addition without lass of a oc’ oct oct & electron ligand because & 2c” site must be present on metal forthe reaction to occu. For example, i) Oxidaiveadton of, on Vasta's complex 05 (CO}s +a p> sO CO}, a 950 +H Ru (CO), (PMes)+ Mel —epr> Ru (CO}s(PMes) (MeL mre tern, Sm ery (PPh), EERE a (PPh) (PI Br ot ae? PS Pa) oc ot a In this reaction OO bond is not completely broken but the bond order of i reduced from 2 tol“4 % Grgnomtalic and Bisinrganie Chessy (Gi) oxidative addition of halogen (X,) on Vaska's complex cl qa Zz +a, 1 PhP —Ir— PPh PhP ie PPh, oc’ ora Gu) oxidative ation of akenes and alkynes on Vases complex cl HES, 2 aw lee a Php ih, oc | eS cH - mez Cry 1 acta Inthese reactions, the trans (CO)CI se of ligands become csi the product. Inthe THP transition state the trong x-aceeptor CO ligand occupies the equatorial poston (9) Oxidative addition of methane = Mh By \ C y ad m+ cH, —+ Se : p7 Nay Phy Phy (@) 5,2 and Radical Reactions : If XY isan electrophilic polar molecule such 25 alkyl halides (CH,CI, CHB, CHD, oxidative addition reactions proceed by S,j2 mechanism involving ‘wo clecron transfer or via radical, one electron transfer mechanism. In $2 mechanism, the clectron pair of metal of LyMdirectly attacks atthe leas electronegative atom of X—Y molecule and provides a electron par to.o-antibonding molecular orbital formally to breakeX—¥ molecule into X~ and ¥~ ions. The LMcompound itself oxidized t0 LqM™. Resco of Onno Compoande a5 en : \7 yes yl eye ot — ea a — BM 7 HC at uf jt PhP —Ir— PPh, + CHjI—— PhP Ie PPh oc’ oc® a ike concerted reactions, these reactions are also second onder reactions but they are accelerated in pola solvents. R and X may be cs or trans to one anther in the final product as expected for the recombination of the ion pair formed in the frst step In the reaction (1) the product istrans, because thecranseffet of CHy group is high and therefore, it prefers the psitontransto the vacant stein the 16electron square pyramidal intermediate. Itis co be noted chain polar solvents, the molecules that dissociates are not restricted to occupy the cs position. ‘The radical mechanism may proceed in two ways—the non hain and the chain mechanisms. ‘Themore nucleophilic the metal (higher electron density on metal, low oxidation state of metal), areater will be its reactivity in S,» oxidative addition, For example, Ni@PR,), undergoes oxidative ‘addition more faster than Ni(PAt,),. Increase in steric hindrance on carbon leads to decrease in the re of oxidative addition. Therefore reactivity of ally halides fllow the order Mel > EM > iPr ‘Thenon-chain reaction involves the addition of alkyl halides, RX to PUPP, )s (where R = Me Ee and "NCH, ¥ = Br). le aon-chain oxidative addition, one electron from M i transferred to theo-antibondling orbital of RX to form M* and RK. First X" iscooedinated to M* forming MX and R radicals, These radicals eadily recombine to give the product. L,M+ CHsl—>L N+ GH ——+L,M(CH For example, PLCPPhs)5~ PeCPPhs)a +FPhs PLPPhs), + Mel P e(PPhg)3 + Mel” 2" »BeePPhy Jal + Me »MePt(PPha)2 1 For a given allyl halide, rate of oxidative addltion reaction increases with increasing basic character of meral and the order of reactivity of alkyl halide is I> RBr > RCL“6 cea Orson nd Bcinorganic Cenisny ‘The rate of oxidative addition zeaction increases with increasing stability of alkyl radical : > 2 > 1 >Me ‘The radical chain reaction occurs mainly between EiBr or PHCH,Br and Vaska's complex as show below RY + Ir(CO}CH(PPhs}z —+ Rie™ (CO}CLCPPg)2 2 > RKIE™ (CO)CLPPhs) +R RR (8) Tonic Mechanisms : Hydrogen halides are dissociated in polar solvents to give proton (CH) and halide ions (X" ) which add to metal complexes in separate steps. Usually the complex in ‘Which the metal isin low oxidation state andthe ligands are basic enough, gets protonated followed by the addition of halide ion to form che final product. PROPPh 5 )4-+H° > (HPAP )]* > [HPH(PPA 3 )2C0) we 28, teed PP ee, ene pine Wea sit im Rate of reaction = k feomplex] {H") ‘There are some rare cases in which the halide ion binds first followed by protonation of the intermediate, These reactions are accelerated by electron acceptor ligands and by the ner positive charge on the complexion, Ur(cod)yLa)" +61” —> Uireosdt ot) fttr(cody gc" 16" 2, sae planar ie" TP tee", ocabedel Rate =£ feomplex] {CI"] Lewis acids such as RCOOH and HCl also reat by same mechanism. r(CO}CIL, — A225 fHIOCOR}(COyL ACH a_i HigCDCla(CO}L 2] Intramolecular Oxidative Addition : C—H Activation or Orthometallation or Cyclometallion “There are some reactions hich involve the transfer of hydrogen atom from a coordinated ligand to the metal atom followed by (rsimaitaneous wih) change in bonding mode to the ligand from hich the hydrogen atom came, These reactions are refered to a5 cjclomealaton reactions or intramolecular oxidative addition reactions. In Vaska's complex, IrCKO\PPh,)2 the coordinated iphenyiphosphine can undergo intramolecular eyelometallation. Mis eclometallaton occurs due to agstc interaction between the Resco of Organometallic Compounds AT ‘metal and hydrogen atom ortho to the phosphorus bound carbon, This reaction i also called corthometallation because the ortho carbon ofthe phenyl group particpates in eyelometallation. a 1 6 aque planar Oxidative addition to M—M multiple Bond ‘Addon ofa ligand may ocr across the MM mukipte bond. In this reaction oxidation sat of each metal ineeases by one unit but the ordination number of each metal nereases by two units ‘The M—M bond order also decreases by one unit. & a Oy wy dtwewla 2. g@SWiWla a Nep a SH Nop Br ,CO 17 ee) 2.0¢5Mn—co 0¢—Sin —— ninco oc” co oc” Neo 485 1 oc co Oxidative Coupling ‘The reaction in which a metal induces a coupling between two unsaturated ligands such as alkene or alkyne to give a metalaycle s called an oxidative coupling reaction. The formal oxidation state of the metal increases by two units, the electron count decreases by wo units but the coordination number remains unchanged. The original two neutral igands form new bonds between them.48 (Oreanomtallic nd Biooraaic Chenity sci oe a] k R oo yuk — x Kk 1 =H, wo NMR signals with equal tens shouldbe obtained Butithas ben observed that on refuning it gives ony one! HNMR signal i, all the 4-1 atoms are in same environment, set. fe) eae i on a sernacicoa — OX Teco Th 7 : . | t ® ne Gn eee ae i Ph” Py’ Ph : Reflux eB, Coupling is netoaly limited to alkene but also carbenes and alkenes undergo oxidative coupling. = uk : ‘Resctons of Oranometalic Compound ry Reductive Elimination ‘The reaction in which toc ligands bound to metal couple together and leave the metal and the formal oxidation ofthe metal i reduced by two units is calle a reductive elimination reaction. The ‘reductive elimination reaction isthe reverse of the oxidative addition reactions. Some examples ae: x a a Ae Me Phy PhP im /CHCH, 6 PDIP ys PPDe mp7) Sw mp7 Sa a Phy Phe Ppt a PS, Pally Pd + CH G&D Xai, Bao CG Cie hy Phy Hon Phyp it Py Page ocf a oc! Some times the molecule eliminated is diferent from the one added oxidatively. For example, Php ft + GH Salient Features of Reductive Fliminations are : 1. Since the reductive elimination involves transfer of an electron pair back onto the metal from two anionic ligands, the metal, therefore, should be in high oxidation state. It means thatthe electron deficient metal faiitates the reductive elimination. 2. The ligands which are to be eliminated should be cis to each other. The ligands which are trans to each other will not eliminate. 8. The x-acceptor ligands attached to metal will enhance the rate of reductive elimination. 4. The low valent product formed after reductive elimination must be stable.remnants and Bcinerani Chemisty '5. The presence of bully groups or steric crowding facilitate the reductive elimination. 6. LE Cpis present cso any other ligand, then Cp will neve elininate cf an? Nordine tintin oH i 7. Theat edaivecminan flow te er momen > cc 6. Tereucie inition ining tweet ao Fon 0 oc Fr exe ° I HCo(CO}, + Me—C—Co(CO,) —+ MeCHO + 003(COIy 9. Inreducive elimination reactions entropy increases. 10. ‘The reductive elimination is most commer: or intermediate oxidation states such as the d® metals Ni#, Pat and Au" and che d° merals PCIV), PdCV), Ir) and RRC. Migratory Insertion The intauction of an unsaturated ligand such as CO, CH, =CHy beween two other atoms inal bound togethers called as insertion. The insertion of CO into M--CHt bond to give acyl complexes is one of the most widely studied reactions of transition metal alll. For example, when ° i (CH Ma(C0). is treated with CO,CH; —C-—Mn(CO), results ° HyC—MixCO}s +CO = CH —C—Min(©03) “Three expected mechanisms are possible for this reaction The mechanisms become apparent if Cabell C0 is used as incoming ligand. ‘Mechanism-t : Direct insertion of incoming CO ligand into meta-alky bond, (2,00 poe oc—Mn—CcH, + !co ——~ oc—Ma—#C—a, 4 Al oc co oC 0 ‘Mechanism-2 In this mechanism the CO ligand esto alkyl group migrates and inserts into the _metal-alll bond resuting in 5-coordinate intermediate with a vacant site available for attachment ofan incoming CO ligand, Reactions of Ornomalc Compounds ant Inramolecular insertion Vacant ste 1 oc co ‘Mechanism: In this mechanism the alkyl (CH,) group would migrate rather than the CO ligand and attach self roa CO ligand cisto the allyl group resulting in aS coordinate intermediate ‘with a vacant site available for an incoming CO ligand. Methyl CH, oh nigeation i i 0 ,co) = =O Ts 17 sco | oF Cy corn — oc—Min—co ocf to oct by wieantste oc by ‘The reverse ofthis reaction is called decarbonylation or deinsertion or elimination, Evidence in Favour of Migratory Insersion ‘These three mechanisms are seen tobe indistnguishable as productin each mechanism is seen to be identical. The reaction of ""CO with CHsMn(CO), gives a product cis{CHsCO)Muxt"°COXCO), which have no "CO in te acy group. Furthermore, none ofthe incoming "COends up transto the acyl group. This indicates thatthe reaction would nor proceed through mechanism, 1, i, no reaction ocutsbeeween incoming gaseous CO and the M—CH bond. “The infrared studies of" COhas revealed thatthe reaetion of CO with CH Ma(CO)s proceeds by the migration of apt group rather than by insertion of CO ligand. ‘The CO ofthe ey group of mechanism 2 has the choice of four is postions to which it may rmigrate by replaien the CO ligand that is initially present. One of these sitesi occupied by "CO. Ax a result, 25% ofthe product would have no !CO and 75% would have ® COcisto the alkyl “Experimentallyithas ben observed that 25% ofthe product has no CO, 25% has "CO transto the alkyl group and 50% has "CO cisto the alkyl group. A methyl migration is eonsistent with these experimental results. As the alkyl group migrates, it may displace the " COligand to give 2 product containing no "'CO (25%), it may displace either ofthe two CO ligands cst che "CO ligands (but ‘ot the CO ligand that ineransto acyl group) to give the product with CH, esto ™CO(S0%) orit may displace the CO ligands trans to "\CO to give rans product (25%).See raee eee ereSSeeTOeEE COTES OES SO TESS OSETOSE SSeS eC ESS Sree ee eee on Crone Birnie Chena 60 coo ve ocs ui — tan, 7 oc ¢o ito Le. : 4 2 CH op 30 100 co CO co 17! 17m Wa if ccrui—co — occk—co occ oc M00 1 | oct Go oct co HC“ Go oct GH 2%) 25% om) 2s) ‘ al No co ‘Equivalent product (trans) Teal 0%) 9 ‘Since the allyl migration is consistent with these experimental results, therefore, when the term CO insertion i used, it often means thet there is alkyl migration ‘An another important evidence in favour of the migratory insertion is the steriochemical evidence. ° r ° CK ame ORS woe we Noe tn iF r L co nserion Rk 00 Ce ee ee oe eesion of onion ‘When the reaction is carted out in CH NOs, the product wit inversion centre is formed which is consistent with Et migration. Insertion of Alkenes ‘The migratory insertion of an alkene Inco M—H or MR bond results in the conversion of a coordinated alkene to a. -bonded alkyl group. This reaction involves migration of an H or alkyl group and results in carbon chain growth. a3 ‘The Hor alkyl group is migrated to the-carbon ofthe alkene to form the metal alkyl complex. It {sto benoted that CO insertion occurs into MR bond but notin M—H{bond. The insertion reactions can be classified into (1) 1,1insertion (2) 1,2-insertion. In ,L-insertion reactions the metal and the migrated ligand make the bonds tothe same atom of the unsaturated ligand such as CO. Fy.0c0 OC—Mi— CO. + PPhy I oct co The insertion of CO into metakayl bond of CHMn(0O) is so an example of 1,L-insertion 1 1,2insertion reactions, the metal and the migrated ligand make bonds tothe adjacent atoms of the unsaturated ligand, Insertion of an alkene into MH oc M—R bond is an example of 1.2inserton. Is general, m'ligands tend to favour 1,1-inserton wheres the n?lgands tend to favour 1,2inserion. 0, isan example which can undergo both 1,1-and 1,2nsertions cis strong electrophile with a vacant orbital on sulphur and therefore it can attack even 18 compleses. ‘Asan electopileit an atack at the a-carbon of the ally group from the side-opposite of the rmetal and forms an alkyl sulfinate ion, RSO3 with inversion ateabon. ince the negative charge is present on oxygen, kinetically oxygen ofthis ion can bound tothe metal o form O-bounesulfinato comple. Since $ is softer than O, therefore, the thermodynamic product is usually the S-bound salina with soft metal Ie canbe coneluded that in this eason sequence SO ist undergoes 1,2 insertion and then 1,1 insertion Kinetic product (A, 2insertion of $0,) ‘Thermodynamic product (2, insertion of $0;)414 ; Organometallic and Bioinorganic Chemistry Salient Features of the Migratory Insertions are given below : 11, During migratory insertion there sno change inthe formal oxidation state of metal 2. The migratory insertion creates vacant sit which is being occupied by the incoming ligand. 3. The two ligands undergoing migratory inversion must be cis to each other. 44. The two ligands which are transvo each other never undergo migratory insertion. 5. Migracacy insertions are usualy favoured on more electron deficient metals. 6. {there are two different alkyl groups coordinated to the metal (Fig. 4.1) the alkyl group ‘whichis more eleeron rich willbe beter nucleophile for migrating tothe electron deficient CO ligand but” > f-prop” > BY > Me™ > PRCH Fig. 44 7. Migratory insertion i also posible forthe ligand the than CO suchas PM, PPh The Tigands which ae beter donors have eater tendency for displacing the ale group far migratory inerton (lor example, PMe, > PPh). 8, La migratory ligand ie chiral ig. 42) han the reaction usually proceds with tenon of configuration at that cal exon. eB wie 170 oc Mi —co 7 ocf fo Fo. 42 9. The bulky ligands coordinated othe metal wil enhance the rate of migratory insertion. 10. The Lewis acid such as AIC, enhance the rate of migratory insertion. 111. The insertion reactions are reversible but usually one direction is observed. 12. CO insertion usually takes place into M—R but not into M—H bond. Whereas alkene insertion is more common for M—H bond but much less common for M—R bond. The repeated alkene insertion into an MR bond produces alkene polymer and the reaction is called alkene polymerization $-H Elimination 8 - hydrogen elimination is the reverse of the alkene insertion. It involves the tansfer of B-hydrogen atom from the alkyl group tothe metal and the conversion of the o-alky! group tothe x-bonied alkene, Le,, CH bond is activated The first step involves a cyelic intermediate with an Reactions of Organometallic Compound 415 agostic MHC interaction, The agostic interaction is a theee centred two electron (3% —28) interaction between the metal M and a C—-H bond in ligand attached to metal ae wai, Nw a @ — oF IN faa mee pets ae £-elimination is responsible for the decomposition of some metal alkyl complexes. Ps, yp HH > ER, op7 Nc ep NCH oH oy tH LyMCH,CH,R —> L,MH (n? ~RCH= CH) —> La MH + CH; =CHR Some Important Features of the Hydrogen Elimination Reactions are given below : es 1, These reactions are usally given by 16electon complexes because thre iS a 2 site available for accommodation of hyde on, except fr PAC) and Pet) which tend wo avd the 18 configuration. 2. 6-41 transfer to metal leads to enovalof alkene. 3. Theres no change informa oxidation state ofthe metal. 4. An 18 complex may giveB -ydrogen elimination reaction ater removing a ligand so shat there would be a vacansie. 5. Electron count increases by two unis. 6. Theallyl complexes that havef-bydrogen in ally group undergo elimination reactions. 7. Thealkyl complexes that lack} -nyrogen tend tobe more sable thermally than those have Banydrogen and therefore they cannot undergo P elimination. This does not mean that 1ethy complexes are necessarily stabl hey vay tndergo other types of reaction. Some examples of ltl groups that have no ‘hydrogens are Me, CH,CMe,, CHSiMes, HP,416 Oreanomalic and Bisinorpanie Chemisty 8. The coowtinatvely saturated complexes (the complexes in which ll the contin sites ae oceupied) containing f-hydrogens asin (q/-CsHl,) Fe(CO),E are generally more thermally stable than complexes having vacant coordination sites. 9. Steric hindrance also prevent H-limintion. 10. The i-limination s much more fase ford? or higher eransition metals than fr d® and ‘main group elemental complexes. a -H Abstraction ‘The alkyl compleres of early transition metals containing one or two «hydrogens but not hydrogens in alkyl groups may undergo a -hydrogen abstraction to given carbene or carbyne complexes. LM=CRy LyM=CR carbene carbyne a ef vaca Lata, (*gyctt)sTa=CC Tool, MES Ta BalCle agg” BUCH) TA= CQ Abstraction ofa two a-H atoms gives a eatbyne complex. Wels tiet> QMexCCH,),W = CMe suey" ants Tal (CHP "+ Cpt THCUGH:Ph)y "> Cp" TaC= CHP) CUCM) Onn getainaon QL ‘The b-climination gives an alkene, a stable compound that dissociates from the metal. Whereas the methylene ligand formed from dea -limination i very unstable in the fre state and therefore does noe dissociate from the metal, Reactions of Onanometlic Compounds “7 Hydrogenolysis Substituion seactions of hydrogen with transition metal complex are called hydrogenolysis reactions. Cp. CH Cp. A Ly a sett Cp’ CH, cp CHy ‘The metal centre has 16 electrons and there is no change in the oxidation statea8 ‘Orsnontlic and Biincrpanic Chemisty mes Objective Questions 1. The resction {(C0),Mn(Me)) + CO [(CO),Mn(C(O)Me)) is an example for: (@) oxidative addition () electrophilic substitution (6) nucleophile substitution (A) migratory insertion 2 Sabsiuton of with other ligand wl be easiest forthe species Me Me @ @ o) ae FA mn, Mn, My @ @ Mm, 3, {CCO}PCCeH15)s a Granschlorocarbonylbis(riphenyiphesphie)iridium(D) also ‘knowns Vaska's complex can undergo oxidative addition with diydrogen. Which ofthe folowing structures is a corect depiction of the geometry and oration state ofthe ensuing produc: H 1A Co PT EPA, © eT HORE, oa rm + o 6 06 trem Hoa # iA (© (eH)? It —PCCH)y © CPT HE och ie och tun 4, The reaction [(Co)sMn(Mey] +. —+ [(CO)gMn{C(O)}M4e] is an example for (@) ovidative addition ©) nucleophilic substitution (©) lectropit subsinton @) migratory insertion TT Rescon of Onan Cnpsnds 719 5. The following reaction (Rh (CO),CHta]” —> (Rh olvent) (COCH Tis: () oxidative addition () reductive elimination (© migratory insertion (@) addition 6 The following reaction i M;{COYo + Be, —> 2MnBr(CO)s (@) reductive elimination () addition (© insertion (4) oxidative addition 7. The following reaction C02(CO)s +H —> 2[Co(H) (00), is : (@) oxidative addition () reductive etimination (© insertion (@) addition 8. The oxidative addition and reductive elimination steps are favoured by (@) electron rich metal centres () electron deficient metal centres (© election deficient and electron rich metal centres respectively (@ electron tich and electron deficient metal centres respectively Oxidative addition of O, to Ir{CO)CI(PPhs)2, the oxidation state and coordination ‘numberof ir changes respectively by @) 1and3 () 2and2 © 3ant (@)2and3 10. Reactions A and B are, termed as respectively : a 9. 1 Stesene, (00.000, a Me 2. Mesh B¥ae(CO), —+ (OO aRe— Se + Me @) iasevon, metathesis ©) metathesis, insertion © oxidative addition, metathesis (@) oxidative addition, insertion | |: e : : 420 11, [Ru(C Hs CUPPh, )s is stable only under a pressure of ethene because : (@) itis a 16-electron complex (0) it forms an 18-electron adduct with ethene (© one of the decomposition products is ethene (@ it prevent a-elimination of ethene 1@ Bo 2 © 20) 3. 10. © @ 4 @ wo ‘Onanotalic and Bivinorgaic Chemisty | 421 ms Subjective Questions 1, Discuss the following with suitable example: () Oxidative addition () Reductive elimination (© Migratory insertion (@ B -hydrogen elimination (© echydrogen abstraction © Onthometaation (@) oxidative coupling (ty Agostic interaction 2 Wi of de folowing comands energnes tte dion raconfaer 7 Ge explanation. (2) Rh(C0}(PPg),Cl oF I(CO}(PPhS)2Cl () tredmpe)(CO)ClorIr{dppe)(CO)CL (© Rh(PPh)sClor Rh(PPh3)_(CO}CI 3. Identify the product (draw stractare) of the following reaction : @ @rgrprbancco) AS, © RNP ct HEAT, 4. How is Mng(CO)y converted into (CH)Ma(O)s 5. Classify the following. reactions as oxidative addition, reductive elimination, migratory insertion, )-hydrogen elimination, oxidative coupling, simple addition or ligand coordination change - - (4) [NiCPPIs)4] — > INIPPh) 3} + PPh (©) [Ni(CO) 14} —> Ni(CO), + Fp (© [NUCNR),} + Cl, —> INICCNR),C1,] (@ [Fe(CO)5] + fg —+Fe(CO),}+ 0 (©) Co3{CO)g + Hy —+ 2H1C0(C0), © Ht (CO). +H, sep" I(COMED(CH) +00422 ‘Oraanonallic ad Bicone Chemisty (@) Mn(COCH, )(CO)s + Hy —> HMn(CO), + CHCHO (hy HzRhCIPh 5)2(E) —4 HRRACPs)2 +C aH 6. Write the mechanism in te fllowing reaction (2) CpCo(Me)_(PPhs) + 300 —>.CpCo(CO}, +CH{COCH, + PPh PR Ph HP Ph oy ZF BSCS gamer myst se KC sans —e MADE mers, XK Ph Ph co) ooo Alkyi, Carbene, Carbyne, Alkene, Alkyne, Allyland “ Buta-1,3-diene complexes Metal Alkyl Complexes ‘An alkyl ligand acts as a one electron donor monohapta ligand and, therefore, forms an MC. single bond. The earliest complexes are well known for s- and p-block elemeat Such as Grignard reagents and methyl lithium. The alkyl complexes of transition elements are less common than the s-and p-block elements. The transition metal complex containing only alkyl ligands are rlasively rare. Some examples containing alkyl ligand only include TiMe,,WMe, ete. The M--C bond dissociation enthalpy (or bond strength) decrease on desending the group in periodic table fr main group metals whereas increases on descending the group for transition metals (Table. 5.1) The bond dissociation energies of transition metal ally are greater than that of PbMeg (Table. 5.1). Therefore, the transition mecal allyls should be much more stable than, for example, ead alkyl, But this isin sharp contast to the observed decomposition temperatures of transition metal alkyl, for examples, TiMe, (decompasition temperature = - 50°C) and lead alkyl, for examples, PoMe, (decomposition temperature> 200%) and PbEt, (decomposition temperature > 100°C). Therefore, the difference in stably betweer the retaalkyls of Ti and PD isnot thermodynamic but Kinetic, Table. 5.1 "Main group metal alls Bond dissociation enthalpy (ki moF*) Satie, 27 Posey _ 152 ‘Transition metal allyls (CHC), 198 ZACH:CMes 250 H{CHCMe,) 26652 ‘Organomet and Bisinorgnic heist In the tetralkyls of Pb, all available orbitals are oxcupied: The four bonds to alls supply an octet of electrons, the Sd-orbitals ae filled, the 6 and c" orbitals are energetically not accessible, Consequently tettaaiyls of Pb decomposes by MC tond homolysis guin a comparatively high energy. PbMey E> PbMe, + Me In contrast to the sand p-lock metals, transition metals possess vacant d-ocbitals which kinetically facile reactions such as -H elimination, alkene insertion, CO insertion and reductive climination which lead to the transformation of the ally ligand iato other groups. In a 8 -hydrogen elimination reaction, an H-atom on the Bearbon atom of an allyl group is transferred tothe metal atom and an alkene is eliminated. LqM(CH;CH;) —+ LyMHT + CH=CH “The reverse ofthis reaction isan alkene insertion into the M—H bond, Both reaction are proceed through acyclic intermediate involving a 3e-2e M—1I—C bond which scaled an agosti interaction, Gypsies HA » MO CHR, wt + pcH—cHty ‘cH, M—cH,—CHR ‘The driving force for hydride elimination reaction isthe formation ofa stronger MH bond than M-elky{ bond andthe elimination ofan alkene ligand that reduces the unsaturation of the metal complex. If there are no hydrogen atoms on carbon or if there is norearbon atom inthe alkyl complex, /b1 elimination is biocke. Since methyl ligands have no {+H atoms, the complex containing methyl ligands are more stable than that of ethyl ligands. 6-H elimination is also locked ifthe BH on the ally is unable to approach the metal such as — C == CH, —CMes,—CHMe and ifthe metal has d? configuration, ‘Some examples of alll ligands having no BH atoms are: : CH, CH; Cell, —CH;CMe;, C= C—R, asst, ase, $7) {PH elimination reaction is energetically unfavourable in bridgehead ally, yet they have HL EoeN : Allg, Carbene, Carb, Allee, line, Alb sd Bats 53 ‘The bonded nary ligands, similar to the alkyl ligands, are relatively strong anionic ligands. ‘Though they have BH atoms but do not undergo elimination reactions. ‘Therefore, aryl compleres are more stable than alkyl complexes having 8 - Hatoms. ‘The allyl ligands are very strong anionic o CpFe(CO)se + F ch {Fey(CO) I + tl, —»(00) fe Ve (C0), +21 2. By Oxidative addition : Te CKCO\PP)2 + Mel —+ Ir" Me{CDKCONPPA 2 8. By Alkylation of Metal Halides: Hl a(S), ES iD TiCL, + Al;Meg —> MeTiCL, + ALCIMey WC), + 3Al,Meg —» WMeg + 6AICIMes 4. By the action of transition metal halide with organolithium, organomagnesium or organoaluminium (a nucleophile attack on metal. WCl, + 6MeLi—> WM + LiCl iC, + APHCH:MgCl ——> Zx(CHaPIy + MgCl4 ‘Organon and Bisinorsnie Chemisty (METAL ALKYLS OF MAIN GROUP ELEMENTS, Alkyl Lithium Lum ays and aryls are most important group 1 onyanometaliceompounds. Lithium alkyl canbe prepared bythe reaction of lithium metal with lly halidesin eer, eyohexane,orbenzene. uit px Lin + Le Lum arys are best preapared by the reaction of n-buy! ihium, -Bul with an aryl halide *pucl+ ani —> "Bubi+ uC BuLi+ Ark —> Liar + "Bu Lithium stlys of aryls can also be prepared by the reaction of metal with dialkyl mercury oF iar mercury 2L+HgRy (or gate) 9 2UR (or Lids) + Hg ‘The crystal structure of methyllithium is body centred cubic with the i<(CH), units at each latice ste Bach units a tetramer in which the four lithium reside atthe comer of a tetrahedron and the ciply bridging methyl groups are located above the centres ofthe wiangula faces (Fig .1). Each catbon atom is essentially a six coordinate (three hydrogens ofthe methyl and three lium atoms) ‘The carbon atoms of the methyl groups are bound to the thee lithium atoms at the corners of the tetrahedron Fig. 5.4 Each fae contains three vacant 2 orbitals or hybrids o 2s and 2 orbitals of thium and one sp* hybrid orbital of CH; containing a pair f electrons atthe centre of a face. Bonding ofthe methyl r0up tothre lithium atoms involves an p® orbital onthe methyl group simultaneously overlapping thee orbitals on the Li atoms (Fig. 5.2). Therefore, the bridging bond isa four centre-two-eleetron, (4e-28) bond. Since carbon is more electronegative than lithium, the lowest energy orbital (containing the bonding pair of electrons) has more contribution fromsp” orbital of carbon. Thus LiC bond is mainly ionic. ‘Alli Cader, Caro, Alken, Alle, Aland Butt, ene Compl 55 p° orbitals + bias -Fig:52. The orbital overlap jeading to the formation offouccaste tg electron bond Aluminium Trialkeyls Organometalic chemistry of aluminium is much mace important than that of other members of ‘group 13. Boron tralkyls and gallium tralkyls do not undergo dimerization. On the other hand aluminium trialyls and trary are often dimeric, Steric hinderance inhibits the dimerization, ie, the tendency of formation of dimers decreases with inerease in the sizeof alkyl groups, Therefore, dimerization of aluminium alkyls oceurs for aluminium trimethyl, aluminium wiethyl and aluminium ‘wiphenyi. The tendency of dimerization with branched chain alkys such as Pr, ‘Bu, MesCCH, and mesity (= 2, 4, Sarimethyiphenyl, 2, 4, 6(CH,) CHa) is less marked and these are usually ‘monomeric wit planar 3-coordinate Aluminium alkyl and tiaryls are colouress, highly reactive, volatile liquids or low melting solids which ignite spontaneously in air and react violently with water. Therefore, they should be handle carefully. ‘Aluminium ays and aryls can be prepared by the reacion of Al with HgMe, or HigPha 2AI+ 3HgMe, —2°° > Al,Meg +3llg 214 3HgPh, AE AL Ph + SHE Aluminium triethyl and higher alkyl compounds are prepared by reaction ofA with appropriate alkene and H gas a elevated temperature and pressure. 2AN+ CHa = CHa + 3H — M822 alg (CHCH)g Structure: The sutures of Als(ly)g and AzPhy ae shown ni. 3 Clg Ny ay Nay Nay, @ CN GN y 2 Cis Cais cats o Fig. $3, Structure ofa) Als(CHs (0) Abs56 ‘Onsaonetlic and Bisinoreanic Chemisty ‘These dimers are similar in structure of the ALC, (Fig. 5.4) but the bonding is different. fn ‘A, Cla, the bridging Al—Cl—Al bonds are 2centreeleeron (2e—2e) bonds, Le, each AICI bond, involves en electron pale [In aluminjum alkyl, the ALC—AI bond is three-cente two-electron bond which is formed by ‘overlap of an orbital on the alkyl group with orbitals on two aluminium atoms. In the alucninium alls, the AI~C-Al bonds are longer than the terminal AIC bonds. Wet yet aw Na Na Fig. 54;Sinctureof AL, tis t be noted that the alkyls of elements of groups Ist, 2nd and 13th are electron deticient, therefore, they ae commonly found as dimers or polymers. llylsof group 14, for example, R,Siare monomeric beouse they have complete octet and do not coordinate extra ligands. ‘Metal Carbenes Carbenes (or methylidene groups) : CH,:CHR, :CR, are rarely stable in free state. They are both thermodynamically and kinetically unstable and tis instability contributes to the very strong binding of earbenes to metal atoms. A free carbene has two spin stats: singlet (#) and triplet (. Singlet carbenes have an eletron pair in sp?-bybrid orbital whereas the triplet carbenes have one ‘unpaired electron in one sp#-hybrid orbitals and one p-orbital (Figure. 5.5) tok : rol . was Pee o™ on Pe i @ ® Fig. 5.5.(a) Singlet. carbene (0) Triplet carbene These carbenes are distinct spin isomers with diffrent HCH bond angles but not resonance forms which always have the same spin. The non-bonding electrons on either ofthe singlet or triplet ‘arbenes can participate in bond formation with metal atoms. Hoth the singlet and triplet carbenes are monohapto, two-electron ligands that form M=C double bonds. The compounds containing M=—Cidoubie bonds are called metal earbenes. The mec carbenes are classified into rw categories: 4 Fischer and 2. Shcock carbenes. 7 an Cas Ne i i as a 1. Fischer Garbenes ‘The fist carbene complex was made by Fischer and Massbol in 1964. I was prepared by nucleophilic atack of alkyllithium on a earbon atom of hexacarbonyltungsten, W(CO), followed by allylation. (oawacg Fischer carbene The carbon atom in Fischer carbenes is electron deficient, therefore, it is attacked by nucleophiles. For examples, the attack of an amine on the elecuophilic carbon atom of a Fischer carbene results in the displacement ofthe — OR group to give a new carbene ligand. OMe Q : ae ats (00,6 Co ME (00), 6-2 PN Ra (OC) Cr = cK Ph Ph 1 (0)sCr group Ie replaced with the oxygen atom, this reactions is seen to be aminolysis of eters to give amides. . o a = ws (oy X=: 005 ap Fen, 00,000 on = . a Dre ron — DE Fen gon Ph * Ph " ‘his reaction is favourable because nitrogen is not as electronegative as oxygen and its x donating ability exceeds that of oxygen. ‘The addition of carbon nucleophiles or alkenes forms metallacycles wich can break down to @ ‘carbene and an alkeneOrganometallic and Bioinorganic Chemisty : ACh (OO),Cr Ph “SoMe Ph R . 2 (oc)scr oom + (OOscr—= CC Ph ome Ina Fischer carbene a singlet carbene [Figure 5.6 ()] containing a heteroatom such 2s 0. N donates its lone pair of electrons from sp™-hybrid orbital othe metal to form a o-bond and an empty otbital on carbene accepts electron density fom filed metal dx orbital to form metal-carbon Aouble bond (Figure. 5,6 (b)] The Fischer carbenes are characterized by middle to late transition metals in low oxidation states having x accepors ligands such 2s OO and x dono: ligands such 2s -OMe or NM, onthe carbene carbon. The electropilcty af the carbon atom bound tothe metal inthese carbons can be explained as: The significant electronegative ie wanstion metals have d-orbitals at ower energy than the carbon p orbitals. As result the electron density of orbital i largely localized on the metal atom, Conversely the vacant x orbital is mainly located on carbon arom whichis, therefore, attacked bythe rucleopiles because direct M «- C donations only partly compensated by M -> C backdonation. ole Vole oe dg “S Sean @ o oO Coe or ocM = c% <> oc— Mh Sp Sp Fig 86 (a) Singlet carbine (b) Fischer carbine ‘The electron deficient Fischer carbene is affected by the presence ofthe lone pair(s) of eletrons ‘nits donor substituents such as —OR because electron pair from filled p-orbitals of oxygen atom ‘may also be donated to empty carbon p-orbital af carbene to form catbon-oxygen double bond. This Indicates hat the metal dx and filled p orbital of OR compete for bonding to carbene carbon 3s shown in figure 57, ~} ‘All, Cate, Cae, Allee, Ali, Aland Bu, 3-ene Comper se ‘The competetion between the M—C and C—O bonds may lead to the resonance structures Figure. 5.8) pork pe Mec — tie’ Nr SR @ o i:58, ‘The pr—psbond between Cand 0 atoms is stronger than the dx prbond between metal and carbon of carbene because symmetry and size of combining p-orbitals are same. ‘The X-ray studies has shown that M—Cond is long and C—O bond is short. The MC bond is shorter than expected for single MC bond and itis longer than the expected M--C double bond, ‘This indicates that the MC bond order is berween 1 and 2. This supports the structure show in Figure 5.4 (6). ‘carbene ligand of Fischer carbene can undergo oxidative cleavage with reagents such a err ‘ammonium nitrate (CAN), dimethy| sulphoride (DMSO) or pyridine N-oxide or even with ato give ‘ketone. 50 LM OM, est (00,M— Cai ° Cee 09M (MesCCH,)sTa=CC + CMe, + 2L5¢1 ‘eve, Schrock carbene onan ear tansiton metals high oxidation states, non nace igands coordinated tothe mel and non-edonatng substcuents on carbon. Resonance pir (ig. 59) uk R dees asciek ype arene Q, te NR, J" ee oN PlgsS 8Sermdlcabene ns isinecaiis ini SADs In a Schrock carbene the «wo orbitals (one sp? and one p-orbital) on triplet carbene each containing one electron overlap with two metal d-orbitals each containing one electron to form two covalent bonds as shown in Fig. 5.10, Bach MC carbene bond is polarized soas to put negative (5-) charge on carbon atom bound to metal because carbon atom is more electronegative than metal leading to a nucleophilic character (ce, susceptible to attack by electrophile carbene earbon). The nucleophilic character of a Schrock carhene is shown inthe following reaction: M=c a (19 ~Cp)2MeTa— CH + AlMey —> (n® Cp). MeTa*—CHAI"Mes, (n° Cp), MeTi = CH + Me, Sift; —+ [(n* ~Cp)2MeTi (CH,SiMes)]" + Br ‘Alene metathesis reaction is also an important reaction of Schrock Carbenes, Q Q Me, Sonal sec —> a> ree Scr aZ (NM a7 "A +H,C=CH(CMes) “This reaction proceeds through a four membered ring including the metal tom. A Schrock carbene als reacts wth ketone ike wit (PhP = CH) reagent. H H = SacX +1Npst Nos Te =, TAO), — op ‘Tebbe's Reagent “The Schrock carbene Op; = CH i a highly nucleophilic carbene complex. The protected form ofthis carbene scl theTebbe's reagent (Figure 5.11) Tebbe's reagents formed by the reaction of Cpa TiCh, with AlMe, as shown below: aan Oe my Aig ae KC Fs cond Yale Fig. 5.11, ‘Tebbe'sreagentis an example of abridging carbene. This reagent gives product similar to given by the wilting reagent. Wiig reagent PhP = CH converts only the keto and aldehyde groups to > CH, group. But the Tebbe’s reagent converts >C=0 group of aldehydes, ketones as well as o ° I 1 i) R—C—OR,R—C—NRy,R—C_OH{to > CH, group. CH + Phy! (omg)512 Organosétli and Biainoreanic Chemistry Tie mga toe Me Aw en T= Ce engl eiemacee | ase sete hai apm eas a = Corti SalMer eps Ti —cth, 7 Then \ Ro. \ cm. gomet #Catio Some other reactions of Tebbe's reagent are: 0. MeO: o “Tebbes reagent Meos “OX CH Meo: ‘ome Meo: ‘ome OMe OMe 2 0 vues 9 reine Wo SSE hoe le Whore Ay _titesreapt >, AYN eee, ay I ¥ LS | ‘Ali, Carbs, Caibye, Allene, Ally, Ally and Buta, 3-icoe Comets 13 Insertion Reaction Sina wo cbene + CR, 0 abo behaves as abe a how seo reactions or cramp oy Foo &. i See? 8, cote gate c0 oc ‘cp cof | Nop R R (€0},Co— CofC), “5 (0c), Cafe OHO R Carbenes Intermediate Between Fischer and Schrock Types ‘These are the carbenes which have properties intermediate between that of the Fischer and Schrock carbenes, because they react both with electropiles such as SO or HY and with inuleopiles such as CO or CNR. One of the most studied carbene is an osmium complex Ci(NO\P,P)Os = CH, which cn be synthesised as shown in he fllawing reaction: PPh ont ont o OcHNOYEP FE CUNOYER,)08—CH, = YO8— Cty a" Phy a ° cugsoy rh P), 6s LcH; — caqwoyerhPosf 8-0 cH Comparison between Fischer and Schrock Carbenes 1. In Fischer carbenes the middle to late transition metals in low oxidation states are present ‘whereas in Schrock carbenes the early transition metals igh oxidation states ar present. 12, inVischercarbenes the carbene is electron deficient, atacked by nucleophiles and stabilized byheteroatam or phenyl group wheteasin Schrockcarbenes the carbene carbon i electron rich, attacked by electrophile and destabilized by hetero atoms. 3. Fischer carbenes usually obey 18e rule whereas Schrock cabenes do not. 4, In Fischer carbenes the free carbene is singlet whereas in Schrock carbenes the fee carbene istrplet514 se “= Onsmoniilié and Bioinorganic Chemisty 5, In Fischer carbenes the M —C bond is relaively weak and has low rotational barrier (10-15-k) mol") whereas in Schrock earbenes MC bond is relatively strong and has high rotational barrier (60 ~ 100 kJ mol”), Metal Carbynes ‘The carbyne or allylidyne ligands have the general formula CH or CR. The metal carbynes are also classified a : 1. Fischer and 2. Schrock cazbynes, In Fischer carbynes, the carbyne ligands are mondhapto three electron donor ligands, stir to the nitrosyl ligand with a pair of electrons in an sp, hybrid orbital and single electron in ap orbital (either p, or p, orbital) and are bound tothe metal by an M==C triple bond. The carbyne ligand ina Fischer carbyne is doublet. An electron pair from sp-hybrid orbital ofthe doublet carbyne is donated ‘to an empty d-orbital ofthe metal to form a ebond. A single electron ina p-orbital overlaps with a orbital having a single electron to form a bond. The second bond between the metal and the carbyne carbon results from donation of an electron pair fom a filled -orbital of metal atom to an empty p-orbital of carbyne carbon Fig. 5.12 a—) 55" Fla:S:12 Fister Catone, Fischer earbyne was ftst synthesised by Fischer from th reaction of Fischer carbene with boron swialide BX, ome Coom=cg + 2BKy —+ [(OC),M = CR]" BK + BX2(OMe) co X(OO},M = CR + BX i 0 ,co M= Cr, Mo, W 7 X= 1,Br,1 1 xSM=Sc—R Allg, Carbon, Carine, Allene, Allyne, Alb and But, 3iene Complees 545 % ‘ +\P + (OC); M: BY flee CP a LOC), M= CRI” BK; ay X (00), “eo In this reaction, frst the Lewis acid attacks the oxygen, the basic ste of the carbene, Subsequently, the intermediate loses a CO ligand followed by a halogen coordination in a postion trans to the carbyne ligand. After Fischer, Schrock also synthesised a carbyne with an early transition meta in high oxidation states. @ H V7 o& R Nal Ta=c— ay mac’ eh wer Ae me al ‘t me? Rome GN Cp, ke atta CARs Pas RICH cI a In the Schrock carbynes, the carbyne ligands is a quant (.e., it contains three unpaired lectrons). The quartet carbyne ligand form three covalent bonds (one o and cwo r-bonds) to metal sia ree unpaired electrons as shown in Figure 5.13.516 ae ‘Onanomiallic and BisinarieChonisty ‘The complexes containing the thee ally, carbene and carbyne ligands are also known. For example Me Me Bu NM KH sete, Wy r Neticates ve Vee ‘The Xray spectroscopy shows iat the meta carbon single, dole and tpl bon diane re 225 pm, 194 pm and 178 pm spectively. These data sugges thatthe M-—C bod lenge che is shorer than the analogous single and double bods, These bond lengths are consent ih the WC bond ener of, 2and 3 respectively “he inflared succhngfequny of CO ligand cordinaed to meta ina enbyme compe is Tower thin that of CO cordate othe metal na corresponding carbene comple. POH \/ co 4 ashe, “i mee? Yeo = 1938 en" ‘This indcates that earbyne ligand is a beter electron donor than carbene and helps in whack bonding from M to CO asthe electron density increases on the metal and, therefore, reduces CO infrared suetchingfrequeny. ‘Metal Alkene Complexes Euhylene is one ofthe simplest linear relectron organic compound fhich has &siglé xboi resulting from the interactions oftw 2p obitason its carbon atoms. Interaction of the twop bial results in the formation of one bonding and one antibonding x molecular orbital Relative Energy * (antibonding) 2S Me x (bonding) ‘Allyl Carbene, Caine, Allene Ally, Albian Buta, 3iene Complexes a The antibonding molecular orbital has one nodel plane perpendicular to the internuclear axis whereas the bonding x molecular rbital has no nodal plane-The x-bonding orbital is completely filled which is the HOMO and x” antibonding orbital is unoccupied, which i the LUMO, Probably the frst and most well known alkene complex is Zeise’s salt, KPICIs(C:H,)} that was discovered in 1827. Zelse isolated stable yellow crystals after refluxing alcoholic solution of KaiPtCla]. Zeise's satis rally KCL (C,H,)]- HO containing a water of crpstallizaton.Zeises sale is now made from the reaction of K3{PiCl4] with ethylene. [Pic]? + CH, = CH, 91PC (CHAI +r “The ethylene molecele occupies the fourth coordination ste of the square planar complex with the CC bond axis perpendicala tothe square plane. The four C—H bonds in the ethylene complex are slightly bent away from the metal as shown in Fig. 5.14. Fig.5.14 ‘The C—Cand C—H bonding abitals are of very low energy and the cantibonding orbitals are of very high energy as compared to the metal d-rbitals. But the C—C x bonding and s-anibonding orbitals (HOMO and LUMO respectively) have energies similar to those ofthe metal d-rbitals. For ‘ese’ salt, the best bonding pictures given by the Dewar-Chatt model. According to this rade, the filled orbitals (HOMO) projects toward the metal and donates electrons to an empty d orbit of symmetry of metal to form ebond. At the same time, the empty x" orbitals in ethylene accept electron density back donated by metal (Figure 5.15). This is another example of synergistic effect of donation and racceptance encountered with the CO ligand. Consequently, the ethylene molecule interacts with metal both as a e-donor through Cw orbital and asa x acceptor through the C—C x* orbital. Due to steric interaction withthe adjacent ligands, there is minteaction berween the metal d- and the CC x" orbital i} Sei 0 4 wy Fig: 5.15 Orbital.overlap.according to. Dewar-Chatt Model in.Z sols.