7 R. K. MALIK'S riitramanovs,neoica son, non eax NEWTON CLASSES Enjoys unparalleled reputation for best results in terms of percentage selection www.newtonclasses.net COORDINATION COMPOUNDS [DRILL ASSIGNMENT] CLASS — XII TARGET CBSE 1. Coordination compounds area special clas of compounds that consist ofa central metal atom orion, which i surrounded by ‘oppositely chargecions or neutral molecules in more than ts normal valence. They are aso called complex compounds or simply complexes. 2. Werner's coordination theory in 1893 was the fist attempt to explain the bonding in coordination complexes. Werner was able to explain the nature of bonding in complexes, and he concluded that in complexes the metal shows two different types of valences: imary valences: These are nor-directional, ionizable and satisfied by the negative ions. In modern terms, the complex commonly exists as a positive ion. The primary valence is the number of ehatges onthe complexion In modern terms, t corresponds tothe oxidation state Seconidary valences: These are directions, nonjonizable and satisfied by neutral or negative ions. n modern terms, the ‘numberof secondary valences equals the number of ligand atoms coordinated to the metal. Ths snow called the coordina tion number. dition compounds are formed when stoichiometric amounts of two or mere stable compounds join together Addition com- Pounds are of two types a), Double sats: Those which lose thelr ident in solution, for example, carnal © Complexes: Those which retain their identity in olution for example, cuprammonium lon Important terms (3), Coordination entity s made up of central metal atom or jon bonded toa fixed numberof fons or molecules {Cental metal on isthe central ation that is surounded and coordinately bonded to one or more neutral molecules or ‘negatively charged ions For example inthe complex COIN) Co” represents he central metal lonwhichspeitvely Charged ands coordinately bonded os neutral NH molecules within the coordination sphere Counter ions are the negative ions that are no ar the coordination sphere are called couter ions These are the species that oe written outside the squere bracket, which defines the cotdination sphere af the coordination complex. IMINH Cl, bod Donor atomis the coordinating atom ofthe ligand whichis actually donating election pai tothe cenval metal ion. Ligands ae species (positive, negative or neutral) which donate the electron pair to the central metal atom. Denti refers tothe number of times a ligand bonds toa central metal ion through non-contiguous donor sits. Depending on umber of donor sites, igands canbe classified as unidentate, didentae or muitidentate. Some examples of each types are unidentate: ‘OH C1, H,0. NH, didentateethylenediamene, ovalate ions and multidertate: EDTA, Ambidentate ligands have mare than cone binding sites but bind to the central atom through any one ite at aime. Coordination number is the total numberof ligands attached to the central metal atom ina coordination sphere. Coordination spheres the part ofthe coordination compound which contains the metal torn and the igonds attached to itand it is enclosed in square brackets. Coordination polyhedron isthe spatial arrangement of igand atoms which are directly attached to the central atonvion. Oxidation number of central atom isthe charge i would cary if al the ligands ae removed together with the election pairs that are shared with the central atom. Homoleptic complexes are formed when the metalion inked to only one kind of donor group, Heteroleptic complexes are formed when the metal oni linked to two kinds of donor groups. Office.; 606 , 6" Floor, Hariom Tower, Circular Road, Ranchi-t, Ph.; 0661-2662523, 9635508812, 7546645949 NEWTONCLASSES.NETR. K. MALIK’S NEWTON CLASSES ‘5, Nomenclature of coordination compounds (a) The general rues for writing the formula of mononuclear coordination entities areas follows «+ Ina coordination formula, the central atom sisted fst. ‘Within the coordination sphere, the symbol ofthe metal atom is writen fis followed bythe symbolsformulas ofthe ligands aranged alphabetically according to their names irespectve of the charge present on them, + The formula ofthe entre coordination entity whether charged or nt is enclosed in square brackets. «Ifthe coordination entity is negatively charged, the formbla is preceded by the cationic formula | When ligands are polyatomic, their formulas are enclosed in parentheses. Ligand abbreviations are also enclosed in paren- theses. Polydentate ligands ae als listed alphabetically. When the igand is abbreviated the ist letter ofthe abbreviation Isused te determine the position ofthe ligand in alphabetical oder. +The ligands and the metal within a coordination sphere should be written without o space. {The charge ina coordination entity without a counterion s writen outside the square brackets asa right superscript with the number before the sig, «The cation charges are balanced by the anion charges For naming mononuclear coordination compounds, the following rules are followed: The name of the ligands i listed before the namels of the central atoms). No space i left etween names that refer tothe same coordination entity Ligand names ae iste inthe alphabetical order (multiplicative prefixes indicating the number of ligands are not consi tered in determining that ord). Thisis opposite to that of wrtng a formula Prefixes are used to designate the number ofeach typeof ligand in the complex ion; for example iy t-and ttf the ligand already contains a prefix (e.g. ethylenediamine) or iit isa polydentate ligand then Greek prefixes bir, twakis penta, etc are used instead. For naming the central metal ifthe complex ion isa cation, the meta is named same as the element. For example, Coin a ‘complex ction fs named cobalt and Pt is named platinum fhe complex ton isan anion, the name ofthe metal end with the sufi ate. For some metals, the Latin names are used in the complex anions, for example, Fe is called ferate (not ironate ‘Anionic ligands should end ino Thus, anions that end in” ide"(e.g, chloride), “ae” eg, sulphate, nitrate) and ite" (eg. nitrite) should be changed into do, to and ito, respectively. For neutral ligands, the common name ofthe molecules used, fr example, H,NCH,CH,NH, (ethylenediamine). Important texeeptions include: water called 3s “aqua” ammonia called as amin, carbon monoxide called 35 “carbony, Nz called a ‘dinitrogen’ and O, called as‘dioxyger. «+ The oxidation state ofthe metalis written asthe Roman numeral parentheses, 6. Isomerism Stereoisomerism arises in coordination compounds due tothe difference in arrangement of igandsin the space around the central ‘metal atom. The isomerism in coordination compounds canbe broadly classified into two categories (a) Structural isomerism: These are further of several type, ionization isomerism, cooidination isomerism, hydrate isomerism and linkage isomerism. ‘Linkage somerism is observed in amibidentate ligands. ‘Coordination isomerism arises from interchange of ligands between cationic and anionic entities of diferent metal ions ‘resent in the complex. + Tonization isomerism arises when the counterion becomes ligand and vie versa {= Solvate isomers (hydrate isomers when waters the solvent) dstingush themselves by whether solvent molecule directly bonded tothe metal complex o itis ditectly bonded to the metal en, Stereoisomerism: These are further of two types, geometrical isomerism and optical isomerism. ‘Geometrical isomerism: Ths type of isomerism occurs in disubstituted (heteroleptic) complexes wlth coordination um ‘bers 4 and 6 having square planar and octahedral geometries, respectively It is nat possble for coordination numbers 2and 3 and intevahedral complexes wth coordination number 4, This isomerism can be of two types (i) When the two identical ligands ae adjacent to each othe, the isomer is known 3 (i) When the two identical ligands are onthe opposite side, the isomers known s trans. In octahedral entities such as [MA 8, fr example [Co(NH, (NO; another typeof isomerism exists When there are three ‘donor atoms ofthe same ligand ox Designate the cooidination entities and counter fons in the following coordination compounds: (a) Ky[PYCld, () KyINHCN),] (6) [CHCKNH,) Cl. (€) Kl FeXCN] and (e) INCOM. Solution ‘The coordination entities and counterion areas follows Coordination counter Entity lon. (a) KPRCL) preg? K (oI KINYCNI ica? Kc Ae) CACINHAISICL, CFC) > ce (ad KAlFOICN. rec K (e) (icon) (NiCO,) Noion How many ions per mole of the following complexes are present in thelr solution: (a) (CoCKNM,),}ly (b) [Ag(NH,) Cl (c)[PNH [Pei and ( (PHCIINHICP? Solution ‘The numberof ions pet mole ofthe complexes in the solution can be predicted from thelr made of ionization. should be noted that ‘the species inthe coordination sphere donot ionize. {a} [CoCKNH,)sICl=(CoCKNH,),)* +2CI-(3 mol of ions) {b) (AgINH,),}e1=1AgINH),1"+ Cr @ molofions) {c)PRNH Pcl = (PRINH). + [rc 2 mol oftons) In this both the cationic and anionic part are complexes. 4) (PICl NH), )C1= [PYClNH,),]° + CF (2 mol ofons) FeSO; solution mixed with (NH,)350. Solution in 1:1 molar ratio gives the test of Fe ion, but CuSO, solution mbxed with aqueous ‘ammonia in 14 molar ratio daes net give the test of Cu" ion, Explain why? (NCERT) Solution {htih50g +Fe504 + 60 —* FeS04 NH 504“ 6H0 Vd Ym Mobs cuS04 + ANH, + 5H — [CUM 150, 5H0 ‘mol «mot Tevaunmnocoppen spate Fe50,(NH,)S0,6H,0 and {CuNy4S0, SHO fall under the category of ation compounds with anly one major difference that is FeS0q(NH),S0,6H,0 san exarpieof a double sal, whereas [CuNH))50,5H,0isa coordination compound ‘A double sat is an ation compound thats stable inthe solid state but breaks up int ts consttuent ons inthe dobved state. “These compounds exhibit individual properties of their constituents For example, FeOg(NH,);50, 6H, breaks int Fee NH nd SOF fons in solved state, Hence gives a postive test forFe™ ions ‘A coordination compounds an ation compound which retains sient inthe slid as wellasin the dissolved state. Thus nd ‘ial properties ofthe constituents are lost. The fons present inthe solution of[CuINH)1S0,SH0 are (CuUNH) and SO. Thus, {Cu 150, $H,0 doesnot show the test for Cu™ 2. Explain th two example ach ofthe follwing: Coordination enty.igand, coordination number, coordination polyhdon, homo leptic and heterleptic (WCERT Office.; 606 , 6” Floor, Hariom Tower, Circular Road, Ranchi-1, Ph.: 0861-2662623, 2695608612, 7646846949, NEWTONCLASSES.NETCOORDINATION COMPOUNDS [DRILL ASSIGNMENT] CLASS ~ XII ‘Solution (2) Coordination entity: A coordination entity isan electrically charged radical or species carrying a positive or negative charge. In '3 coordination entity, the central atom or ion is surrounded by a suitable numberof neutral molecules or negative ons called ligands. For example, (i) INiINH,)P* and (Fe(CN),1 are examples of cationic complexes. (i) PXCkJ* and (Ag(CN),1-are examples of anionic complexes. {i}, [NCO and [Co(NH) 1, are examples of neutral complexes. Ligands: The neutral molecules or negatively charged ions that donate 2 pair of electrons to central metal tom in 8 coordina ‘lon entity nd form a coordinate bond with tare known as ligands. For example, NH H;0,CI-, OH Ligands are usualy polar in nature and possess at least one unshared pair of valence electrons ‘Coordination number: The total number of ligands either neural molecules or negative ions) that get attached to the central metal atom in the coordination sphere is called the coordination number ofthe central metal atom, For example {il Inthe complex. K,[Pxlg there ar sx chloride ions attached to Prin the coordination sphere. Therefore, the coordination numberof Pt is 6. i) Sian, in the complex [Ni(NHs)qICl, the coordination number ofthe central atom (Nis 4 because four ammonia (NH) atoms ae attached tot Coordination polyhedron: inthe coordination entity, the igands are directly attached to the central metal atomvon in definite directions in space, thereby giving a definite geometry to i. This spatial arrangement of the igandl atoms which are directly attached tthe central atomv/on is called coordination polyhedron. The generally observed coordination polyhedra ae tetrahe ‘ral square planar, octahedral square pyramidal and trigonal bipyramidal Homoleptie complexes: These are those complexes in which the metal ion i inked to only one type of ligands, For example, ICownt)., (Pec ete Heteroleptic complenes: These are those complexes where the central meta ions linked to more than one kind of ligands. For example, [CoINH,)1, [CoN CIP “8. What is meant by unidentate,didentate and ambidentae ligands? Give two examples fo each. (ncerr) Solution A ligand may contain one or more unshated pats of electrons which are called the dono sites of igands. Now, depending en the number ofthese donor site, igands canbe casified as follows {a} Unidentateigands Ligands with ony ne donor site ae ale unidentate gas, For example, Ny. et 1b) Didentateligandss Ligands hathave two donor sites are called dentate ligands For example (i) Ethane 2dlammine HCH, 0) Oran 08 01 0O™ Hi—G, 00 \o)-Ambidentate ligands: Ligands that can attach themselves to the central metal atom though two diferent stoms ae called mbidetat igands For example 1) NOjand ONO" igends ° Me na Nitro group So -O Nitrite group 10) SeN and NCS" igands Me=SCN Thioeyanato MNCS lothioeyanato 9. Spec the oxidation numbers of the metas in the following coordination enties:() ICotONCNVenls (xc? (CoB fen 16) Kec) (rN) Ch (nce) Solution a) [Co(HONCN)(en))": Let the oxidation state of Co be x. The charge on the complex i +2. Now, x +0 + (-1) +2(0)= +2 => x~ 25 ) (PrCig:Let the oxidation state of Pte x.The charge on the complex -2.Now,x+4(-1) =-2=>x=+2, Office.: 606 , 6" Floor, Hariom Tower, Circular Road, Ranchi-1, Ph. 0861-2662623, 9636608612, 7546846949, NEWTONCLASSES.NETR. K. MALIK’S NEWTON CLASSES {Coffer Let the oxidation state of Co be. The charge onthe complex is-H.Now x +2(-1)+2(0)=41 x 2=41 = ws ‘lFe(CN) Let the oxidation state of Fe be x. The chrge onthe complex Fe(CN)q”Is~3.Now x +6(-1)=-3-9x-6= 33 wad (6) [Cry Lethe oxidation state of Cre The charge onthe complexis 0 Now, + 310)+3(-1)=0=9x—3 0-13. 10. How many lons ate produced from the complex [Co(Nl,ICl; n solution? INCERT) ws m4 3] Solution [@) Theajven complec canbe waten as [CotNHg* +2C1 Thus [ColNHs)" along with two CI tons are produced. 11 The oxidation numberof cobalt in KICo(CO),)s an m8 wweern) Solution (@) We know that CO is a neutral ligand and K caries a charge of +1. Therefore, the complex can be written as K'{Co(CO},). Therefore, the oxidation number of Co the given complex s~1 9.3 NOMENCLATURE OF COORDINATION COMPOUNDS Conceptual Questions 1. Write IUPAC name of the compound [Cr(NH,),NCS] [ZnCl Is this compound colored? Solution Pentaammineisothiocyanato-N-chromium(l) tetrachloridezincatet). ‘The metal lon chromium has incompletely filled d orbitals. Hence, the complexs colored in nature 2. White IUPAC name of [mnercen> con 054 Solution Citethane-12-iamine)obal-simide-j BaS04b vemos Icons, + AgNO, —> Noreaton [ctN,80 + 8 —>No acon {Cont},5040 + AgNO; > Aga veo 13, Lrtnevatous ype of womersms post for corn compounds ging anal of each, (ween) Solution Stereoisomerlsm:|t arises on account of the different positions and arrangements of ligands in the space around the metal on. It Isof the following two types. (9), Geometrical isomerism: This type of isomerism is common in heteroleptie complexes. It arises due to the diferent possible {geometric arrangements ofthe ligands. When two identical groups (igands) occupy adjacent postions, the Isomers called is {and when arranged opposite to each other, the isomer is called tans. For example, oe a7 Snr NS Net ‘isisomer——trans-isomer (0) Optical isomerism: This type of isomerism Is common in octahedral complexes with coordination number ix, invalving one, ‘wo or three symmetrical dentate igands.For example, in (Coten,)* ine exe ‘Structural isomerism: It arses due to the difference in structures of coordination compounds tis of the following types: (a), Linkage isomerism: This type of isomerism s found in complexes that contain ambidentate ligands, For example, Ioan) NO3ICh, [owns (ONOKCI, Yellow form fea orm (b) Coordination lzomerism: Thistype of isomerism arises when the ligands are interchanged between cationic and anionic enti- tes of ferent meta ions present inthe complex For example, (Co(NH,)(Cx(CN)] and [INH [CO{CNI {)lonization isomerism: This type of isomerism arises when a counterion replaces ligand within the coordination sphere ‘Thus, complexes that have the same composition, but furnish different ions when dssolved in water are called ionzaton is- mers. For example [Co(NH,},50,}Br and ICo(NH) 81150, (a) Solvate or hydrate isomerism: Solvte or hydrate isomers have the same compasition but differ in the numberof solvent ‘molecules presents ligands and as free solvent molecules inthe crystal latce. For example, croc, (cryoyscich, 4,0 [cet,0),c1,1024,0 let ‘ue green bark green 114. How many geometrical isomers are possible in the folowing coordination entities? (a) [CACO (h)(CoINH),Cb] Solution {a} For [CHC,0,),, no geometrical isomer is possible a (0, is bidentate ligand, {b) For Co(WH,),Cly, two geometrical isomers are possible. NH, NM vn Me ee oh Fecal Merona ai a | Office.; 606 , 6” Floor, Hariom Tower, Circular Road, Ranchi-1, Ph.: 0861-2662623, 2695608612, 7646846949, NEWTONCLASSES.NETCOORDINATION COMPOUNDS [DRILL ASSIGNMENT] CLASS ~ XII 115. Draw the structures of optical isomers ofa) Cx{C,04))™(b [PtCyfen,} () CHINE Chen Solution (a) iG093"" (o) (PrciyenisP* oe" “Sy io stat OY gy Ly ev (cio Meroe Kon (2) (CNH) ;Cfenn” “or WwW woe 16. Drawall the Isomers (geometrical and optical ofa) [CoCl (ena, b) [CofNH)Cfen);},() [CotNH),Cl fen” Solution 7 {a} [CoCl,ent In total three isomers are possible. trans CaClen"womer- opal inactive 2s |C0C, en), wamer apna active non superimpose miror mages) {b)_(CoINH,)Cfen)": In total two geometrical tomers ate possible. Out ofthese the trans isomer is optically inactive, whereas rere cease q+ 2+ ad ne Ses Naa “Ty ye Ae i reiomeris optical active Minor pon superimpesae ‘rer images) {c)_[Co(NH)C,(en:In total, four eine Isomers are possible. Office.: 606 , 6" Floor, Hariom Tower, Circular Road, Ranchi-1, Ph. 0861-2662623, 9636608612, 7546846949, NEWTONCLASSES.NETK. MALIK'S NEWTON CLASSES a, ST" ay an NI NI wen LIN, Ie snchenwnemneninst en 117, Write all the geometrical isomers of XtNH)8CHpyI] and how many of these wil exhibit optical isomers? Solution The geometrical isomers are possible as follows: ee KHLINYEY, FES, From these isomers, none will exhibit optical somerism. Tetrahedral complexes rarely show optical isomerization. They do so only in the presence of unsymmetrical chelating agents. Textbook Exercises 1. Define and give one example of each ofthe following: (a linkage isomerism, () optical isomerism, (c) geometrical somerisr, Solution {a}, Linkage isomerism: This type of isomerism i found in complexes that contain ambidentate ligands. For example, ICowne)(NO3IC!, {otN)5 ONONIt, Yellow orm Fes form (@) Optical isomerism: This typeof isomerism arses in chiral molecules tomers are mitior mages of each other and are non- superimposable. For example, {Co(or) PSL St fy SS (entry Minor (neo) (6) Geometrical isomerism: This type of isomerism i common in heteroleptic complexes (Complexes having mare than one type ‘of igand).itarises due to the afferent possible geometric arrangements ofthe ligands. For example, (Coten) (Ds) Nre4 UN JN 2. What the typeof isomerism shown by the rs(ethylenediamine)cobaltl) on? Draw the structures. Solution ‘Optical somerism is shown by the trisfethyleneciamine)cobalt(l) on. The structures of optical isomers are: Office.; 606 , 6” Floor, Hariom Tower, Circular Road, Ranchi-1, Ph.: 0861-2662623, 2695608612, 7646846949, NEWTONCLASSES.NETCOORDINATION COMPOUNDS [DRILL ASSIGNMENT] CLASS ~ XII Icoten?* (here) 3. Which ofthe folowing complexes wll show optical Ixomerlsm: MABXY (tetrahedra), MABXY (square planar), MA;B;X, (octahedral? Solution ‘The complexes MABK (tetrahedral) and MA;8;X, octahedral show optical somerism since they contain chiral centers. Square planar ‘complexes do not show optical isomerism since they contain a plane of symmetry. 4 trans-dichlorobis(ethylenediamine)cobaltl) ion does not exhibit optical lzomerism while the cs isomer does, Explain, Solution ‘The cisisomer does not have a plane of symmetry, sot shows optical isomerism, whereas the tran omer has a plane of symmetry and 0 cannot exhibit optical isomerism. a ale S | A 9.5 BONDING IN COORDINATION COMPOUNDS Conceptual Questions 1, Account for the fact that [Ni(CO),) has tetrahedral geometry whereas [Ni(CN}4]" has square planar geometry. Solution (a) In [NXCO}qL the electronic configuration of Ni(0) = 3a 4s? u “ we=20 [(W[N[N] A] 4] [A Inthe presence of CO (soni ligand) paring of electrons takes place Nios hybicaesd [NN] TU] TVA wwicong [NTN Because ofthe sp* hybridization, the complex acquires t (b) In NKCN)4 the electronic configuration of Nit) = 324s! w sion [ATTA] Inthe presence of CN” strong fd ligand) pang of lectons i Niwnidsp? hybridize) [NV] NNN 606 , 6 Floor, Hariom Tower, Circular Road, Ranchi-1, Ph.: 0651-2662623, 9836608812, 7546846949 NEWTONCLASSES.NETR. K. MALIK’S NEWTON CLASSES wena? [NNT [A]xx) [rex] [xxx] Four cron pars erated by case ofthe dp hybridization the complex acquires square planar geomet. 2. What ies file spiting? Solution According o crystal eld theory, the interaction of the central metal tomvon ad the ligand inthe complex purely electrostatic Nevtalas wll a negatively charged igands can donate an electron pio the cenzal metal atorvion anagenerte an elec field bpproxmately equal toa et of negative point charges around te cenzal metal atonvien Hence this interaction of drt the Central metal tom/on wth the lgands gives ise to cyal el. na fre atom athe ve deals are degenerate that shave the ‘me energy Ina complex however this degeneracy scestroyed and the oral spt int wo groups of orb, andi having diferent energies Tis eect which aures te piting of degenerate orbital scaled ery ets or ene evel iting. This vin of orbs into two groups is based upon the orientation ofthelobes with respect coordinates: (a) Thee,setof orbitals comes dad gf orials which areal orbitals tats have thei obes along the aes The'ein P and the configuration f tye A, A T rooney ETT COINS) ‘The sixvacant sp? hybrid orbitals will be occupied by the lone par of electrons given by si NH, molecules. The hybridization 's @4sp" (forming an inner orbital complex). The complex has octahedral geometry and is diamagnetic as it has no unpaired electrons, 10. Mention the geometrical shapes of the complexes involving the following hybrd orbital: (a) sp () dsp) asp? ive an example ofeach ofthe above. Solution (a) The geometrical shape ofthe complexes involving sp hybridizations tetrahedral and the example is 2ntNH,)*. (} The geometica shape of the complexes involving sp” hybridization is square planar and the example is [NICND >. [e)_ The geometrical shape of the complexes involving sp hybridization i octahedral and the example is [CoF Explain on the bass of valence bond theory that [NKCN),|* ion with square planar structure i diamagnetic andthe [NIC lon with tetrahedral geometry s paramagnetic (WceRT Solution In NI(CN1,P*, Nis inthe +2 oxidation state, that i, In 3d configuration, Office.: 606 , 6" Floor, Hariom Tower, Circular Road, Ranchi-1, Ph. 0861-2662623, 9636608612, 7546846949, NEWTONCLASSES.NETR. K. MALIK'S NEWTON CLASSES ™ « won (Puy) tL Co “There are four CN" ons, s0 the complex can ether have a tetrahedral geometry or a squae planar geometry. Since CN" lon isa ‘strong fleld ligand, it causes the pairing of unpaired 3d electrons. Ni** ion then undergoes dsp” hybridization and forms a complex ‘wth square planar geometry Since allelecons are pare, the complex lamagnetic. Pi “ ” wena [ALATA x] box] foxhexl J] 7 9 ieaton Four eeton pa donated by Toure tons In case of [NICI,}*", CI” ion is @ weak field ligand. Therefore, it does not lead to the pairing of unpaired 3d electrons and Ni?" under- {00s 5° bybrdzation formes complexwith tetrahedral geomety and since there are two unpled electrons present complex te paramagnetic x “« ° ona? [8A ex] fexhexex] eo ‘o!brdaton our election pais donated by 12, (NICIGP*is paramagnetic whereas NiCO),)Is diamagnetic though both are tetrahedral. Why? (weer) Solution ‘Though both [Nici and [Ni(CO),] are tetrahedral their magnetic characters are diferent. Tiss due toa difference inthe nature ‘ofligands. In {NICF™, Nisin +2 oxidation state. CI”isa weak field igand and it does not cause the paring of unpaired 3d electrons. Hence, [NCI Is paramagnetic. ~ ° won [(NTRTNT 14) I In (CO}y Nisin zero oxidation sate that thasa configuration of 3 42. Osa stong fel igand, Therefore, causes the paling of unpaired 3 electrons and itcauses the 4s electrons to shift tothe 3d orbital. This gives rise to 5p" hybridization. Since no "npalre electrons are present inthis case, [Ni(CO),]is diamagnetic Md “ “ wolNIN TNT tit] Cx) CT 1. [FeltO)g*i strongly paramagnetic whereas [F(CN),]™ Is weakly paramagnetic. Explain Solution In both [FetH,0)g)* and [Fe(CN),)™, Fe exstsin the +3 oxidation state, thats n 3e° configuration. uM rem [t[ tT] t]t] Since CN” isa strong field igand, causes the paring of unpaired electrons. Therefore, there isonly one unpaired electron left inthe orbital, oo Fed) @25p*hybricized)| AU] 10 | Magnetic moment, = Va 2) = JAie)= V3 =1732 6M (On the other hand, HO ie weak fed ligand. Therefore, it cannot cause the paifng of electrons. This means thatthe number of Unpaied electronsis5. Office.; 606 , 6” Floor, Hariom Tower, Circular Road, Ranchi-1, Ph.: 0861-2662623, 2695608612, 7646846949, NEWTONCLASSES.NETCOORDINATION COMPOUNDS [DRILL ASSIGNMENT] CLASS - XII w= nin+2) = Y5(5+2) = 35 =5.916 BM Thus, itis evden that [Fe(H;O),)is stronaly paramagnetic while (Fe(CNIg"Is weakly paramagneuc. 14, Explain (Cos an inne orital complex whereas [NUN an outer orbital complex. wcent Solution In{Co(NH,,), the oxidation state of Cos +3 and electronic configuration is 34%, NH being a strong fil igand causes the paring of electrons, therefore Coll] undergoes ds hybridization, Hence its an Inner orbital comple. uw * ” con [U4] ott (sp? rybridaes) [| 1 4 In INUQWH) the oxidation state of Niis +2 and electronic causes pairing of electrons leaving only one {3d orbital empty. Thus it cannot undergo ds hybriizatio Nii undergoes sp%e hybridization instead of dsp’ and forms an outer orbital complex. Py “ won [TNT] PT) TI © iQ (spd? hybridized) [14] NAV CT 15. Predict the number of unpaired electonsin the square plana PiCNI fon, wcen) Solution In this comple, Ptisin the +2 oxidation state It forms a square planar structure. This means that it undergoes dip? hybrldeation, Now the electronic configuration of Pr 2) is Sa se (winnie) CCN” being a strong field ligand causes the paring of unpaired electrons. Hence, there are ne unpaired electrons in [PCN 16. The hexaaquamanganesel fon contains five unpaired electrons, while the hexacyanido ion contains only one unpalred electron. Explain using erystal fel theory. (NCERT) Solution (MAnthO1P Pantera ‘Mn in the +2 oxidation state, ‘Mn isin the #2 oxidation state ‘The electronic configuration is 34° ‘The electronic configuration is 3% The crystal field is octahedral. Water is @ weak field igand The crystal eld Is octahedral. Cyanide is strong fel ligand (ue, Ay < Py Therefore, the arengement ofthe electrons in (ie de (cura? + 44,0 (Geren) (b) When Kclis added [cuthog?* + acl” —s tcuchs?~ + 440 (argh green In both these cases, the weak fl ligand waters replaced by the and CIlons. 19. Whats the coordination entity formed when excess of aqueous KCN Is added to an aqueous solution of copper sulphate? Why It ‘that no precipitate of copper sulphide s obtained when H,S() i passed through this solution? (NCERT) 2USO4(aq) + 10 KCN(aq) > 2KICUICN, aq) + 2K;S04(0q)+ (CN), [Cuth,O)g* + ACN” [CulCN,? + 44,0 ‘Thus, the coordination entity formed Inthe process i [Cu(CN),)*. This complex is ver stable, which does not ionize to give Cu** ions Hence, Cu" lons are not precipitated when H,5(g)s passed through the solution, 20. Discuss the nature of bonding inthe following coordination entities onthe bass of valence bond theory: (a FetCNI I b Fel, (@1Co(G Ody a) oF cen) Solution (a), InGFtCN Fe exits in the +2 oxdation state with electronic configuration 3 x “ reo (NIT tt] 0) [AS CN" Isa strong fed ligand, it causes the pairing ofthe unpaired 3d electrons. Since there are sb igands around the central ‘metal in, the most feasible hybridization i 5p FeAn spPhybriized) [YN oa ‘The six electron pais from CN” fons occupy the six hybrid dspPorbtals. Then, ua racna [WINNS be) febobol ‘Sx pairs flectros om EN ons Hence, the geometry af the complex is octahedral and the complex is dlamagnetic (a there ae no unpaired electrons) In F ef), the oxdation state of Fe is +3 and the electronic configuration Is 3d rem [Tt] t1*1t] C] lf = There are 6 ions. Thu, Itcan undergo 2p? or spd hybridization. ASF” Isa weak fil ligand, it does not cause the paring ofthe elections inthe 3d orbital. Hence, the most feasible hybridization is spa Office.; 606 , 6” Floor, Hariom Tower, Circular Road, Ranchi-1, Ph.: 0861-2662623, 2695608612, 7646846949, NEWTONCLASSES.NETCOORDINATION COMPOUNDS [DRILL ASSIGNMENT] CLASS ~ XII u “ ” “ Fett p'rybraes) (FT P1414) ] COI aL pene we Ferg ie eam fee] ‘Select pis rom six F- fons Hence, the geometry ofthe complexis octahedral (@)In{Co{C,0,);}*, cobalt exists inthe +3 oxidation state and the electronic configuration is 3c ws “ » “4 com [NEATH 14). ‘Oxalate sa weak field gan Therefore, it cannot cause the pairing ofthe: scons. Therefore Co™* undergoes sp'd? hybridization “ “ Cott (sp' hybridizes) [1 ‘The six electron pairs from the three oxalate ions (oxalate ani ligand) occupy these sp?d* orbitals. x “ “ reocour [Nt] t] Ft] t] ex) I Hence, the geometry of the complex s octahedra. (qn {CoF,}, cobalt exists in the +3 oxidation stateand the electronic configuration w o ” com [Nt] t] 414) I [Again fluoride ion ls wesk field ligand. It cannot cause the paling ofthe 3d electrons As a result, the Co!” ion will undergo sp'@ hybridization, Cont (sp? hybidizeed [TU] tora [WV cs fe ‘Siero pis from mF fons Hence, the geometry ofthe complexis octahedral and itis paramagnetic. 2), Draw a diagram to show the splitting of d orbitals in an octahedral crystal fed (NcERT) Solution ‘The spitting ofthe d orbitals in an octahedra field takes pace insucha way that da_,:, dj: experience risen energy and form the level, while d,,d,,and dy experience a fallin energy and form thet, level Fig. 9.2. 606 , 6 Floor, Hariom Tower, Circular Road, Ranchi-1, Ph.: 0651-2662623, 9836608812, 7546846949 NEWTONCLASSES.NETR. K. MALIK’S NEWTON CLASSES a amir | “eal hy Ge det) satel Figure9.2 22. Whats spectrochemical series? Explain the diference between weak eld and strong feld ligands (ncerr) Solution A spectrochemical series i the arrangement of common ligands inthe increasing order oftheir crystal field stabilization energy (CFSE values FeBr [ [| 40) ‘Simtecron pas donate by sx WH, Hoan Since [NiINH,)P* is pd hybridized, the structure octahedral SS. What are the salient features of crystal field theory? Solution _Afterthe failure ofthe valence bond theory the crystal field theory was proposed around 1950, This theory s based on the assump tlon that theligands are considered to be point charges which interact electrostaically with the central mena atonvion. tis assumed ‘thatthe fved orbitals of the isolated metal atomvion tobe symmetriealy arranged and are degenerate (.e. have same energy).This degeneracy is maintained til symmetrical fel ofthe charges surrounds them; but when the negative Feld is due to elther anionic ligands (or due tothe polarity of neutral ligands like NH,) i becomes symmetiical an the degenerate d oritals split up into two parts depending upon the field generated by ligands. This spitting ofd orbitals isthe basis of crystal eld theory {6 Explain the crystal eld spliting of d orbitals by the ligands in octahedral complexes with coordination number sh Solution Let us consider how the d orbitals split in an octahedral field of ligands with coordination number 6. In octahedral complexes, the ‘metal ion i atthe center of the octahedron andthe sixligands represented by point charges ie atthe sixcorners along the three axes xyand2zas shown Fig. 93, Office.; 606 , 6” Floor, Hariom Tower, Circular Road, Ranchi-1, Ph.: 0861-2662623, 2695608612, 7646846949, NEWTONCLASSES.NETCOORDINATION COMPOUNDS [DRILL ASSIGNMENT] CLASS ~ XII Figure 9.3 Letus suppose that the metalion IM™Jhas singled electron id! configuration, example Ton in [TF eamplix on ton when there aeno ligands, the electron ean occupy any one ofthe dorbitas because al are af same energy and recalled degen: erate orbitals. However, n the octahedral complex, MX, al the five d orbitals ae not of same energy. The phenomenon of spitting of dotbitalsin an octahedral complex ilustated in Fig. 94 bey dele) ‘O88, 1 S08, | © Se dt) state Figure 9.4 Spliting of¢ orbitals nan octahedral complex. Inthe fee metalion allthe fvedoritals are degenerate State Fig. 94). When the sic ligands approach the central metal cation along the anes they exert an electrostatic force of repusion onthe outer d electrons thats thed electrons are epeled by the lone parsofthellgands “This epulson raises the energy ofthe degenerate d orbitals to give five excited degenerate orbitals State, Fig, 84) Since thelobes of d.. and d,._,» orbital (, set of orbitals directly in the path ofthe approaching ligands the elections in these orbitals experience greater repulsion Gxerted by the electron clouds ofthe ligands than that experienced bythe elecvonsin the dy and dort (se of orbit als which aredretedin space between the xy andz axes Hence, under the influence ofthe approaching ligands the obits dy and dz ate raised energy, whereas the orbitals dd, and d, are lowered in energy relative tothe excied d levee State Fig. 94), 7 Both {ColNH,),"* and {CoFy are octahedral complexes. Use crystal field theory to predict the magnetic nature of the two complexes, Solution In(CotNtye™", ohas oxidation state, and its electronic configuration is 30 coum [N] t] tt] t Since NH, isastrong field ligand and > Pthe pairing of electrons occursandthe electronic configurations Since alelectrons are paired the complex sciamagneti. in (ofa) the oxidation state of Co is +3, adits electronic configuration is 3d as above. Since Fis a weak field ligand and Ay

Na,(AglS,0,)n1+ NaBr 6. Discuss briefly giving an example in each case the role of coordination compounds in (a) biological system and (b) medicinal chemistry (NCERT) Solution {a} Mary biologically important natural compounds exst a coordinated complexes For example, Chlorophyll the green pigments in plants central tothe photosynthesis process, is a complex compound of Mg Haemoglobin, the red pigment of blood which acts as oxygen cari, isa complex compound of Fe. Vitamin By chemically called cyanocobalamine isa complex compound of Co™. ‘Other biological important compounds with coordinated metal ions ae the enzymes such as carboxypeptidaseA and carbonic anhydrase (catalyst of biological systems). Complexing agents are used for removal of metal posoning A platinum complex [PtINH,),C] known as csplatin has been used in cancer therapy. There is growing intrest inthe use of chelate therapy in medicinal chemistry. The common example is the treatment of problem caused by the presence of metasin toxic proportions in animal and plant systems For example, excess ‘of copper and iron are removed by chelating ligands D-penicilamine and desferioxime Bthrough the formation of coordination ‘compounds. EDTA s used inthe teatment of lead poisoning, Textbook Exercises 1. Give an example each role of coordination compounds in (a) metallurgical process and(b) catalysis Solution (a) Complex formation techniques ae used forthe extraction of metas such as gold and silver. For example, sive extracted from its ores by the cyanide process. In this proces, silver pastes into solution with formation of complex Na(AgiCN) [Ag;S + 4NaCN —> 2NaIAQICN)3] + Nays ‘The solution containing the silver complex removed and treated with zinc dust when siver precipitates out 2NalAafCN3ll + Zn > Nap [2n{CNg)+2AQ Simiaty, the cyanide process i used forthe extraction of gold. Its based onthe fact that gold dissolves in aqueous potassium Office.: 606 , 6" Floor, Hariom Tower, Circular Road, Ranchi-1, Ph. 0861-2662623, 9636608612, 7546846949, NEWTONCLASSES.NETR. K. MALIK’S NEWTON CLASSES cyanide solution in the presence of atmospheric oxygen to form a soluble cyanide complex: “4hu + BKCN + H;0 + Op(fromair) ——> 4KIAUICNI3) + 4KOH ‘The solution containing gold complex filtered and treated with zinc dust to get gol, 2KTAUICN),}+ Zn > KylZnICN))+2AU Similaty, purification of metals can also be achieved through formation and subsequent decomposition of their coordination ‘compounds. For example, impure nickel s converted to IN(CO}4, which is decomposed to get pure nickel Certain coordination compounds at a5 catalysts for ifferent reactions. For example, pentacarbony/cobalil) acts as catalyst in the hydrogenation of alkenes. During hydrogenation, Col) is oxidized to Coll). The coordination compounds are used 35, hhomagenous catalysts fora varety of reactions in solution For example, Wilkinson’ catalyst (Ph,P),RHCl chlordotistripheryt phosphinehodiur)] i used as a homogeneous catalyst in hydrogenation of alkenes. These are also used as heterogeneous catalyst in many reactions. For example, Zegler-Natta catalyst (solution of titanium tetrachloride an tritkylaluminium) is used for polymerization of olefins 2. What is the significance of coordination compounds in analytical chemistry? Solution ‘The complex formation method is used in qualitative scheme of analysis. The familar color reactions given by metal ons with 2 umber of igands (especialy chelating ligands) asa result of formation of coordination entities form the basisfor their detection and fstimation by classical and instcurnental methods of analysis. Some common reagents used are EDTA, DMG (dimethyiglyoxime), cupron, e-nitroso-B naphthol, etc A numberof basic radicals ae confirmed by converting them into suitable complexes Office.; 606 , 6” Floor, Hariom Tower, Circular Road, Ranchi-1, Ph.: 0861-2662623, 2695608612, 7646846949, NEWTONCLASSES.NET