Unit co-ordination Com pens frase tis Us YOU be abe to: | qpecil te posuats of Werner theory of co-ordination {kor he meaning ofthe terms: co-ordination ‘ecentity, central ligand, co-ordination number, onan pabmedron, oxidation number, homolopte op rete 1, kan he nies of nomenclature of co-ordination compounds; {wf be formulas and names of mononuclear co. ordination |y_ a ifret types of isomerism in co-ordination compounds; |+nktad the nature of bonding in co-ordination compounds in temsclthe Valence Bond and Crystal Field Theories; |s-ban stably of co-ordination compounds; | sprecie the importance and applcat ‘pads cur dey today te, wt 0 €2-ranation dag tttination compounds refer to a particular a compounds in which the central atom or ion, aie 2 eta is surrounded by cluster of ions or tmeyt These compounds are widely present in meats Plants, ete. These compounds have many rat applications like estimation of hardness in [lentes plant treatment, electroplating, textile Mas Pounds a W) B80, + Al(80), + 24,0, *Poalgonamo Gii) (NH),80, + FeSO, + 64,0 FeSO, (NH,),SO,6H,0 (Mes st (iv) CuSO, + 4NH, — Cus0,4NH, (Termine oper mgt) (v) Fe(CN), + 4KCN —> Fe(CN),4KCN (Pot. ferrocyanide) These addition compounds fall into two categories, namely; double salts and co-ordination compounds. (a) Double Salts. These are the addition compounds which are stable in the solid state but break up into its constituents in dissolved state. In such compounds the individual properties ofthe constituents Scanned with CamScannercarnal ost, For ution of ite (KC example, an aqueous solute. arnallite (KCL MgCl, 6H1,0) shows the properties 1° Mgr and Ch ieee : i re the ___ (6) Co-ordination Compounds: These RT tng addition compounds which retain their identity Ot gy Solid as well as in the dissolved state. In 5 fear ‘ually a individual properties of the constituents cea samofeopper sulphate @ On mixing aqueous solution PPP cop blue with aqueous solution an cou coloured solution haar? eresence of Cu? solution does not show he immonium ions; bt instead it nta e ombina- [CucNHt which are forme ecules. tion of Gu ion and four Om os. mixing aqueous (i) Similarly, in definite [Fe(CN), J is solutions of KCN tions. ‘The sale ofthe complex ions are called complex compounds or co-ordinate compounds. The ier7 coordination is eoined for such addition compoun Fees tn all such compounds the central metal ion forms. dative or co-ordinate bonds with species surrounding it ; The branch of inorganic chemistry’ that deals with the study of co-ordination compounds is known as co-ordination chemistry. 2 Zmenber ‘Some common difference between double salts 1.The constituent simple salts may or may not be in equimolar proportions, 2. The complex ion does not in aqueous solu- Mateo sili chloride (CotNH,),] Cl, Parente Seca {Co(NH,),H,OICl, co cake iltc chloride | (Co(NH),CICl, | ty obi clr trans-(Co(NH,),Cl,1C! tie chloride cis-[Co[NH,],C1,JCl | In this unit, we shall st principles of the chemistry of gy n° the by. the nature of these compounds wunttion «by to bonding in these compounds anit” Sein, applications of these compounds 4 "°° any fa" shall also briefly study the chemise from compounds which contain metal aa bon WERNER'S THEO} CO-ORDINATION ony Uy; The early study of i merely dealt with the atten To oe oy and structure of hydrated double sail the carnallite, ete. Though, the earig ("Ma during the era could provide a satigfn "deny of the formation and properties of s." S offered no adequate explanation of theo molecules with ions to form complex ec" in Table 9.1. The chemists wondera atoms in these complexes were connec, and the possible effect of the arcs properties of the complexes, : The first successful theory ex properties of co-ordination compounds ine structure was proposed by Alfred Werner ot long before sophisticated techniques wera! the concepts of electronic structure were chemical system. In recognisation ef his vot was awarded nobel prize in 1913. The briet 2 of his theory are: ” __ @) Metals have two types of linkages (aly ie., primary and secondary linkages. The pr linkages are satisfied by the negative ions whens secondary linkages may be satisfied either by thn tons or by neutral molecules. The primary valet ionisable valencies whereas the secondary valencia non-ionisable valencies, According to the modern concept about pe fed to each Ngement on Scanned with CamScannerple, ‘yy the prima; pores hen addition ofammenia iran fC Jex compound CoC oy gs a comple nd CoCl,. 6NH,, ee tne arsine yer it oxime PGs the secondary valencies are satishiea by oot gneremoyecules. Thus, every metal atom pug A cis ey metal atom can have i) ee sndary valencies about ti A ire projected in the oor oncies are Projected in th 4 characteristic the central atom, Space about th, iy ‘manner that the = je a insuch a manner that these assign a define Fire 0 he co-ordination compound, ae ont? example, in CoCl,.6NH,, the six see ° F onday For @ arranged in an octahedral fashion jes 0 ; tee central metal ion. On the other hand, itthere 7 valencies as in the case of 7 rave either a tetrahedral on oan : Se “ an Not only the neutral molecules be co-ordinated jecentral atom but ions may also be co-ordinated in woth pion. When an ion replaces a neutral molecule 7, eoordination sphere, it loses its clectrovatent ‘orecer and gets attached to the central ion by non- sisable linkage. For example, the co-ordination compounds od (NH,),Br]*SO,?" and [Co(NH,),SO,]*Br- have the ‘ane formula, In the former, as the SO, ion is present jutside the co-ordination sphere it gives a white precpitate with BaCl,, When this ion replaces the Br- ju (in the latter) in the co-ordination sphere it loses it ‘onic character ie., no precipitates are obtained with BaCly O00 You Keou? ‘The ions present outside the co-ordination spherelentity_ | are called counter ions. The above point is also illustrated (Table 9.4) in formation of complex of Pt(IV) ion with ammonia and Cr ion. aa ares nee ASSIGNMENT OF STRUCTURE ON THE BASIS OF WERNER’S THEORY Werner, on the basis of his auxiliary a heory, assigned structural formula to a number o ordination compounds. For instance, cobaltic a onbines with NH, in different stoichiometric ratios to 449, Yield a number of compounds are listed in Table 9.1. In all the compounds the co-ordination number of cobalt is ‘ix but these differ from each other in respect of the ions oF neutral molecules present in the co-ordination sphere, Structure of CoCl,.6NEH, ith alo, The complex is found to give white precipitate With AgNO, indicating the presenee of onisable chlorine ‘tom(s), Quantitative analysis reveals that AgCl Precipitates corresponding, three chloride ions are chia ned indicating the presence of three ionisable orine atoms. Thus, chlorine atoms are bonded to cobalt by three primary valencies NH, ay NZ HN (i) The solution of the complex does not give test for Co ions indicating that cobalt and NH, molecules constitute the co-ordination sphere, whereas the neutral ammonia molecules satisfy the secondary valencies. De You Kuowe? ‘The six co-ordinated compound can have three Possible structures. Among these the octahedral structure is more favourable owing to minimum clectronic repulsions. (@) planar hexagon (©) octahedral. () trigonal prism ‘This is supported by the fact that Werner isolated only | two isomers for this compound which is + aia acre The Scanned with CamScanneri drat 'x co-ordinated complese has an octahed sna emp “ the complex may be formulated ‘ICL, and is pictorially represented ab For the sake of distinction the primary are shown in dotted lines whereas the seconda"y are in bold lines, On the basis of similar discussion, the of other cobalt complexes with ammonia T° iencies Chlorine atom with bold and dotted line indicates that it satisfies both the primary as well as secondary Werner also explained successfully the structure of ammines of Platinum (II). *e2ing point of - 9, 0373 ince the depressi ution. $i Pression in fog, 0 the effective molality of egy 2% py, theatre thw fete lay ag m = 20372 or Lag = 002 Since the molality incre therefore the number of fons for th from 15, "Lin motu ™ he atructuire, (CONTE), CLIC ing 1. Onthe basis ofthe following obyep, aqueous solutions, assign soegy metals in the following compar”? Formula (@ PAC, ANH, (i) NiCl, 6H,0 (iii) PtCl, 2HC1 a (iv) CoC], ANH, : (v) PtCl,.2NH, a 2, Arrange the following in the ordey sp electrical conductivity: : @(CoNH, CLIC Gi) KPrc), (i) NINH, ),Cl] Cv) K, racy L@4 G6 Gi) (6 W4 2 (iii) <(W) < (ii) < (iv). A WORK OF LAXMI PUBLICATIONS (P) Lip, DEFINITIONS OF SOME IMPOR TANT TERMS PERTAINING 10 CO-ORDINATION COMPOUNDS (4) CO-ORDINATION COMPOUND A co-ordination compound contain acta atom or cation which is surrounded by asi memes anions or neutral molecules and ws Toad 2 identity in solutions as well as in slid st ofspecie nt further, in these compounds, the nish its elect erring the central metal atom she! (Cui got OF covaleney. For exampl it is surtging’'st® electrovalency of copper ist! unded by four NH, molecules. These io metal Scanned with CamScannerated group or donor} 8 (or are alled. ligands. “* hed tg tye etl ion compound enero Ga cottons. For example, ONLAINS ong © eee, contains (CUNE) 1 2* com outst 4 contains IAg(CN).|- oo, Plex ion ‘al VCNs1, contains [Ag(NH,),)* Mplex ion, Gili let contains (Cr(CN), Somntex ion i wows [ce niu) ‘(NHL ), ys itive comple IN ENTITY o NATIO) (COMPLEX) rept on isa electrically charge Bg com ying positive or negative char he i ror ion is surrounded by a suitablenet eer rolecules oF Negative ions Ceattgg ale num. Ne gacatron examples are ligands), He 2, 7 Seyi a [Count + (PRO, Laon), nl {Fe(C,0,)sI INKCO),, (Count, or soe plex ion carrying a positive MCh) ne conve complex, the one wi harge is ation} ith a negati ailel Aeted anionic complex and the on. ative Sei Sed a neutral complex, e with no eo gnTRAL ATOM/ION oe nati i In co-ordination ent ity, the atom/ion to which a or ter of ions/groups are bound in a definite geo. ef arangement around it, is called the central tel Fin the examples given in (B), the stom 0 2+ Cot, Pt, Agt, Fee, F central Seon are: Ni, COU, BO Gee » Fe, Ni and fe respectively. LIGANDS The neutral molecules or ions that surround siemelal ion in a complex are known as ligands iderived from the Latin word ligare meaning to bind). [ignds are normally polar molecules such as NH, jL0soranions such as Cl, OP, CN’, ete., which have itleast one unshared pair of valence electrons. They seattached to the central metal ion by a co-ordinate or Jive bond, The atom in the ligand which is involved ‘nthe formation of co-ordinate bond with central metal ttom is called co-ordinating atom or donor atom. A dinar atom may contain one or more unshared pair of cketrons which are known as donor site(s) of the ligand. Aligand may contain one or more donor sites. Depend- ing upon the number of donor sites, the ligands may be dhssified as: unidentate: With one donor site. di or bidentate: With two donor sites. ter or tridentate: With three donor sites. 'd radicat With four donor sites, catalan oe WA ioe ly atten more than, 1 alled mul fone donor sites are Aongy A be matey iantate ligands, Winer site a eg fata atom ean have only one “le can have more than one donor of the are given the vain gth® common exampt " 82 fap a multidentat ig ENTICL 1 SUTYy. Ucanpg) © ND CHELATION (CHELATING hen a multide on iates toa metal en a ringtike trond nlate ligand simultaneously thalat, ON We tetas ccc eee a ligand, ring and the |i « obtained. It is called a Tita and the ligand is ienoon ; Dumber irom Greek word chele mensiny eating ote oF Such ligating groupe meaning elaw). The ligand Sroups indicate the denticity jome common e, 8 fellowes MMO examples of chelation are shown HC: 7 : cH nt HAN, Nike a” \yecn, te tT i a” Ny-cH, (@ (Pecyeny, prea acne i a 4X GN CH Ny7 Nyc, H, K, (©) [Ptitrien)} A didentate ligand is symmetrical if the two co-ordinating atoms are the same. In case the co-ordinating atoms are different it is unsymmetrical. Vatue Basep Question 1 Chelating ligands form a cyclic structure on their coordination to the metal ic EDTA is one such ligand. ‘The use of such reactions involving chelation are being widely used in chelation therapy. “Answer the following questions: A) What sul form of EDTA ond what its dentiiy Gi) As a student of chemistry, what do 00 understand dy the erm chelation theron? Explain guofing one example. What values are agents? efletedin the use ofsuch chelating Scanned with CamScanneraceate i 9.2. Som (C,H,)5P os Not No, NE No,- NH; H.NCSNH, Common Unidentate e cyang oxo Peroxo, carbonaty Phosphing Ritrosy, carbony] sulphato itro oF nitritgs thiocyanate op isothioeyanatgs acetato Pyridine (py) sulphido thiosulphato nitrato sulphito triphenyl phosphine thiocarbonyl nitrosonium nitronium imido nitrato amido thiourea (tu) Scanned with CamScannersalneatiarine 4,2: oxalate ion slacetonate pimethylelyoxime ion Glycinato 1, 10 phenanthroline or ortho-phenanthroline Diethylene triamine or N-2-aminoethyD|-1, 2-ethanediamine 2, 2: 6, 2"-terpyridine One ny ‘ietnylene t tetraamine CH)NH(CHa)2NHa NN’ -yie(2aminaethyD by srtcH SH, — Scanned with CamScannerEthylenediamine triacetate ion acetate ion S-hydroxyquinolinato J bed ean a \o=e: a ‘complex with water. This is because when chelation cffectis called © membered S-membered chelates “™™® *F° Ethylenediamine totra- Ortho-phenanthroline (ph) ‘@ Chelating ligands form more stable complexes than the monodentate ligands. For example, the complex ofethylenediammine with cobalt is more stable than the ICo(Ht,0),}?* + 3en —> [Co(en),]* + 6NH, increase and the process becomes more favourable. This lnsaturaton in the ing 27198 double bond o + _cHr,co? ot, N~oy1,c00. " eo GO 1, -8— 4,c00 on} —ony Carbonate ion In occurs entropy Li, p Answer giving specific ram, |, What is the oxidation num. * of the following? IMber of ev @ ([PLONH) J Cl, (ii) Ni(CO), 5. What is the co-ordinati atom in the following? @ (Pt(NH,), Cl) Cl (ii) Be EDTA Gn) tay 2) 6. How many moles of Cl- ions are Hy mole of each of the following? @ MOH), CLICL Gi Kip Gi) Pt NH), Cl) CL 7. Which of the following GO Fe tp, ODN hy on number, bes Toy Kime, 4 . Go) Crest with AgNO, solution?» °° ite Pr! ( [Co Py), (H,0), C1) cL () (Co y,) H,0 Cl.) H,0 8. What is the EAN of central metal the following complexes? atom in ad @K, (Fe(CN),] (OK, Facey Gii) NIH Cl, Go) (Cuemyp 9, Whatis the oxidation number ofionin theta complexes? @ Fe(CO), Gii) K,{Fe(CN).) (ii) FelC,0))* (iv) Fe[FACN), 10. Designate the co-ordination entities and come ions in the co-ordination compounds : K,[Fe(CN)gi K,{Co(CN)) INi(CO),}; K,{PEC\, 11. Specify the oxidation numbers of the metasiat following co-ordination entities: (@ [Co(CNYH,O}(en),]* (i) [PCY (ii) (CrCl(NH,)5. (iv) (CoBr{en)]'- Scanned with CamScannerTeun owed +h , ii) 6 0) ine) Lm i) 3 mo 1S lg ehlorde ators Dretent i ionte sphere eco i 98 (0) 86. 1g 5 Gi + 3 + 2. go Gt ign entites are: ne dina coordi (CCN) 4]: INUCO)4] ond 1PICIP at pac ins outside co-ordination sphere) ter io! ‘ou nm fl . Fe ng counterion) and K* fone respectively, BM 2 4900+ Se TARA PUBLICATIONS (P) LTD, S{ENCLATURE OF NOIORDINATION COMPOUNDS ynclature is important in Co-ordinatio: Nomenclaty ofthe need to have an unambiguous ett jeecrbing formulas and writing systematic sas ot oetarly when dealing with isomers, The js5% POT names adopted for co-ordination entities ot on the recommendations of the International ae “pure and Applied Chemistry (TUPAC), (ni FO! OF MONONUCLEAR CO-ORDINATION ENTITIES (©) There Of the til be 20 space bet o-ornin anes ad the weet the don eeraination ayaa the meta ne names When the format ithin a entity tr be hanged Souter tony the ena ithont thas an he aquare brakes tR* i indicus th ct ated out © Number hefner Teh nu ott before he “Perveript y MAT pore the wna ete with Wit) The charge os UELO)g Pane, OF ample, he catin charge of the aha cationts i Mion (as Balanced by the (G OF MONO. YUNDS “ORDINATION As the co-ordinati -ordination com can be sufficiently complicate) ens (oF complexes) Suggested by the TUPAC ta naa te" ral rales we toname Beneral rules (R) for writing the hee ompounds, The formulae and names of (a) Ifthe compound is ion mentioned first followed by the u examples are discussed below: Example 1, K,[PACl,) is named as potassium hezachloroplatinate (IV), the name of cation is name of anion. A few (Cation) (Anion) Example 2. (Co(NH,),CIICl, is named as penta-amminechlorocobalt (III) chloride (Cation) (Anion) (b) For the non-ionic complexes the name o| complex is written in one word. For example: [Ni(NH,),Cl, is named as tetraamminedichloronickel (1D). Rule-Il, Naming of co-ordination sphere. naming the complex, the names of the ligands are writ first followed by the name of the central ion. 7 ‘oxidation number of the central metal atom is expres by Roman numeral in parentheses just after the nam the central metal atom. ‘The sequence of nam co-ordination sphere is summed up 28: ‘The formula of a compound is a shorthand tool sajtoprovide basic information about the constitution ‘Fhe compound in a concise and convenient, manner. Nownuclear co-ordination entities contain a single ‘eal metal atom. The following rules are applied while siting the formulas: (i) The central atom is listed first. (ii) The ligands are then listed in alphabetical order. The placement of a ligand in the list does not depend on its charge. (ii) Polydentate ligands are also listed alphabeti- cally, In case of abbreviated ligand, the first letter of the abbreviation is used to determine the position of the ligand in the alphabetical order. — Scanned with CamScannerme of central J (ramet! [it tom [este ert For example in the complex ion, [Co(NH,)! = co-ordination sphere is named as Hexa-amminee™ (IID ion. Similarly, for the co-ordination sphere is ‘named (IID ion. Rule-IIl. ‘Naming of ligands. ‘The central m* jon ina complex is surrounded or neutral ligands. ON), the ion [Fe(C complex jon IFe(CN ‘as Hexa-cya) etal i by positive or negative (a) For the ligands carry he name has a characteristic ending wot 0", A few example are quoted below: a CH,COO- Acetato NCS" N* Nitrido i Tsothiocyanato : : NH; Amido NO," Nitro ‘§% Sulphido or thio Cl Chlorido 0% Oxo H- Hydrido HS- Hydrogen Ny Azido CHO" Methovo sulphido CN-Cyano (0,2 Peraxo 0, Carbonato 0° Oxalato OH" Hydroxo SO, Sulphato NH® Imido SCN- Thiocyanato PD Rmenbes ——___——- ‘According to 2004 TUPAC ‘recommendations, the ‘name of ligands like F-, CI-, Br-, I" (whose name end in |etters -ide) are named as fluorido, chlorido, bromido, ‘etc. instead of fluoro, chloro, bromo, etc. ‘Similarly, CN- should be named as cyanido though the name cyano is still used. Hydrogen as ligand is always taken as anionic (hydride) and is named hydrido. (8) For the ligands carrying a positive charge, the name of the ligand has a characteristic ending of “ium”. For example, NO," Nitronium (NH,NH,)* Hydrazinium ‘NO* Nitrosonium, (6) For neutral ligands istic endit tone characteristic ending NH,CH,CH,NH, Ethylenediamine* HN Pyridine The following examples are, how however, excepti 1,0 Aquo™*, NO Nitrosyl, coca NH, Ammine, CO Carbonyl, “The name cthane-l, 2dlanine shld ogy 1e nas el, di to ethylendiamine. should be used in preference **H,0 is also named as aqua these days, Co pret, such, For example, Cyl Phenyl C,H,N Pyridine 2 Thi PCH) Triphenylphosp) : Rule-IV. Order of ya to old conventions, the nan ™™% ligands surrounding the ee order, (i) Negative i) New», separating them with a hyp same kind present in the nt Pir tie! names are written in ona. "tina alphabetical order. For eat" th ICo(NH,),CKNO, C1, the nga chloro, nitro (negative ligany ligand). Thus, the complex 1p named as chloronitrotet,” chloride. eae According to the late. names of ligands surronmie 8% atom are written in algn ptt "nt preference irrespective of pi" negative or neutral. For era httter ii” (Co(NH,),CKINO,), the ligands ane te ammine, chloro and nitro. 1 mages prefixes di, tri, etc., are not to be tins determining the alphabetical order, "4. In the present text the been followed. ad TUPAC rm, ‘The oldest convention of writing - ligands was Metal atom, neutral, ‘trae ligand. ao 2. According to 1990 recommendat changed to Metal atom, eee ligand. If there were a number of ligands of the uw ‘category (e.g., negative), it was reeommendedit them alphabetically according to theft sb oftheir formulae, eg, Brandl, ifbotharepret these will be placed in the order Br Lites! H,O and NH, both were present, H,0wilixis! first and then NH,. 8. The latest IUPAC recommendations of | have suggested to list the formulas of te i= alphabetically according to their namesire#™ | of the nature of charge on them. } Rule-V. Numerical prefixes 0 iti number of ligands, The number ofeach ki! ail Scanned with CamScanner~gxes di, ti tetra, ete. Tt should efi ilar monodentate ligands = “ complex then we shall write attacent need ty pag ee eg. Insta OF Ne rd ira'e'ot FORD Which teria Fat Som #8 the Be gained. Ifthe ligand is complex, such (Ce renames Fore (estes (Conn, i [ pager, etistondiaminettraacetan {one pseemtro i oh egedti ropented three or four times then oe Moun ea to FO rk ese used followed by alternative modes sey ee ame wath egs Oi parentheses. Itis illustrated when Tink as loge or ce, ie wh enh ise am ish O i written as nitrite, ns MM ate Mytamine) cobaltID chloride —gomerys Gannon ot isomers. Geo) Visomers are na “cH, CH,NHCHACHNHiINOd, is thetermecisor tans designating mite Es erm cis or trans designating he pation cee lating the position of a tically active ee selec e designated bythe es giethytenctriamin?) cobalt(II) nitrate symbol (+) or d fi sonore hen mono tate ligands The Totatory, For exessolen aay 884 or far owe” repeated, the word bis is I a =“ o! used dk, {Ix(C,0,),}; Potassium (4) trioxalatoirid ralatoiridate (Ut. ne eae yf on Tt is because if di is used, it becomes Rule-X. Abbreviati reviations for complicated ee jecause 4 oftge which 8 different compound. ‘mol A padingofname of the central atom, eT Complicated ligands are us ‘Eeations and neutral molecules have abbrev ed by abbreviations. Some en at ring termination but in the case of anionic Seer nce “a vate” is attached to the name of ses the SU ‘om. For example, the names of some ‘anionic complexes are: ethylenediamine pyridine acetylacetonate oxalate or a aaa OY RNIN Potassium tel Nay(Colos),] is named as Sodium tris(oxalato) cobaltate(II). K,{Fe(ON) is named as Potassium hexacyanoferrate(IID). in writing the names of an acid, the e ued For example: HPX(CN),] is named as Hexacyanoplatinic (ID) acid. Rule-VII. Oxidation state of c atom or ion. The oxidation state of the central metal tum or ion is designated by a Roman numeral (1, 1, Tete) in the bracket at the end of the name of the mplex without a gap between the two. It is illustrated ‘nthe names given in the Table 9.5. ent or Naming of Rule-VIIL Point of attachm ‘When a ligand 9° cosrdinsté anbidentate ligands- J is named as tracyanonickelate(0). urea nding is entral metal Scanned with CamScannerps maple 4 : roy (Pec) 1a Na{CrOF s0.K0BF a1 KOs 12 (Clen 1010, 2 oa CY ICHCNY 24 gy, S0, AR PACNY, 2% NCO CHIN), 2.NaJSF) 2 laco,) eC a.m Ra Tor, nds onthe basis ofthese upg,» ination - uPAC Names of Some Comp) is Tetracarbonyinickel (0) Hexaamminceobaltty «4, Pentaamminehoridcai gn Tetreaguediheiecromg te Potasium tetaevaNEickelag, ng, Triamminetrnitrocobateqn, Hesaammineplatinumyty) chan Potassium hexseyanoterriggny Triammintrioqoehrominner, ; Diamminedichloridoplatinun, loridg Potassium tistosalatoeraqy, Pentaamminecarbonatocshaiy Diamminesilver(D chloride Didlowbidetivertininita, | Tetraammineehloridonitrocobay Potassium trioxalatoiridate(tt) Mercurie ttrathioeyanatocobataty loride W ch, Nitrate tetrachloroplatinate(t!) Sodium tetrafluorooxochromate(ty) Potassium tetrafluoroborate( ttl) Potassium Pentachloridonitridoosmateyy) Bis(ethylenediammineMiftuorocobaluti) te. Tetraamminedichloridoplatinum(tyy ‘Tetraamminedichlorido cobalt(III) hexacyanochromate(III) Diamminesilver(1) sulphate Ferric hexacyanoferrate(II) | Pentaamminechromium(III) -whydroxopentaamminechromium(II1) chloride Scanned with CamScannerLithium tetrahydridoalumi Tro | 44 problems Based Nomenclature Formulate the compound tetraam. 1 (I) chloride. pe lex ion) [CoCl * we [CoClGH,0XNH,),} on the complex ion. the te of cobalt + charge on the ligands ‘yidation stat eigelet2 se ral groups and no char; are neutral groups and carry no charge. 110. charge each) oar ‘on one anion =~ 1 (Charge on c0 is we ymplex cation = + 2 Charly two anions will neutralise the charge of the aac formula of the given compound is (CoCKE,OVNH,),JCL,. Explain, why the word bis is used while ving the name of ligands like (CH,) NH, though it is a ronadentate ligand. Gsation. Although methylamine is a monodentate ligand, wth word bis or tris is used when two or three ligands are preent, Ibis because if the words di or tri are used then zethylamine o trimethylamine would mean (CH,),NH and (Ci) N respectively and not CH,NH,. For example, (Cu(CH,NH,),C1,] is named as Dichloro bis-(methy- ‘unine) copper (II). Aqueous solution of copper sulphate (blue) ‘$0es a green precipitates with aq. KF and a bright green ‘lution with aqueous KCI. Explain these experimental results. ‘lution. Aqueous copper sulphate solution contains ‘CaH,0),"*fons which is blue in colour. On reaction with Witforms, (Cu(H,0),)% + 4 — [CuF,P + 41,0 ot Potassium bis (dithiooxa to-8, $1), nickelate (It) Ammonium hexathioeynnatoplatinate ayy Mm (IIL) hexacyanoferrate (ff) Pentanquohydroxoaluminium ({1t) ion Bis (acetylacetonate) oxovanadium (t¥) __ Tetrafluoro eu Precipitates. On reactio is water soluble, (Cutt, Prate (II) has a m with KCI it eodaora aur and cena chloride which, 6 ace : scr — cucr,P-+ 44,0 Selie What happens when exces added to aqueous CuSO, solution? Why ist that re oon of copper sulphide is obtained when H,Sia)is prot y the solution? ne Solution. {Cu(H,0),) +4CN- As CN isa strong ligand it form: i ee \S a highly stable ions this on passing H,S, the weak li S* cannot replace CN- ion. m= — [cue —aeee NOERIT INTEXT QUESTIONS ERTINTEXT QUESTIONS WERT Write the formutos for the ftowing co-ordination compounds: (j) Tetraamminediaquacobalt (TI) chloride ii) Potassium tetracyanonickelate (I) (iii) Tris(ethane-1,2-diammine) chromium (IID chloride (iv) Amminebromidochloridonitrito-N-platinate (T) (v) Dichloridobis(ethane-1,2-diammine) platinum (TV) nitrate (vi) Iron (II) hexacyanoferrate (ID). Solution. (@ [CoNH,)) (HOC, (i) KNICN),] Géii) (Cr(en),JCl, (iv) [Pt (NHL) BrCl (NO, (0) [PtCl,fen),10NO,), (vi) Fe(Fe(CN) gy Write the IUPAC names of the following ‘eo-ordination compounds: Cl, (ICoNH,,ICly — IColNHCt i (iv) KfFelC,0)) oO ea wi) Puce, cH Scanned with CamScannerao RC,0)) (a FeChy Gin) DNKNEL),JCly (Kacy —— (i) CaylFe(CN,) OAC, (ei) (CxCL(H,O)JNO, (ICACINO, NH, NO, KPa, pp ira) 5. Wite OPAC name of “emma, 'Caea),CLONOy, i “ISB, 1961; rp, (i cr po ‘sam 1993) 4 None t filloving c-ordination compounds using TPAC. pte aiceney* Gi) (Mat HH,0),)* ma hie, wv) Haleoengyy ~ MSR, 999) Give TPAC namey 4 ( IMnA1,0,\96)"e HD (Cofonyicy,, | Mis yg F& K 199, orgie (ICON ACO jo) tng 7. Using TUPAG following: 4) Tetrabytroxori (i) Hexa amin Cy (iit) Diammin dich ie (i) Pentaammineniets yi" (0) Teteabromcupate yi (vi) Potassium tetrachloride (vi) Potassium trioeany, 7 (citi) Hexaammineptatin,y ‘, (éx) Potassium tetra anni (x) Pentaammine nitrity 40}. chat 8 Write the formulas fr tng ‘compounds: (@) Tetraamineaquachlorig, (6) Potassium tetrahydroy (© Potassium trioralatoauminae i (@ Dichlordobis (ethane, 20 (€) Tetracarbonylnickel (9), : (NCERT Testbooh 9, Write the TUPAC nam, co-ordination compounds: OPAC GH Kero, " (ii) [Col fen),IC1 (jy) [Con C0 (v) HgICo(SCN),} (NCERT Textbook Solved 10, Write the formulae ofthe falling compas ( Pentaamminechlorocobalt (Ill) ) Lithium tetrahydroaluminate (II) (iii) Bis (acetylacetonato) oxovanadium (¥) (jv) Dichloridoplatinum (IV) tetrachloride. nate (11) (Ur Norms y, rete 4) cba eaiteate Shi Solved eS of the fs ig 1. (i) In correct names are (i), (ii) and (i). 2 () KJFe(ONO),), (ii) [PtCl,|PCl,) (iii) [Vo(acac),] (iv) K,f2n(0H),) () Na {Fe(CN),NOS). Scanned with CamScannerin istne amine EE y nttte sae “te 4, anictelate ID 0 Fig ta onto cluminate (TD eat remium (IID ion, (i) hexoague si Peeemineen or) hexacyanoferrate (Ii ian richet OD chloride. (0) hex er fecnt tn) ton, (Wt ealeluns hexacyano. ate Mcgamminecabat HD Mori vigieniridochromium (IID) nitrate, 9 uadlentoridonitrocobalt (11) nitrate far enarchordopttinete Pima) cho “ ‘oD. at OT ginechloridocobolt HID horde, Fe toa grotenediamine) nitrtocobalt iD oridobis i cehromium (IID) ion, (i) herr eae eloride. 0) mercuric. tetra. ich gltate (D, (0) potassium dicarbo. proeo" rosocobattate (ID. on reese sulphate, (i potesiam cae r ealenctanind il de) Potton tent seat D, (2) examine ‘carbonatocobalt (IIT) ‘alo i (8), J* Gi) (CONH,) JSO, (ii) [PONH,) Cl, i He ag (NOQ)FP* (v) (CuBr gP- (vi) refbace) to ecrONa] (viii) [PUNH),}* (ix) K[Ni(CN),) (p 1CANEE)NORIP* 4. formula of he coordination compounds are: ide. (i [COUNH,)(H,OVCUCL, i Kf2n(0 (i) K{AUC,0) fi) (CoCl,(erd* (@) [Ni(CO),) 4. i Diaminechloridonitrito-N’platinum (1D {i Potassium trioxalatochromate (IID (aii) Dichloridobis (ethane-I, 2-diamine) cobalt (II) chloride (iv) Pentaaminecarbonatocobalt (III) chloride (o) Mercury tetrathiocyanatocobaltate (III) (@ICONH,) CIF* (ii) LifALH). (ii) [V(acac),0] (iv) [PCl,]{PtCl,]. WORK OF LAXMI PUBLICATIONS (P) LTD. __ a ISOMERISM IN CO-ORDINA- TION COMPOUNDS he two or more chemical compounds with I chemical formula but different structures are b tromerin i and the phenomenon is known as phenomenon is not restricted to carbon ompouruds only bits ae found ra aay Muna fund, hooghn ess requenty, : atom or ion, Some 3 pes re shown be depen "x upon the ponition nnd seranoemen at "round the metal ion. Ino mand arrangement of ligands iment et mers can be broadly classified steroeinen 2% catsxorien: ntructural isomers and forthe mers. Each of these kinds of sean t tb-divided an described below an Octahedral ‘Tetrshedrst LN ge NH, HN Square-planar (A) Structural isomers (B) Stereo isomers 1, Ionisation isomers 2, Co-ordination isomers 3. Linkage isomers 4, Hydrate isomers 5. Co-ordination-position isomerism 6, Polymerisation isomerism ‘Let us now briefly discuss the different types of isomers. 1.Geometrical isomers 2.Optical isomers ‘A. STRUCTURAL ISOMERISM. These are the isomers which have different arrangement of | ligands around the central metal atom. ‘The various types of structural isomers are being discussed as follows: 1. Ionisation Isomerism. Compounds which ave same composition but yield different onsin slut Scanned with CamScannerIn this type of jon isomers. ee foninatiomnterchange of groups between there is an called ‘ {the metal ion and the ions are isomer here 0 the eedination ‘compounds have he 0-0 fence, the two f utside this ree fer with respect to Ue onic Rroups, sae Ferma but For example, ) sulphate, [Col bromecstafmomer of red coloured pe aaa ee it) bromide, ICo(NH,),SO, IB. 7 [Co(NH,),80,]"Br- Pentaamminesulphato cobnlt11P) bromide ontaammino- jolet coloured ps : (NHI,),BrISO,, is an ntaamminesu- ICo(NH,),Br]*S0,2- and Tentanmminebrom shalt ID rulphate ! (red) , (wioten in aqueous solutions, gives ‘The violet compound, in aqueous s: : / recipitate with BaCl, and not with AgNO, solution | Gereas the red compound gives a precipitate with ‘AgNO, solution and not with BaCl, solution. Some other examples are: [PUNH,),Cl,] Br, and [Pt(NH,),Br,] Cl, ICo(NH,), NO,] SO, and [Co(NH,),S0,] NO, [Co(NH,), Br] C,0, and [Co(NH,),C,0,] Br [Co(NH,), CI(NO,)] Cl and (Co(NH,),Cl,] NO, [Cr(NH,), SO,] Br and [Cr(NH,),Br] SO,. 2. Co-ordination Isomerism. This type of isomerism is shown by compounds in which both cation as well as anion are complexes, Here, the isomers differ as a result of different groups being co-ordinated about @ particular co-ordination centre. It is shown by the compounds in which cation as well as anion are complexes. For example, CoH, ),NCHON),] and [Cr(NH,)g]ICo(CN), In the above example, cobalt occurs as a cation in the first and anion in the second whereas the situation of chromium is reversed. Other examples of this type are cited below: (Co(NH,)ICHCN),) and [Cr(NH,),]ICo(CN),] (CNH), }ICH(C,0,)) and {CrNH, [Co(C,0,),] (Cofen),]ICHON),) and (Cr(en),]ICo(CN)g (Cu(NH,),PtCI,] and (PLNH,),}{Cucl,] (PUNH,),JPECI,) and (PICINE, JIPICL (NE) (CrONH,)JICH(CNS),) and (Cr) F (CNS),}IOr0NH) (CNS). 3. Linkage Isomerism, Thi ‘is ty i esult from two possible ways of attach ee oot ittachment of a ligand to the central atom. Por gy to the metal either throug Pl, it 0 Brouping N= orthroy, 0 RN Open (4-O-N = O) grouping. Foy [CoNT),NO,IG1, 8 Pentoamminenieg “Ic cobalt(II) chlorite P ‘The unidentat, central atom throu, called ambidentat are: it ligands 18h two Doss ite ligands hich, dong ome ni men nitro (NOY) and nity eyano (—CN) ana ‘is0eyang thioeyanato CNS) ang Some more examples of linkags (Cr(H,0),SCN}? ang (Cre, (NEP Y),CotNO,) No, 2” to ong, isor 3 and aig (yo, [Mn(CO),SCN} ana tinge 2% 4. Solvate Isomerism, This arises because of capability of watar aoe ina variety of ways, inside and outside he sphere to give a number of hydrate example, there are three hydrant formula CrCl,.6H,0 as shown belon, (CrH,0).1 Cl,, (creH,0) Hexaaquo ihe Chg Pentaay rif chromium(I1) chromivent chloride chloride Monch; (violet) (blue green) and [Cr(H,0),CL] C1.2H,0 ‘Tetraaquodichlorido chromium(III) chloride dihydrate (green) Other examples of hydrate isomerism are: (Co(NH,), (H,0) CIICL, and {Co(NH) (Co(NH,), (HO), ClIBr, and (Co(NH,), (H,0)01 Bre (Co(NH,), (H,0) Cl] Br, and [Co(NH),BrJC18l [Co(en),(H,0) Cl] Cl, and [Co(en),Cl,}CLH0 [Cr(Py), (HO), CL] Cl and [Cr (Py), (HOY Scanned with CamScannerA 1 re < Seo wtta.c, 80, cv a’ | CotNH),C1|80, | | gn isomerism. This is not a true pete to denote compound having same ree Nl Dut different molecular formulae, For al a piy,Cl,| and (PUNH,) IIPtCH| oak NOs and [CNH ICO(NO, Solved Problem WGERT INTEXT QUESTION ee Give evidence that [Co(NH,),CUSO, and ),ICl are ionisation isomers. are dissolved in water, they give different Sa eae can be tested by adding AgNO, ‘and BaCl, solution. Both one by one when cr = vye counter ions, a White ppt. will be obtained with AgN( es ee SO} ions are the counter ions, a white ppt. will ne with BaCl, solution. 1, Which type of isomerism is shown by the following airs ? “i CaN) (NO,KCDI Cl and [CotNH,)Chy) NO, (i) [CoNH,),(CN)g1 [CaN y{OND and [Co(NH,),(CN)JICHNH,XC! MH (ii) (Ma(CO) (SCN) and IaiCONN A (iv) (PUNE) JIPECI,] and Pu ee 2 Write the structural formula of ¢o-0 of (Co(en),][Cr(CN),)- ties and the hit differ ty in the MOF UFOMDY abe 1 “ one on dination numb oe tha Number fie oe grea ‘The two important typow nf yo ree described as follows: nee : I Geometrical Stereoisomerism arises in due to the difference in geon ligands around the central ligands occupy position ad cis-form and if these are op called trans-form. Thus, this ki Teferred to as cis-trans isomerism. This type of isomerism co-ordination complexes with a co-dina of 4 and 6. (a) Isomerism in Complexes with Co- ordination Number 4. These complexes can ether have a tetrahedral or a square planar geometry, The tetrahedral complexes do not show goometriel isomerism because the relative positions of the atoms with respect to each other will be the same. The square planar complexes on the other hand stow this kind of isomerism as follows: Teomer: he ion. If the mnt to ind of isomeris oe Tr CIS AND TRANSPOSITIONS IN 3QU PCP Nica cadet Scanned with CamScannerjerism. This type of oa Foam ea eomplexex nd revula mailed by bre Tigands. For example, + (ionisation ti fjntation Gi) enordination ty Unbnge 2 The other coon ort ancient The other ervordination teamer is (Crten) ICCD yar A WORK OF Axo PORTICO . Pasa 80, JBLICATIONS (P) LED. ie ot } | on yl ° 7 Scowty,eh 80, [aes Na ton Isomerism. This is not a true i payne to denote compound having same 1. Geometrical tis <2 gta but diferent molecular formulae, For nic : oP ycls and (PUNE) JPACI, i fcant\NO2 and (Co(NH,),]ICo(NO,),. il ve e ‘This TL Oomerism arises in the en-ordination due to the difference Mn geometrical arra: ligands around the central ion. If the ligands occupy position adjacent to each cis-form and if these are opposite to cach called trans-form. Thus, this kind of isomer = referred to as cis-trans isomerism. This type of isomerism is very co Solved Problem co-ordination com si iplexes with a co-ordination num “NGERT INTEXT QUESTION _ er NGERT IN Ui ee, (a) Isomerism in Complexes with Co- ordination Number 4. These complexes can either oon Give evidence that (Co(NH)_CUSO, and have a tetrahedral or a square planes geometry. The E57), S0,JCt are ionisation isomers. tetrahedral complexes do not show geometrical jon, When they are dissolved in water, they givedifferent isomerism because the relative positions of the atoms ssutthe solution which can be tested by adding AgNO, with respect to each other will be the same. The square a and BaCl, solution. Both one by one when Cl ions planar complexes on the other hand show this kind sethecounter ions, a white ppt. will be obtained with AgNO, of isomerism as follows: slutio. IfSO%- ions are the counter ions, a white ppt. will be cbusined with BaCl, solution, Ben re bee ee Ma aa 1, Which type of isomerism is shown by the following pairs? (@ (CoH) (NO, XCh) C1 and {Co(NH,),Cl,) NO, (i) [CoNH,) (CN),](Cr(NH,),(CN)) and [Co(NH,),(CN)ICrx(NH,(CN),] (iid (M(CO),(SCN)} and [Mn(CO),(NCS)| Cv) [PLONE JIPtCl,] and (PLNH,),Cl] (PtCl,). 2, Write the structural formula of co-ordination isomer of [Cofen),[Cr(CN),]. rt 3 i 3 Cy ‘Square planar geometry Octahedral seometry In case of square planar complexes, the positions 1-4, 23, 12 and 3-4 are cis with respect to each ober while the positions 1-3 and 2-4 are trans with respect | each other. On the other hand, in octahedral complexes positions 1-6, 2-4 and 9.5 are trans. Scanned with CamScannerco-ordinated square planar © MAX beg (o Tetra ‘and can pon afone oi ion ; B are neutral By raat at. eve tene vn es NO, é, nt te, whereas example of this type is “a ‘ott i ike HO: , NH, CO, NO, OsHgN, ete W200 = ie Tigunds like Cl, NO}, SON’ € oe me Re i : Some common examples of different types ome follows: mre WAXe.(Co(NH,Cb (Peaiti),Ch PN cananabow tia PE Pat), NiiD, Cul, AWAD ee ; im of isomerism. no, nd et | ‘Type MA,XY: (Co(NH,),Cl(Br)], [Pt(Py),(NH)C WZ Lo i) Square planar com, y ple HN e ' ! je, the complexes in which ung thay ; i i : ligands are present also show cig yr, } i i : example, Bis(glycinato)platinum (yaa. i i gly = H,NCH,COO- eta HN ‘Br . Similarly the complex of type MABX, will show cis and trans isomers in a similar manner. ‘Type MABXY: Complexes of this type will have three isomers, trans-isomer complexes ‘These wn ee position of one of the i H,C—H,¢ I f BQ Mey, 000 cisisomer HP—HN 009 Pe OC Sank trans-isomer © Do You Kuou? | Geometrical isomerism is also shown by bled a complexes of type M,A.X,, For exanpl,t complex (PtCl, P(C,H,),l, exhibits geonet isomerism as shown below. — a a (HYP No" Naic,t, cis-form Scanned with CamScanneron —— ‘Pt: oi? i a trans-form i teh tT ae howe econ show geometri 7 Ja patil arrangements for all a | MORE ligands, Somes heFeas X INiCon,chy aie 2? MES are and Y refer to {Coten) C1, Bye eca3e : Ge mommplexes will Be equivalent. wi —_, in Complexes with toners Co. 5 tsometer 6 Such complexes have an (0) 5 Numa! Ujon Nemeary. Some common examples of Mal g ofeamplexes showing this type isomerism oye 9% os under. oe od varal complexes of the type MA,X,, go (i) OF st exist as cis and trans isomers, woe MAS oF MAY: [Co(NH,),Cl,, examples of this type include metal it), RhOD, Ir), PAV), OstD, INH,, Py, H,0, CI, Br-, CNS, ete, (cpnOa} 9 mon com McollD, i 05 gods 25 eo NH oo 2 Remember ‘The octahedral complexes having six different ligands of the type (M(ABCDEF)] would also exhibit ‘geometrical isomerism. These isomers can ‘be written by fixing a ligand at one position and then placing the other ligands trans to it. ‘Theoretically, 15 differ- cent isomers are possible for such type of compleses ‘The only compound of this type that bas been (Gree) prepared is UPyAOH}NO,ACIBAM. trans-isomer {has been possible to isolate ony thre diferent {somers of this compound. plue or Violet) cis-isomer or the complexes of tyPe MAX, ¢8. (i F » (Rh (py),Cl ete. the é; _| | cont catia ithe similar ligands Ga) The compents contin ae al Le eRe man nase re i 4 |. Here: scapfper geometric isomer of the om gant is called example: (Ca¥) neridional (mer). , x v x _ | cate Scanned with CamScannera a ic d ds left is called vb ised ane towards: equal ich rotate pli tes the P! ‘hat whicl “ es with a rates i ite : ator? Ww. Complexe a . facvor dex i end 6 show this salled 4and 6s right is & mber of in Complexes with ‘ber 4. The tetra co-ordinated aera ptanar geometry do not show y eal these contain a plane of Vevever, it has been observed that po exes which contain unsymmetrical tetrahedra, M(AB), show optical activity. For ais teveinatonicke(D also exhibits optical femerem as shown below: Co-ordination complexes with a square optical acti symmetry 0, 0, ~, 7: ) o \, / oN N ‘NH; Glycinate = cH A “coo” Boron (II1), Zn (II) and Cu (II) can also form this kind of complexes. It must be noted that tetrahedral complexes having four different groups to central atom do not show aptical activity because these complexes are labile* and zannot be isolated. (b) Isomerism in Complexes with Co-ordina- tion Number 6. The different type ofhexa: co-ordinated complexes in which at least one chelating ligand is 2resent can be resolved into a Pair of enantiomers and ave been isolated. Some examples of different types of omplexes showing optical activity are discussed below. \0 Complexes of the type [M(AA)K,Y,] eg, Zo(en\(NH,),C1,}* show optical activi i Octahedral comptes gy or IM(AA)X¥1 also show gps Sy, symmetrical bidentate ligand ang yg ligands. Some common CT [Rh(en),Clyl*, ete. rete "ig cisisome (optically ext) It may not be out of only cis isomer will show trans isomer is optically ina of symmetry, mer (optically in acto) “Labile complexes are the complexes which can easily undergo exchange of ligands. Scanned with CamScanneryMPOUNDS ‘ ral complexes with threg «id Gare (olen) Wil aleg shown ane a vi sie ' Tam ihe em by Inelicate 5 the Fone te the typeof aomerim exhibited ‘omer npleses and draw the structure for these (Kieran), “MMC Gi Coen, eto 1 449 ane Gi Pun, : Sotatton Mt Orc. (0 (@) Both geometrical isomer (cis and trans) containing hexadentate ligands such as how optical isomerism. For example, be resolved into a pair of enantiomers. exo also © gota ean ved Problems Base WO o} on Isomerism ‘ Po . Wi ot ol ER Pech comes a wt saw Ry Feared isomerism, why? * jon, It is because the relative position of the ligands —_‘t*xtrorotatory-form Mirror evorotatory-form lution. i ga Srached to the central metal atom are the same with respect (i) Complex will exist as optical Isomers. peach other. Peano 222] The trans-isomer of complex CoCl (en), Sy Peercally inactive, why? ‘ SN ' SI 7, lation. It is because the trans-isomer has a plane of 4 i ‘ : ‘ety and ean be divided into two equal halves QUAN ¥ jas en: en. Eom Why chelated complexes are more stable Ee plees me extoroatonform Mir vortatnsem : will show Tonisation as well as linkage Solution, When a chelating ligand attaches to the central ae ‘Compound will show Ionisation a5 sal atom the process is accompanied by the increase in ee een yremalttag to tse format ble complex. iii) To er: SSE eter {Co(NH,), (NO,)(NO,),» (COANTL){NONNO,) (NOs) CE Give an example of square planar complex Linkage Isomers ‘heh is optically active. {Co(NH,), (NO,)] (NO), {COANH,), (ONO (NOs)2 Solution, The following square planar complex can beresolved (jv) Geometrical Isomerism (eis and trans). into two forms: Wy cl HN 1 H, yp" \ NH, NH;— ©. Pe cut NS J H i CH NS / NH; a H,0 Cl: a H, NH; CH” 0 Hy cissform trans-form Scanned with CamScanner1. How ming geametsiea omens witb rt {he following eemmploee ai (0 [PLCS ANE BE) HH) [ColtT,OHEN (4) Cotwm,CL a " Fclylt (CNH XOHCH a a (0 fervent i) [CANE CHBO BE (Git) [CANT BryleSOe Draw the strctures meal om vi) [CoCL INT sh 4. Drow the strncture of optical iarmers (0 [CRON Gi (PUCI,(en?s (it) [CoC fen NH) 5. Sketch the geometrical of hybrid orbitals @ dsp? (itt) dsp" 6 Draw structure’ NI Fr SEAT Textbook Solved Problem) 7. Out ofthe following two co-ordination entities which is chiral (optically active’? (a)cis-(CrCly(ox)gI*” (6) trans-[CrCl,(ox),]* (NCERT Textbook Solved Problem) sometrical isomers of shapes of the following sets ii) dsp* (iodsp ; 1s of geometrical isomers of LW 3, i) 2, (iti) 2, (iv) 2, (0) 2. 2. (i) optical, (i) geometrical, (iii) geometrical. ‘A WORK OF LAXMI PUBLICATIONS (P) LTD. @ BONDING IN CO-ORDINATION COMPOUNDS Werner’ theory was the first successful attempt to account for the nature of bonding in case of co-ordination compounds, But his theory could not answer basic questions like: (i) Why only certain elements possess the remarkable property of forming co-ordination compounds ? (ii) Why the bonds in co. ordination compounds have directional properties? (iii) Why co-ordination compounds have characteristic nagnetic and optical properties? However, with the levelopment of modern theories like (i) Valence bond ‘cory, (ii) Ligand field theory, (ii) Crystal field theory = ular orbital theory, ithas he, ‘properties of these compe” Pn rand (iv) Molec! ’ ceplain eoetey and maWeC propery colour Hite nome of UNe% OND egy Ma A. VALENCE BOND THEORY (vizr, ve phe valence bond treatment of ,, unda was developed by Pauling ‘Ty. theory are as follows: iy A anitable number of vacant or, present on the central meta! ny formation of co-ordinate bony 2” fl ligand orbitals, woth Git) Depending om the total numey formed the central monn”! ny appropriate number of atomig por d for hybridisation yon equivalent orbitals called hyp"! og (iii) The hybridised orbitals arg ay lap with those ligand orbing Mt dan electron pair for bonding. "4 (iv) The outer orbital (high (ow spin) complexes are upon whether the d-orbital, the d-orbitals of the inner 5; hybridisation scheme. (v) In addition to a sigma bong possibility of pi bond formar, orbitals are available on the m the ligands. A few examples are discussed to i above points: (@) Hexaamminechromium( II) [on,: complex, the chromium ion is in +3 oxidations has an electronic configuration of 3d°, as stova Wei compo i of the hat SPIN) OF ing Fred of ou Atomic orbitals of Cr (II) ion Scanned with CamScannerone 4s and three 4, Ip. \d six d?sp°-hybrid orbiter then 70 a 10 9" ads of an octahedron, Tho gi 8 ibys : emia sion donate pe ofelectronstocnen ait ets Consequently, the structure ‘these Ht od edral. The Presence of three 4 of the 5 OE gesaining orbitals of rN) sed agmetic. ©8 the sracarbonylnickel(0), In this co o je configuration of nickel (0) ines oe tions of formation of chemical bon ‘4st, | epee forced to pair with 3d electrons ee 98 ee prorbitals hybridise to give 4 or tals oriented tetrahedrally. Bach co) ett Og pair of electrons to form a tetrahedral co on pagnsistuties reveal that the compound fee Te ge in nature and thus supports the forced ergs electrons with 3d electrons. The “8 oq scheme and formation of complex ig jx on : Thus, 6 9nd 4s 4p V Four pairs of electrons from CO molecules (o Tetracyanonickelate(I) Ion, It is a square ganar complex in which nickel is in + 2 oxidation state tndhas the electronic configuration of 3d®. In this case tetwo unpaired electrons of the 3d-orbitals are forced topairin the presence of strong ligand, CN ion. Since fut ligands are to be accommodated, therefore, sikelOD ion- undergoes dsp?-hybridisation forming four equivalent dsp®-hybrid orbitals. These accommodate the fur pair of electrons from the ligands. In the formation of the complex since the inner | Gurbital is used in hybridisation, [Ni(CN), is called ‘inner orbital or spin paired or low spin or hperligated complex. atlon selene in as fhllows: {Nien J Bon mF pairs from CN e N groups is diamague a n mnpeied electrons, the complex aos cause of daphybridisation of square planar geometry. epee Ion. In this neta ae configuration of cobalt in a Le, under conditions of formation of plexes is 3d8, Since F- ion provides a weals ligand field therefore, one 4s, three 4p and two 4d-orbitals hybridise to yield six sp'd®-hybrid orbitals pointing towards the six ends of an octahedron. The six F- ions then donate a pair of electrons to each of these vacant orbitals to have an octahedral geometry. The presence of unpaired electrons in 3d-orbitals makes the complex paramagnetic, The schematic formation of complex is illustrated below: Atomie orbitals of Co(IID ion “om A) Oo Coe tp spd? -hybridised orbitals of Co(IID ion 1t beh ‘The formation of complex involves d-orbitals of autor shell and hence is called outer orbital or high spin or hypoligated complex. ‘The state of hybridisation and the magnetic behaviour of some co-ordination complexes is listed in Table 9.6. Scanned with CamScanner474 WvaH,0)" eran)" isation and Mtexes of Hybridisr ation CO Table 9.6. State vr ‘Co-ordinadl ieee ° ired Magnetic Behaviour Hi Paramagnee 2 3 4 2 [Mag 1 = | - ‘amagnet in(CNh ie mcrae 5 Paramagnet UFe(CN i . ie | ‘ aramagney,, | Fer, etic | 1: 4 Pai (FeCl, a SrAMagnetic | (CoP, Diamagnetic | [CoANNH)6"” is Paramagnet wNiccD, co Diamagnetic axen ; Parent touch - iamagnet fn NH | 20 : etic Behaviour LIMITATIONS OF V-B. THEORY It provides only qualitative exp! «a saris isto explain the optic absorption spectra and magnetic properties of co-ordination compounds. _ iii) The theory does not give a quantitative ? interpretation of thermodynamic or kinetic lanations for stability of co-ordination compounds. (iv) It does not provide exact explanation regarding structures of 4-co-ordinate complexes i.e., whether these are tetrahedral or square planar. (v) This theory does not explain as to why in some cases inner orbitals and in some cases outer orbitals are used in hydridisation. (vi) It does not predict the relative stabilities of different complexes, (vii) It does not take into account the splitting of d-energy levels, (viii) The valence bond theory does not tell as why water and halide ions commonly form high spin complexes with cyanide ions from low spin complexes, (ix) It does not explain th i poss cee ae electronic spectra and wlio al ca ta ea rystal Field Theory, B. CRYSTAL FIELD THEORY (cf) ‘The valence bond theory of bon ions has many shortcomings. Inorder to provide suitable answerstom questions, erystal field theory proved farmon and a better alternative, It was developed yy and V. Bleck (1935). The major difference between the two thay that the valence bond theory considers tie tg between the metal ion and the ligands as puny where as, the crystal field theory considers the between metal ion and the ligand as purely cet ‘The CFT is based on the assumption tht metal ion and the ligands act as point charges al interactions between them are purely electra case of negative ligands (anions such as Cl, Br (Nk intersections with metal ions are ion-ion int If the ligands are neutral molecules (such as NH CO), the interactions with the metal ion are ar interactions. The name crystal field is ass theory because the electrons of the central a! the environment of other ions or molecus i" are affected by their non-spherical det an electric field is ealled erystal field and crystal field theory. ding in Scanned with CamScannerrmaportant FENCUreS OF CRT gy. 0 eM ansition metal ion is surronn he Ie pairs of electrons and the git the il ere ntral fon surrounded by yyy PI% ie teat Spleens hale Su iypes of Higands are roy ie) ta farded a, 1 08 poiny interactions between the mo vie of anion (or ion dipole ae ithe bond between the meta ti ionic ae Tigands surrounding the moray ; 2) THE field and this electrical feta inf Sf the orbitals of central metgi ne tal io ion and ®) is purely Hand Tigarne) yet fet ‘g-orbitals. cle Sine case of free metal ion, all the jp, He ene same energy. Such orbitals jaf” gals ha called degenerate ‘aving eae nee aie : cnerate d-orbitals of the me The fee te orbital having different onan fe tectrcal field of ligands. This ean” ve tne rhe number ofigands and their arrangement WiMround the central metal ion will have cm) tect on the relative energies of the five cc is. In simple words, the crystals field splitting ite different Es different structures having different al nation numbers. ete The magnetic properties, spectra. and seen for particular geometry can be explain in terms Meputng of orbitals in different erystal fields, Thus, to understand the crystal field theory, itis anf to have a clear picture of the disposition of the fudapitals in space and the geometrical arrangement ¢{te ligands arround the central metal ion. We may dlutrate this concept by considering the complexes with cvardination number 6 and 4, which are very common. ORIENTATION OF d-ORBITALS AND CRYSTAL FELD SPLITTING There are five d-orbitals. These are designated Sd dy dy, dia_,2 and d2, The shapes of these stitals are described below: cada! Te three orbitals d.,, d,, and d,, are similar leach consists of four lobes of high electron density 1,28, ye and zx planes respectively. These lobes inbetween the principal axes. For example, in case 7 “ital, the four lobes lie in ay plane in between “and y-axes, f way The day _,2 otbital also has four lobes of high Aensity’alone the principal axes x and y. t ng lit! «long th ey plane Orientation of five d-orbital ‘The five d- ital: “di orbitals ean be divided into two row depending upon the nature oftheir orientation te sous, @ The three d-orbitals (dd ent in the regions in be ord , i tween the co-ordins designated as t,* orbitals ) which ori ate axes are (i) The two other orbitals (d,s, and dz) Which orient along the axes are labelled as e,* orbitals. In the case of a free ion or in a isolated gaseous metal atomvion all the five d-orbitals have the same energy i.e., they are degenerate meaning energetically alike. This degeneracy is maintained if a spherically symmetrical field of negative charges surrounds the metal atonvion, However, when this negative field is due to ligands (either anions or negative ends of polar molecules like H,0:, NH, ete.) in a complex, it becomes assymmetrical and the degeneracy of the d- orbitals is lifted. In simple words when the ligand approaches the central metal ion, the electrons in d- orbital of the central metal ion will be repelled by the lone pairs of the ligands. As a result of these interactions the degeneracy of d-orbitals of the metal ions is lost and these split into two set of orbitals having different energies. This is known as Crystal field splitting (8) and it forms the basis of crystal field theory. ‘The energy gap between f,, and e, sets is denoted by ay (octahedral complexes) or A, (tetrahedral complexes) or 10 Dg, The energy difference arises due to difference in electrostatic field exerted by ligands on tayand e, sets of orbitals ofthe central metal ion. 10 Da of Ais called erystal field splitting energy (CFSE). ¥t,, and e, are spectroscopic terms and beyond the scope of ts book.” Scanned with CamScanner476 ___Tt must be noted hero that the crystal field splitting largely depends upon the number of ligands approaching the central metal ions. In simple, wort the crystal field splitting will be different in differe! structures with different co-ordination numbers. os Lat us, illustrate this iden by comsiger't complexes with co-ordination number 4 and 6 i tetrahedral and octahedral structures CRYSTAL FIELD SPLITTING IN OCTAHEDRAL CO-ORDINATION ENTITIES In an_ octahedral pele ion is al cami aa shown in figure below. ‘The three axes X, Y ant along the corners of the octahedron and are in the figure. Free ion STATE -1 STATE -I1 guppose that the metal fon, yy. vet tron (d! configuration, e.g, Te + hay single free ioMs when there are no ligands 4) In In the spy any one of the five d-orbitals recat, i can be vpitals are of same enerEy (degeneraty ” al five d-oF tahedral complex MX,, all the fy, "i In the acttpain of equal ENETEY when vi nach ‘the metal ion. The two orbitals lig arate and df orbital point direty tina, ofthe octahedron, where the negatin, . re concentrated. ri, corners the Jigands a4 ‘hs the ligands approach the contra, orbitals are repelled more than je) th Bativeg., * axes, thee, nother words, the energy of the d.? and increases much more than the enenty ofthe inerivtad, It should be remembered har ‘eipepelled by a similar charge, its poteny increases. The greater the repulsion, the greny. increase in energy). ‘Thus, in octahedral complexes, the five. eplit up into two sets: one set consisting of ty, ofhigher energy (¢, orbitals) and the others of there orbitals of lower energy (¢,, ovina phenomenon of crystal field splitting in an complex is illustrated in the figure below. The energy difference between tuo xy d-orbitals ; tay and ¢, is called erystal field si energy and is symbolically represented 2: 4, subscript (0) stands for octahedral). The magi A, varies for different complexes. The cystd Splitting of orbitals in Octahedral (4,) field er iy STATE Il Crystallfiéld aniittines tern te Scanned with CamScannermeasured in terms of ang two are related as: 4, =10Dg two paTAMELETS Are Very common spy be noted that the crystal Goyg 09%)" woy that the average ena. Plt tives vat eha04®. This is ln which is similar to ‘centre of : that the decrease in he sae that le at the lower energy level my et ls Mone corresponding increase in gin | : f total energy 10 D, a | tt, in terms of total energy 10 Dg, the en inet vo ¢, orbitals i8 raised by 6 Dy ang’ foots ofthe three ty, orbitals is lower te |e terms of 8, the enerEy of each of the tye {ne 8 Srised BY 158, (or 08 ,) and the ener tite eee fy, orbitals is lowered by 215 4 po % °Y 25 A, (or He ipe value of 10 Dg or a, sroseopically- ‘ - hown above we observe that inii in figure 8 e at initial genie ofall the five d-orbitals are raised equally seem state I This Would be observed ifthe field by the ligands was spherically symmetrical, the dorbitals split into two sets of different wees because of the different orientation of the ol towards the ligands as shown in state II, sols me "Parameter IY used, ing TRY of the WN as bay is measured # eel (gYSTAL FIELD STABILIZATION ENERGY (CFSE) We have learnt that in an octahedral field, the cong of five orbital split-up. Three orbitals are ioered in energy (ta,) and two orbitals are raised in cacy €,). We know that electrons always prefer to ccupy an orbital of lower energy. For example, in the case of d? system (eg., Ti* in FJ, the d-electron will prefer to occupy a ty, atital and is, therefore, stabilized by an amount equal 1004, or 4 Dg. The amount of stabilization provided by splitting of the d-orbitals into two levels is called cnstal field stabilization energy. It is abbreviated ‘CFSE. Thus, in octahedral field for each electron ‘aernginto the, orbital, the crystal field stabilization 's-4Dg and for each electron entering into the e, orbital the esta field destabilization energy is +6 Da. Thus, ‘h CFSE is caleulated as the algebraic sum of ~ 4 Da Peeecron int, level and +6 Dg for each electron in ¢, it th ion) electron will be ation mate thee ty, orbitals, The elec- Ly be writt tion energy fia — a a one of the = 14D) == io ADq) == 4Dq ; For ad? Will occu System (e., V¥* ion) the electrons IPY bay orbit accordane. ‘a (nbitals with their spins parallel in configuration Hund's rule, ‘The electronic is 1,2 energy ig py." md ervstal a DOO ; crse=2- 409 =-a04 (ii) Similarly, for ad? e tronic confi , for ad? system (eg., Cr), the elec- nic configuration is t, 9, The a zation energy =o Be : ‘The erystal field stabili- @OM ; crse=3- 4pq =- 12D¢ Fora d* system eg, Ma** ion), there are two es: __(@)All the four electrons may occupy f,, orbitals with one electron getting paired. The electronie configu- ration may be written as tag’. (©) Three electrons occupy fa, orbitals and the fourth electron goes to one of thé ¢, orbitals, The configuration may be written written as t,2e,!. Os | 3, Low spin complex DOO} | ‘sveng ld ks (a> P) ‘The actual configuration may be decided on the basis of 4, and the pairing energy (P), ie, the energy required fo pair the electron with one another. ‘The configuration (a) is possible if A, > P. These complexes are called strong field complexes because js large. In this case, the complex has less number of ‘unpaired electron and is called low spin complex. possi Scanned with CamScannerThe configuration (b) is possible i pT possible if A, < P. It is caltea Weak field and the complexes are called weak ield complex. In that case, the maximum numbers of electrons remain unpaired and the complex is called high spin complex. As shown above, for a low spin complex having ‘a, configuration, CFSE = 4(- 4Dq) = ~ 16D7. Howeves if we take into account pairing energy (P) also, the CFSE becomes: Net CFSE =- 16Dg +P On the other hand, for a having the configuration f,6 %," Net CFSE = 3(- 4Dq) +16 for a d®, d® and d” syste high spin complex, 6 Da fms there (v) similarly, are two possibilities ‘The dd? and d® systems have only one possible configuration. ‘The CFSE: of d electrons (d to above. CRYSTAL FIELD SPLITTING IN’ ‘TETRAHEDRAL COMPLEXES The tetrahedral arrangement of four ligands surrounding the metal ion may be visualized as shown in figure below: formetal ions having different number d®) can be calculated as discussed jn tetrahedral field, none eis clear that 1, towards the ligandy! orbitals point tr) 7 of eneray will be less ittind % d-orbitals d., and ¢, Hare to the direction in which KE ‘while the twoorbitals 4... ang he ligands. Therefore, the lyi ia will be raised while the engi i tals will be lowered. Thus, inthe p the tedral fields the degenercy of five d-orb therefore, the spun octahedral field fare pointing © oachin8 "iy the two orbitals, dy». and 4.1 becom and their eneraies are lowered. These are deg: ‘as ‘¢’ orbital Co) Is. ‘The three orbitals d,,, d,, and q d their energies are raised, qf, table an ‘i are \ a a a shown in below. ‘The magnitude of crystal field spit difference between ¢ and t, orbitals and is desi gs A, (the subscript indicating tetrahedral comp Jt is.also measured in terms of Dg and a, = 19 py compare the magnitude of crystal field spit setahedral and tetrahedrals complexes (havin tnetal ion, ligands and metal ion-ligand distayy has been observed that the crystal field spit tetrahedral complexes (A,) is considerably less octahedral complexes (A,). It has been found complexes. (i) In tetrahedral complexes there ligands while there are six ligands in ct complexes. Therefore, lesser ligands producelessa field splitting. The crystal field splitting in tetra field is about two third of the octahedral field. (i) In tetrahedral field, none of the ott pointing directly towards the ligands and, splitting is less. Since the magnitude of crystal field split tetrahedral field is quite small and is always I pairing energy, therefore, the pairing of electr™ never be energetically favourable. Thus: tetrahedral complexes are high spin complet tetrahedral complex with low spin has been 8 exist, Scanned with CamScannerota a A) od Ado ans, Eno Fh Shona gta 10% Sdnor v, Fre ion L, ATE“ , et STATE -1 STATE geometry is paramagneti diamagnetic though both are tetrahe dation state of DICKEL iS 2ory yp ox. Due to the strong ligand feign Bs ed electrons of nickel get paint ra of Cl does not pair the ele is Femagnetic while the [NiC1 > jg Tar [00F gP* forms outer orig, ‘o a (CoF ¢* F ions provides aw. electrons of cobalt do neq 2 lgaag st uhe orbitals of outer shell are useq, 00 8 Lipa efor hybridisation (fey) Sly AF strut ‘on with ttt INICL J? is paramagnetic white Sicoy (Fe(H,0),]°* is strongly es a [Fe(CN),|* is weakly paramagnetic cle Explain (Co(NH,),* is an inner orbital» whereas [Ni(NH,)¢l** is an outer orbital iS a Predict the number of unpaired Sec square planar [PUCN),)* ion, a ‘The hexaquo manganese (Il) ion contains unpaired electrons, while the hexacynoion ey only one unpaired electron, Explain using Ca Field Theory. In [Ni(CN),P-, OS of Ni = +2, conf = hybridisation = dsp?; no unpaired electron For tetrahedral (NiCl ,P*, hybridisation =p two unpaired electrons. INiCL,P- is paramagnetic (refer to hint th Ni(CO),, OS of Ni = Zero; CO forces paints electrons in d-orbitals and hence the cont diamagnetic. i OS of Fe = +3, Conf = d°, in presence of CNH electrons pair leaving one unpaired “et Hybridisation = dsp’. H,0 is a weak ligand and therefor not pair. = re 3 elec Scanned with CamScannerFa Cem xays” inner dorbitae 76 Teo opens ite 6 fails ofualence shell are used in nf got, planar [PUCN,P-, og nd 6 Poa = ott 5d. oe presence of 7008 ligand field of Gy or 6s, nthe Pr pair. Hybridisation is dsp? qv t® Sd ae ear! PY and hence quot Tal complexes with d tod? configu g ocanere to either high or low nae vation can get Fe, nD has ad? configuration, prerete pore crystal field this spits to give ty Sok cctoherong crystal field it gives 5.0 In'yhe but ing Mpg of lector occurs, fin tne et com pir of ct are present leaving od case tired electron. "8 only GOLOUR IN CO-ORDINATION COMPOUNDS in the previous unit, we learnt that one of the niin properties of transition metal complexes ovat ange of colours. This meane that sme of i spectrum is boing removed from whit ight setger thrdigh the sample, so the light that © colour i xnlanettP€einaton compounds can fr exams en tthe eral fl theory. ell sour tg em ITO) 0, which Te Se clectnon er” 2% etahedal complex where Orbital ig i THN i934 nyse) is the tee gate) in the metal next ign tl in the ground state of the TDAY eel er tate availabe forthe electron Ot yellow gry ey light corresponding to the energy Ould en ion is absorbed i cite he ed by the complex, it, yee ot, oe ‘tron fom ty evel to the ¢, level Vile in colour Pig orn ean crystal field the £ the complex appears 'g-9.1) In simple words according to ‘ory the colour of the co-ordination ‘compounds arises due i i —— es due intra d-d transition of the ee particular compound depends nea of A, the crystal field splitting which Tr lurther found to be dependent upon the nature of ligand (or ligand field). For example, on Octahedral Complexes of Chromium (II) are all oA ‘ystems, yet the colour of the complexes is different. \tis because different ligands present around the central ‘metal ion produce different ligand fields and hence different crystal field splitting (A). The magnitude of splitting observed in each case can be explained on the basis of spectrochemical series. sil 4 * isno longer white. The colour of the complex is aumipentary (0 that which is absorbed, The Tomer [Colour [Tomer | Colour | ‘onplementary colour H the oe generated from the | {CrlH,0),)C1, [Violet | (CrONHy)ICl, | Yellow gavelength left over; if green light is absorbed by the 7 ‘ample, it appears red. Tabel 9.7 gives the relationship [Cx{H,0),CNCI,| Blue-green | (Cr(NH,),CICl, | Purp amp fiferent wavelength absorbed and the colour | (CrH,0),CLJC1| Green| {CrNH),C1JC1 Violet tbserved.. Table 9.7. Relationship between the Wavelength of Light Absorbed and the Colour Observed in Some Co-ordination Entities Co-ordination Wavelength of Light! Colour of Light Entity, “Absorbed (nm) Absorbed 7 Violet ‘eel 2 35 Yellow (oI CoCr Fegreen GEE | Red rere Ione) H,01* Bis eet | Yew orange AL (CoH,)* “ ae let EEE | Pale Yellow — Icon), a Red Gem | Bie = (CutH,0),)"* - Blue green ME | Purele = (midH,0,)*" S Scanned with CamScanner6 * h t 1 Gro tog -- “a nnd state Tei tate - Yi. 9.1. Transition of an leetran i (TKO 1 the absence o Tis i , 5 imports note that in aedeagal and hence li the ctl field splitting docs nat occur and PT acetbstance is colourless. For example, removnl er from [Ti(H,O),ICly °F heating eee ut colourless, Similarly, anhydrous CuSO, is white, a CuSO,,51,0 is blue in colour. The influenss ofthe gam ‘on the colour of a complex may be illustrat i considering the INidH,0),? comples, which fom e nickel (II chloride is dissolved in water- Ifthe didentat ligand, ethane-1, 2-diamine (en) is progressively added in the molar ratios en:Ni, 1:1, 2:19 , the following series of reactions and their associated col0Ur changes occur: [Ni(ET,0),)** (aq) + en (09) = [Ni(H,0),(en)I”* (ag) + 2H,0 green pale blue (Ni(H,0), (en)]** (aq) + en (aq) = INi(H,0),(en),]** (aq) + 2H,0 plue/purple [NiO (en)? (ag) + en (ag) = ENiCen),}* (0) + 2H,0 Violet ‘This sequence is shown in Fig. 9.2, INi(H,O),F"(aq) INipOyeni*(eq\, fNenst“tea) INi(H,0),en,f"(aq) Fig. 9.2, Aqueous solutions of complexes of ni (A) with an increasing number of ethane, 2-diamine ligands. : or rmetal Ons. trai aly ia B05 hich contains about 0.5 1 fhe fof these ions in the alga” "Piz transitions at these contra li to colour. ei Tig has Cr? ions in the m, Fi Si Oy) Te greenish in csioue LIMITATIONS OF CRYSTAL FIELD ‘The erystal field model is succesefuy OR formation, structures, colour 4,7 fovea of co-ordination compounds an%, {i On the basis ofits assumptin care point charges, and hence the anionic fs are Mephe greatest splitting effect. Howey figonds actually are found at the Ing spectrochemical series. ow end (ii) It does not take into a character of bonding between the ligand wy atom. nd the the prope These are some of the weakness are explained by Ligand Field These arsiccular orbital theory which are beyond tee the present treatment. 7 MAGNETIC PROPERTIES ‘The transition metal complexes are be paramagnetic in character. CFT helps w understand the magnetic properties in tems magnetic susceptibility — measurements magnetic properties of a substance depen the oxidation state, electronic configuration ordination number of central metal and the notin ligand field. An unpaired electron because tis} is equivalent to an electric current flowing ina conductor. Hence, it behaves as a mst magnetic moment will thus be expressed 38 att Hp Game Here, e=charge on electron, m = mass of electron, h= planck’ ¢ = velocity of light. and / a The value of i, sbteined ben ‘ 4 x 10 ergs BAUS expression is 9.27: as a unit of magnetic mome (BM). Scanned with CamScanner nt called.ce containing one or more site value of magnetic momen 4 dat magnet fel. Such substancensue emetic substances. On the other haat ang paired eesione wl hve ae gnees Pd hence do not possess magnetic fre known as diamagnetic etiemoment ofa substance depends upon empaired electrons ic. grenter is the nparplectrons more is the magnetic ugbeon show? that the magnetic moment of a in tn’ unpaired electrons is FA en Be ‘expression below : ate eee eat Jan +2) Bohr magnetons. qnship is used to calculate the number je in anion. ge+D Ft Value of gyromagneticratio=2.0) | ABE -rauelewledgeofoumber of unpaired electrons ibenveofmagneticmoment (0) it is possible to find yalence state of the metal fon is given com a «aaature of bonding in the complex i.» spin free xg paired type. Thetalues ofn calculated by this expression for heat magnetic moments* are given in Table below: > ‘A ‘Sim et le device known as Guoy’s balance is il measoreparamagnetism. Further discussion dpe of this book. rent tnt als to It doth ia disation with 4. our of these free jn Ye ailable nd Ap-orbitala, is simi sand their er-ond 1". When ‘hen more than three the Fequired pair of 3d-orh innovate Thus, for d* (Cp2+ Mn cases, a vacar icf fares a vacant sited na 3d electrons which leaves te ean 2 leon wh enn al ra 4d electron ahedeal high conse qu tals for cet stan re one inp | The magnetic data agree with i pairing in many cases, especially with eooni compounds containing i ions. Homever, wth ag containing d' and d’ ions there are c mph a omplications spin @ (Mn(CN),]* has m: agnetic moment of two tanpaired electrons while [sCl™ has oe magnetic moment of four unpaired electrons. [Fe(CN),|* has magnetic moment of a single unpaired electron while [FeF,J* has a paramag- netic moment of five unpaired electrons. [CoF,J* is paramagnetic with four unpaired electrons while (Co(C,0,),] is diamagnetic. ‘This apparent. anomaly is' ‘explained by valence bond theory in terms of formation of inner orbital and outer orbital co-ordination entities. [Mn(CN)* (Fe(CN),)* and [Co(C,0,)4I* are inner orbital complexes involving mer two complexes are d?sp'-hybridisation, the for paramagnetic and the latter diamagnetic. On the other hand, (MnClj!* [FeFeI* and {CoF,(* are outer orbital fvolving sp'd?-bybriisation and are paramagnetic corresponding ° four, five and! four unpaired ‘wed Problem B I tognetic > Pexample 1g asptain with ame The bond type * Bxplat ria of the bond can be etic criteria of ; Solution. The generalisation magne te type means predicted on the For example, Scanned with CamScannerimental intry bat experiment we anne shape and geometry DY EST C4 shold hee eae hn erage eet ean Tene teen unpre Hen MT are ailethe secant hne tape et arg eee INUCND is dep WPT idiged tne vtston Nin EN" paar structure) while in Motrabedral structure). > is moment of (MnBr,] Te ein only magnetic memento Mg "Sopa. Dei The ee CO ing tie mom 2 Calculate the magn Nel (i (CANE) aii) FACN) 1, Tetrahedral | 2 (i) 2.828 BM (ii) 3.873 BM (ii) 1.73 BM. STABILITY OF CO- ORDINATION COMPOUNDS IN SOLUTION ‘The formation of a co-ordination compound involves reaction between a metal ion and ligands. If the force of attraction of the metal ion with ligands is strong a stable complex may result. Mostly the complex ions are highly stable, However, their possibility of dissociation in aqueous solutions cannot be ruled out completely though these may be dissociated to a small puient Thus, a chemical equilibrium may be established between the undissociated complex and the dissociated ions, OLY Mey ate Here a*, x- and b+ are atoms, ligand and comare e cnttBes on the metal Plex respectively. Thus, the he above reaction is given as tanilty ofthe complex. The value of, fic) fora few complexes are given inp, the mageitude of stability gon, that what kind of ligand wigh yh Prrvields amore stable complex, fy enon vate of ability constant for cong hg bitty. For examplea ery ng that complex of Cu’? with ‘be be leg IN Is ty 8 that will ammonia, More a Alternatively, WK values ap, instability constant, min ‘The stability of any complex eq, in terms of its formation ¢q, a . understand thisidea with thehelp jst (,) 7 below. “amg (MGLO)J+nb <= iy, Follows the following, ‘Steps, * ni Step I. (M(H,0),} +L = IMLH,9) The formation constant A for this step = MLO, BIOL Step Il. MUO J+ = yn, a4, The formation constant. ofstep2 Meal = MLH,0), © MLA), i Similarly, (ML,(H,0), 41 +1, Thus, for nth step the con = mM). stant, a(H0), all] Now for the overall reaction By = Ky x Kx yx nt HereK,,K,,K,.....etc, arestepwisef constants or stepwise stability constants is termed as overall formation constant or cumulative stability constant, While studying the formation of com solution, two kinds of stability of complexes ox! question. These are: (i) Thermodynamie stability. tis of the extent to which the complex’ alia form into another species when the ste equilibrium. This kind of stability deals! bond energy, stability constant, etc. aly cons *As concentration of water remainsessentil itis ignored. Scanned with CamScannerCa + 40Nn- pcarcn 67100 tac) {cot} Oe ge [ou(CN)” Cut+SCN- aoe [Coat * Te 108 | = wc 45 e109 {outNHt cv save, a - | h == Icunny,p 107 acd oe A - = [recy Ao pre(cNe Fe*+6CN- === : Lao " pe [Fe(cn),)- *10 | roc) +3ck == poo Lee gc)” Hg? +4 == gC, 24x10! e re taxis | ial = may | sien Nit +4CN/ == INCN) a | 1x10? iAgiHi)l” Ag'+2NH, <== . : wD. 7 7 i (AgtNH)I 16107 | (CN),I- +2CN == i: tagicel . fagiCN),) 56x 108 1aas,094h Ag'+28,0° = [AgS,0n wren 2 = (2a NH) Zn +4NH, <= [én(NH,),!* aoc (ann) Zn? +40N- == en(CN,1 1x 108 a) a inetc stability. This refers to speed with sssdetransformations occur so as to attain equilib- sae netic view point a complex may be inert Or biersherthan stable or unstable. ‘Complexes in which ‘earn rpily replaced by others are called abile or 7 K,[Fe(CN),] is more stoble ‘Sivtconpleres while those in which substitution Lead =e Esplin why KAFACHIS ‘reson are called inert complexes. than KFACN J! ic — 7 Solution. It is because the stability of complex depends VS a .canplis discussed below toillustrate the above Seton ie creme te the charge density ereater iS the stability. cae tan +NH, — [Cd(NH)I"* ie mae in twoortnesenensn oT ‘MHI + NH, —> [Cd(NH,)”* : Te iy forthe following serotype tans +NH, > [Ca(NH),)**- he species cul esse Cal For 2) Ay ce pre — tare oe ons econ ie wm me Te Coke ution. vmod | RKixK, «Ky x Ky Sotto nnn we 19 around it = 1088 19210 x 1014 x 10°99 = 107. Scanned with CamScannerNe — SRT INTENT QUESTION iation eauilibrias Calculate the overall complex dissociation this compre 0 at forthe [CuiNty san, given that BaF Solutio, sro 1 1 1x 109 CACTORS AFFECTING THE STABILITY OF COMPLEX The ‘stability ofa complex depends upon * the nature of central ion and * the nature of ligand. re 1. Nature of Central Lon, Th term nature means the charge density on the central ion ‘dias ratio, is the charge density or larger the charge/rat le, out of more is the stability of a complex. For examp "stable. complexes of Fe** and Fe**, those of Fe** are more =4.7x10" For example, Fes 6CN- <== e(CN),I> 5} K = 1.2 x 10% Fe + 60N- <=> [Fe(CN), J"; K= 1.8 x 108 For the ions which carry the same charge the one with a smaller size gives the more stable complexes. For example, among Cu”*, Ni**, Co**, Fe** complexes as the size of copper is the smallest therefore it gives the most stable complexes. 2. Nature of Ligand (a) Basie Character of Ligands. More basic is a ligand, greater is the ease with which it can donate its electrons and therefore more is the stability of the complex. For example, the complexes involving F~ ions are more stable than those involving Cl- ions or Br-ions. () Charge on Ligands. For charged ligands, the higher the charge and the smaller their size, the more stable are the complexes, (©) Chelate Effect. Also complexes containing chelate rings are usually more stable than similar complexes containing no rings. This is termed as chelate effect. For example, Ni*(aq)+6NH,(ag) <== INi(NH,),)2"(aq) log 8 = 7.99 == Milen),!(aq) log B= 18.1 Ni*(aq) +3 en(ag) tal Field Effects 3. the stabil ty of high spin compe + Mn? and Zn® with a give Sof Tigang ge Mn? < Fe? < Co” < Nits 6, ‘This order is also called natuyay sistent with charge to radins retin. ofthese ions ar ; fe Mn (0.91.A); Fe 0.89 4), (0,78 A); Cu*? (0.69 A); Zn"? (0, 4A) “4, Class a and Class 5 Ahrland have classified the metalg ie, a, & and borderline on the acceptor properties. @ Class metals, H, grow 2 alkaline earths) the elemery C1; Zn to Br, In, Sb, Sn, 1 The stable complexes with ligands and F groups. i (i) Class b metals. Rh, Pa, 4 ‘These elements have ful therefore form more stabie » ligands whose donor atoms ae ber of N, O and F groups "I (iii) Border line metals. Elements from p, Tl to Po, Mo, Te, Ru, W, Re, Os, can not follow a particular stability crise ‘The stability onder of complexes thas with ligands follow the following order: Class a elements : F>Cl >Br sf 502858 >Te>N>>P>As>SboBi Class b elements : F’ [Ag(NH,),* (aq) + Cl (aq) ‘illexcess of CN-. The following reaction occurs %u248CN- = 2ICu(CN),* + CNA) slubility in hot water. AgCI(s) is separated from Hg,Cls) tyits solubility in NH,(aq) with which it forms a soluble Similarly, the separation of ‘Ca*? from Cu‘? could ‘lobe achieved by treating the solution of Cu‘? and Cd* CA44CN- = [Cd(CN),}> «ns bp= TA 108 . ye hy = 2 «10 washing it with a solution of sodium thiosulphate. AgBr(s) +3Na,8,0,{aq)—+ NalAa(S,0,),Kon) +NaBetaq) 4. The nature of ligands, changes the redox behaviour of the metal ions. For example, in the presence of some ligands cobalt is easily oxidized from +2 oxidation state to +3 oxidation state. 5. Estimation of Hardness of Water. The hardness of water is estimated by simple titration against EDTA solution. EDTA forms stable complexes with the metal ions present in the hard water. Since stability constants of calcium and magnesium complexes of EDTA are different, even the selective: estimation of these ions is possible, 6.Electroplating. Many co-ordination complexes are used as clectrolytes for electroplating. These complexes deliver the metal ions in controlled manner. For example, for silver plating the complex KLAg(CN),} is used. 7. Extraction of Metals. Silver and gold are extracted from their respective ores by treatment with, sodium cyanide solution, This also involves complex formation, ‘Ag'(aq) + 2NaCNtaq)——> NalAg{CN),Mag) + Noe ‘Aut(aq) + 2NaCN(aq)— NalAu(CN),\(aq) + Na* 8, Biological Uses () The complex of calcium with EDTA is used treat lead poisoning, Inside the body caleius Scanned with CamScannerthe complex is replaced by lead. The more stable __ Pb-EDTA complex is eliminated in urine. (i) The platinum complex cis—[PUNH,)Cla} known, ‘as cisplatin is used as. ‘an antitumor agent in treatment of cancer. : (iii) Many natural compounds, exist as co-ordination complexes, For example, haemoglobin comple of Fe’), chlorophyll (a complex of Ma?) a” vitamin B,, (a complex of Co™). Mr ean mae) ‘The co-ordination complexes are known to be ae ‘medicinal properties. Many such complexes are BOA used as drugs for the cure of contageous disense Te such complex is cis-platin and marketed a5 C, DDP or cis-platino. Answer the following questions: " a @) What is full form of DDP and how its prepared? (ii) Asa student of chemistry explain how the cis isomer of DDPis used in cure of lung cancer? 2 iit) What values are associated with the preparation of complexes? 9. Plant Growth. Plants need various nutrients for healthy growth. The essential nutrients include a number of metals such as iron, zine, copper, manganese ‘and molybdenum. Iron in its +3 oxidation state in the soil is mostly hydrolysed to form insoluble iron hydroxides such as Fe(OH), which cannot be taken up by plants. ‘Thus due to deficiency of iron plants develop a disorder ‘known as iron chlorosis, evidenced by yellowing leaves. The standard treatment for this problem is supplying Fe(II) EDTA complex. This complex is soluble in water and readily enters the roots of trees, where it is eventually converted into a utilizable form. 10. In Living Systems. Coordination compounds play many important roles in animals and plants. They are essential in storage and transport of oxygen, as electron transfer agents, as catalysts and in Photosynthesis, Haemoglobin, a protein present in. blood serves the Durpose of carrying oxygen inthe blood from the lungs to issues. Porphine molecule is an important part of semoglobin structure and is shown below. Porphine ' Complexes derived fy * Pomp porphyrins. In the structure shoo,?°'Phing can replace the two H atoms on tha et co-ordinate simultaneously with porphyrin is thus a tetradentat, pur X for the central metal jon, M8" ori af @ In chlorophyll the centra} 5 (i) In haemoglobin it ig po2 OS Me Theiron-porphyrin = Metal carbonyls of tra; another important class, oforganomer rl d-block elements which contain only a a called homoleptic carbonyls. "ili, Amond in 1890 prepare carbonyl, Ni(CO),. Later orale sa binary carbonyl like, Fe(CO),, CxO) Mixed were prepared. In addition tomononuee mentioned above, rt 1, ‘2 transition metals form polynuclear metal carbonyls such Is Pe Ma,(CO) 9. The metal carbon bonds in mel possess both a and character. CLASSIFICATION OF METAL CARBONS Metal carbonyls are classified intotwotyp (@ Mononuclear (or monomeric) carbo ‘These are such compounds which contain oly nem atom per molecule. For example, VCO), CxC0) (ii) Polynuclear carbonyls. These cutit or more metallic atoms per molecule and are ofthe M,(CO),. These carbonyls are also sometimes @ bridged carbonyls. Polynuclearearbnys may nuclear e.g., Fe,(CO),» or heteronuclear ¢g-." MnRe(CO),». Scanned with CamScanneroe ace ctaleaba ne’ . of some metal tures carbonyls are y; kiven below, tet co ¢o an oc— CO oc” s Z \ = oc wd | co [Ni(CO).1 0 Wre(coy4 cq £0 bo oR Lr /° /\ Fe o¢ \ / | Ce j co co co [Fes(CO)I [Mn,(CO),4 OF METAL CARBONYLS sone (CO) we pia me carbonyls the metal atom is in zero (CO},—CoCO},—CuCO), , gist state’ therefore jt may not be mentioned. Di itis | gp iethe ‘metal atom appears two or more times (tai | oo the word di, ter ete» js added before the name of | (CO), i = yleobalt) =| toon. ieee”, Bis tetracarbonyl cobalt) val (CO4FACO ip the CO BrOURS aC as bridge between the two FACO,FACO), Tar Cartons is pals atoms the ‘the Greek letter mu (u) is written. (tricarbonyl iron) tere their names: (CgH,) CXCO), (qh benzen)trzarbons! {y) When metal-metal pond is present between ot (benzene smilar atoms than multiple prefixes, bis, tris, ete. are chromium Fe(C0), (CH (v) While writing the names of n bonded organe suullgeompounds the symbol hapto (n) is used before th name of molecule indicating the n¥} per of carbon aL CARBONYES sonsin the carbon bonded ligand. BONDIN cage ett a some examples are given below to illustrate the ‘as already mente er. a carbonylshi eet rypairretectom formed by thedonsl | chon se | ws shown in FB 3. The mt atti pythedo! a pairofletes alent y valint® tibonding P*™ | Rog ofme oxide. pon mom se) Enneacarbonyldiiror (nt) of co jon Scanned with CamScannerCIOS Overlap Fig. 9.8, Honing in metal eartonyta, 0 ligand bonding creates a synergic eh ‘The metal t sions the Nond between CO and de Nickel can be purife ta nes el ied by fing he volatile Ni(CO), and Subsequent oom 7 of Ni(CO),. This procerg is kno gry ; * Monts aa PROPERTIES OF METAL Cap, 1. Metal carbonyls ana Mostiy oC . temperature and Pressure. i a carbonyls are liquits . . 2. The Mononuclear ry _ - e e3FcatbOns ay in a carbonyl complex. 3. Mononuclear: 8 are either aes man ONYLS light coloured whereas Polynucieny Finely divided nickel reacts with CO at room age eine PREP. | coloured liq iture to form Ni(CO),. reen soli tempera Ni+4CO-—> Ni(CO), ae = Fe,co) ‘ higher temperature and 4. With exception of C0), anny Iron reacts with CO at higher temperat soluble in hydrocarbon solvents pressure. Scanned with CamScannerng in co-ordination compounds pondis sain the oe postulates. " eter ra postulates of Werner's theory of ip THe ads are a8 follows: ae COP types of valences called 7 ejence which are ionisabe. (a vi which are non-ionisable. dary valence . (som ce is satisfied by the negative fons in iE etal exits inthe formation of it pase ample, in the co-ordination compound, Feel rence between’ CO ‘and Cl is primary valence ot end 'NH, is secondary. a der theories based on electronic con- he ae ‘valence is now referred to as ‘oxida- eo etal possi me alences are satisfied by neutral ligand «ia Seon re those which metal exercises in the oe fx ions. Every cation has a fixed number are directed in space about central tec ene Gzed directions. The six valences are Jocarners ofa regular octahedron whereas “ather in square planar manner oF ‘This explains the shape of co-ordination ‘etal complex ion or compound) ‘erexample in er-ordination compound (CoCl,.6NH,), :amamia moles linked to Co by secondary valences | Srancted to six comers of a regular octahedron and thus | Sew fr structre of (CoC, GNH,] as follows: SL Fe0, Ite mixed with (NH,),SO, solution in aie Tato ives the test of Fe* ion but CuSO, Rib dog nt With aqueous ammonia in 1: 4 molar ‘not give test of Cu‘? ion, Explain why? — 491 NCERT Textbook Questions Answers/Solutions Solution. FeSO, does not form any comple with (NF, ),50, Instead, it forms a double salt FeSO (E),80 61,0 which dissociates completely into ions. CuSO, when mixed with NH, forms a complex [Cu(NH,),)80, in which the eoraplex ion CulNH,)2* does not dissociate to give Cu” ion. 9.3. Explain with two examples each of the following: co-ordination entity, ligand, co-ordination number, co-ordination polyhedron, homoleptic and heterolepti Solution, Co-ordination Entity: A co-ordination entity constitutes usually a central metal atom or ion, to which are fttached a fixed number of other atoms or ions or groups by co-ordinate bonds. A co-ordination entity may be neutral, positively or negatively charged. Examples are: [Ni(CO)4), [CoC (NF), (CoONH,),, [PtCI,]*, [Fe(CN),)*, Fe(CND,J*, INiCI,(OH,),] ete. Ligand: A ligand is an ion or a small molecule having at least one lone pair of electrons and capable of forming a co-ordinate bond with central atonvion in the co-ordination entity, Examples are: CI-, (OH), (CN-, (CO), NH, H0 ete. A ligand may be neutral or charged specie. It always act as a Lewis base. Co-ordination Number: The total number of co-ordinate bonds with which central atonvion is linked to ligands in the co-ordination entity is called co-ordination number of central atonvion. Pi-bonds, if any, between the ligating atom and the central atonvion are not considered for determination of co-ordination number. Co-ordination polyhedron: The spatial arrange- ment of the ligands which are directly attached to the central ‘atomvion defines a co-ordination polyhedron about the central ‘atom. For example, (Co(NH,),!* is octahedral, (Ni(CO),] is tetrahedral and (PtCl,|* is square planar. ‘Homoleptic and heteroleptic. Complexes in which ‘a metal is bound to only one kind of donor groups are known as homoleptic. For example (Co(NH,),)**- ‘Complexes in which a metal is bound to more than one kkind of donor groups, are known as heteroleptic. For example, [Co(NH,),Cl,)*- 9.4, Give evidence that [Co(NH,),CIISO, and [Co(NH,),]C1 are ionisation isomers. Solution. When they are dissolved in water, they will give different ions in the solution which can be tested by adding ‘AgNO, solution and BaCl, solution. When Cl ions are the counter ions, a white precipitate will be obtained with AgNO, solution. If SO? ions are the counter ions, a white precipitate will be obtained with BaCl, solution Scanned with CamScanner4 naSO, (@) D ; ing) + BC, (00) Or ction IeaINH\ 10, (aq) —-» No reaction + ARNO ia No reaction seat C 4 Ind) * Bac (oa) MgCl) I INH C1 (aq) + ARNO, (2 pot Aoi) fa Specify the oxidation Wy mnbors of the metals in the nt Hein jon entition! o (my ICLP oat SND toni” DYUPICLT mnie eal) foe ICotirslonyh fe) ICANT ICH (CNY) ' NH yaa wen Sotution. (0943 Las : +3 : UeAC norms write the formulas for th 2.6, Using following: te (ID) (e necsmmminccobatt ID) sulphate Rae tetrachloridopalladate (IT) Pr Potassium tri(oxalato)chromate (III) (¢) Diaminedichloridoplatinum (11) () hexaammineplatinum (IV) (©) Potassium tetracyanonickelate (11) (h) Tetrabromidocuprate (II) (i) Pentaamminenitrito-O-cobalt (III) () Pentaamminenitrito-N-cobalt (II) ‘Solution. (a) (Z0(0H), > () [Co(NH,),1(S0,), () K,{PdCl,) (@) K,[Cr(OX),] (© PUNH,),CL,] # (UNH, ),)* @) KINWCN),) (A) (CuBr, @ (CONE) (ONO) () [Co(NH,),(NO,)12* 9.7. Using TUPAC norms write the systematic names of the following: (a) ICONH,) Cl, (6) [CoCINO, (NE, ICL (©) [NNH,),ICL, (a) (PtCI(NH,CH,)(NH,),1C1 (e) [Mn(H,0),* (py [Co(en),}** (@) (TiH,O),* = (4) ENiC1,)> INiCO),1 Solution, (a) Hexammine cobalt (II) chloride (6) Tetrammine chloronitro cobalt (IID chloride (c) Hexammine nickel (QD chloride (@) Diamminechloro(m chloride (e) Hexaqua manganese (II) ion f) Tris(1, 2ethane diamine)cobalt (HD ion @) Hexaqua titanium (11) ion (h) Tetrachloro nickelate (II) ion @ Tetra carbonyl nickel (0) ethylamine)platinum aD ist various of co-ordination compounds Solution. See section 9.1 of 9.9, How many geometri following co-ordination (9 (CeO), Solution, © isomer, eNtitieg, a (9) Only m0 kind of gy, eometric inomerinny 2 (©) Isomers are possnjg ce antl meridional form gr the example given, (oh stereoisomeriam 0. Draw the structures o (@) (Cr0H),)>- Cy) (CrCl femavn,y 1. Solution. (a) Here OX stang for oxalate ing (OOH Pig} is a bidentate chelating ji “On sible. Me Hand To op ime, (cxox,p. Optical isomers of [Cr{OX),)* ion, (6) Only cis-form show ‘optical isomerism, em represents NH,—CH,—CH,—NH,. IPACl,(en)l cis form en~y Cl en end * Optical isomers of is (Pte! Scanned with CamScannerforms, both show optical omer, tra at Mh {enitNElyt* es form Mirror | am ot T r NW trans form 0 a Smiley (©) [Coc Possibes | °CHenvNH, (enXNH,)3)" trans-form ogi oe of [CrCl,(en\(NH,),}*. ape isomers (geometric and optical] of: J‘ yn cote" (&) [CoCK(en),(NH,)* 7 cect (en NE)" ca tcoctycenl” eo geometrical isomers Cis and transforms are All the four geometric isomers are un-symmetrical and each show optical isomerism ie,, forms two optical isomers d and / forms which are mirror image of each other in similar way as shown in (a). ‘Uioymmetnical and show (symmetrical 9.12. Write the geometrical isomers of (PtiNH,) eileen dand? iw eptical womerism) —_ (Br)(C1)(Py)] and how many ofthese will exhibit optical ee isomerism? Solution, The complex PXNE,(BeNCUXPy) wil frm three ‘geometrical isomers ) f Kl or Br Br Pi and I forms of cis (CoCl,(en),]* By * Scanned with CamScannerdo nat show 0 mes ed exam 25 : Jue in cole inte solution (bl pitate with aqueous potassiu eect on olution with aqueot (a Ni sien expermenta eel ae 1s co-ordination iCu(H,),) hich ‘are blue in colour, Water molecule ti dehy Cand F (a) On addition of aqueous KF ‘solution, formed which is green colour. [cudt,0),1" + 4F a t Green pot (tom fioal” ——Cngouble complex entity) iddition of aqueous solution of KCl, an another eles ty formed which is soluble in water 1CuH,0),/"* + 4c ——> ‘from KCI a9 selution) jour) per sulphi anew complex (CuF,)> + 41,0 (cucl* + 4H,0 Bright green solution (a soluble complex entity) 9.14, What is the co-ordination entity formed when ‘excess of aqueous KCN is added to an aqueous solution of copper sulphate? Why is it that no precipitate of copper sulphide is obtained when H,S (g) is passed through the solution? Solution. Aqueous solution of copper sulphate contains Cu?+ ions in form of complex entity, (Cu(H,0),]* and HO ligand is ‘a weak ligand. When excess of KCN is added, a new co-ordination entity, [Cu(CN),]* is formed due to following reaction : [Cu(H,0)* +4CN- = —> (from aq. KCN) [Cu(CN),* + 41,0 (highly stable co-ordination entity) Cyanide ligand CN~is a strong field ligand and stabil- ity constant of (Cu(CN),]* is quite large and thus practically no Cu** ions are left in solution. (On passing H,S gas, no CuS is formed due to non-avail- ability of Cu’ ions in solution. 9.15. Discuss the nature of bonding in the following tion entities on the basis of valence bond (a) [Fe(CN),.J+ (©) (FeF,J* (e) [Co(OX),]* (d) [CoF,]*. Solution. The valence bond theory, VBT was extended to co-ordination compounds by Linus Pauling in 1931, It involves the basic principle of a suitable hybridisation in central atom/ion in presence of ligands and making of bonds between FerVed py he MR in | State of Rg; ‘omplex (a) Nature of bona The oxidation number is 6, The e experimental study shows ey a hat it The bonding in this on the basis of overlap of gyn init, the six lone pair orbitals o¢ ey 24 ms, N= ‘Tho outer elec T lectronie eo formation of complex ing ™atinn, hybridisation and six yer? Pe ion 1 mn and six hybrid erbjgg 2 bila eg clectrons each trom six evan; rani te is lef and thus [Fe(cy) je i ion ang ion is brid an nh ligand "ly Fe" ion Bd eel Fe" ion i444 41414 6 pairs oes 6 It is an inner orbital complex. (b) Bonding in [FeF,}* ‘The oxidation state of Fe is + 3 and its number is 6. The complex has octahedral ge experimental study shows that itis paramagnetic ‘The bonding in this entity is explained «=! overlap of sp°d®-hybrid orbitals of Fe™ ion (one 4s, and 4d-orbitals have been involved and not stb six lone pair orbitals of eyanide ligands. Five i= unpaired which make it paramagnetic.Tisit 0 configuration of Fe™ ion is 34% whichis _ ei pairing of electrons takes place evenin prs of F- ions. Here, 4d-orbitals of Fe™ (nti involved. Scanned with CamScannernote isan Comair al complex ny : {@) Bonaing inte hag 9,1 tation ty ion number is 6, a experimental sto ing that there mre = ing of eetrons ta Fg Maire electrons kes place in Cai 7 ap’ d'-hybrid orbitals st are formed strong field of ligand ion even in " ie bonding tat Teeny onan ego El — ft co ix pairs of ¢ from 6F ions a jg strongly paramagnetic due to five vlalayaya nis e280” Djs an outer orbital ‘complex. jg in (CoO) (q Bonde "arate of cobalt is + 3 and its co-ordina- essa Complexhascets LS femal ie cgperimental study 7 : TPE) EEE six pars of from 6 ions cceupying 6 sp'd-bybrd orbitals As there are 4 electrons unpaired in complex speci, it . is entity is ding in this ent w ee of overlap of 47sp*- a" an sss is paramagnetic adit isand ner bal complee enree 0 ligands. - potas ara ration of Co® ion is Sa®. 9.16, Draw igure ta show sniting of ener dar a cea creatty, under the influence of strong Bel ssrution, The figure of spliting of orbitals shall a pestirma? aj six electrons gets paired UP (disobeying ows. Las become available for jealste ital: ; 4 two Sd-orbitals n 4 ee mle) any electron is left unpaired and entity 00, bewmes diamagnetic. . Bnerey vey ry 4p 4 1 tpt L_| =) ined orbitals in ree ion 6 pairs of e from 30x" ions Scanned with CamScannertds and sak heen produce wer fing of bial in order of increasing argo whereas ot i al lit af the ions 1 of he rochemical series, 120,00 < 1,0 split eEitequently Fo “re arrange aie known 08 Dee ScN-< cl <8?

pairing energy, ‘then pairing of electrons will occur and hence configuration tf, ie., low spin complex is formed. i) However, if 4, < pairing energy, then high spin complex is forme ‘Thus, strong ligands will have greater value of 4, and hence low spin complexes results and vice versa. 9.19. [(Cr(NH,),]* is paramagnetic while [Ni(CN),]* is diamagnetic. Explain why? Solution. See section 9.7 of text for explanation, 9.20, A solution of [Ni(H,0),}* is green but a solution of INi(CN),}* is colourless. Explain. Solution. The ground state configuration of Ni (2 = 28) is 8a°.4s2. In Ni* ion the configuration becomes 3d®, Water (H,0) provides a weak ligand field and as a result Ni undergoes spd? hybridisation in formation of complex [Ni(H,0),!* ion. 3d is p niet" DOOD OOO OG) sp'd! hybridisation rystal field splitting energy). tis there are of wn aied absorbed and the complex apnea” Me Inthe canwaf Nicene fateona ligand eld wnt tt Bd orbitaln to get paired. WE un, dlp? sbrisation, Sinen agg =°Png orbitals, no d-d transitions Complex is colurlean ul wera? OOODS 9.21.{Fo(CN41 and (Pett In dilute solutions: why? Solution. In bath the eomplezen water molecules exert diferent ete 2 ae etna iw gt Accordingly, different compan" (VIBGYOR) shall be absorbed any nt" tha colour would be different i., the nictér= be different (see section 98 of tox ny 9.22, Discuss the nature of bonding. Solution. See section 9.12 of text, "hey 9.23, Give the oxidation state, co-ordination number of the following complexes: mur of Orbital cee, ental maa @ K{COC,0),) «oy (6) cis {Crlem,C11C1 (a) (Mani Solution. PMso, (a) Oxidation state = + 3, ¢; Pa et at complex ie, fe, the 3 (6) Oxidation state = 6 2, Coon meat @ (et,$) tetrahedral, unpaired. cea (c) The indication thatthe compound means it must be square plana sine configuration in a tetrahedral shape «, (d) Oxidation state = + 3, Co-ordination nuste. @ (t,,8), unpaired electron = 3, 4 9.24. Write down the IUPAC name for each i following complexes and indicate the oxidation sa electronic configuration and co-ordination nie Also give stereochemistry and magnetic monet complex. (a) K{Cr(H,0),(C,0,),13H,0 () CrCl,(py)y (c) K{intC®) (a) (CoNH,),CHCI, ——_(@) Cs{FeC) Solution. (a) Potassium diaquabis(oxalatokhronst drate, oxidation state = + 3, d, enig=\'y' CN =6, shape = octahedral, 3 unpeirel e* Scanned with CamScannerjainechromiuum (IID, oxidati # s: = octahe. Jou SE hoxacyanom an am He ganate (ID), oxi q je, confit = (a CN D, oxidation acl, eye red ele 6, she io wesc 1 v0 tron. ee ee AID chloride, mmr momen eh prete + d® config = (tag80,0), CN = € oxidation eth momen (oHlowin, + tea fie > a umpaired electron Ojsharae Sokiion. (Cran, Mone whe NE ocr ye ver juloroferrate (II), oxi bet LO a ome has’ peti age tN = D, oxidation state ital ee Ith ae ta Neen ep cnt ro. ahaa ede ang 9TH "ny ete aang f ions arah® efinveain at A octahedra nat by stability of a co-ordl Ey ion of chroma Yer ama? State the fctors whi oe Henee te 1, ett) ant Zn ch Rove paieed eens hath Maa ' rons ant ne ie ra 4% see ection 9.30, The oxi Zn has neato, Fe ati areas Pha a. ee een chelate effect? Give an exam faye atian mumber of on teen spe complexes which are formed by chel aan (e=1 “a se canlen® .e (en), EDTA, ete. are more me lution. (c) The oxid (h-3 ont formed DY ‘monodentate ligands such as H,O ‘8 hence oxidation number af Gon 7 * 2 aoe ‘of complexes contai ) or 9.31. Amongst ofCo=— 1 Ca = 2009 an fi ends called Be effec ning, ieetowt yi * ca t. For example, the (a) [Fe(Ht,0) ing, the most stable ie sci end enis ore : Gwe ee _— ‘th " le than [Fe(C,0)* SH) eg ces A ammonia ligand. Solution. (c) Oxalate (o) (Rech ge Si 6 (oP Se [Ni(NE,),)* (a0) Jog B= 86 Sebel) Oras YOO woes ae aye) — Irion." (aqhlog B= 1828 Srayeraion inthe ones - 5 5 . of abso : order of the pisos briely ving an example in each case the any ee aes vr eoordination compounds in (a) biological (a) (NiNO,) I (by (NNT) F* reas () analytica! chemistry (c) medicinal (e) (NiO aecisey jon/metallurgy of metals. Solution. sision See section 9.11 of text for solution to the given Tete ie ition 0- unpaved electron WER Give 1PAC name and draw the structure of: (ONWCO), (6) Fe(CO), (e) [PtCL {Cyl JF (a) (Cr(CO) Solution. (a) {Ni(CO),) TUPAC name: Tetra carbonyl nickel (0). It has tetra- hedral structure as it involves sp?-hybridisation. (tetrahedral structure) (©) (Re(Co),]; TUPAC name: Pentacarbonyl iron (0). Tthas trigonal bipyramidal structure. cl CH ac (Cipyramidal structure) () IPCL{C,HIr; TUPAC (accetylene) platinate (Il) ion, (@) (CXCO),]; TUPAC name: Hexa carbonyl chromium (0). It has octahedral structure, name: Trichloro 0 au co co. (octahedral structure) “ 0c’ WERE Discuss the nature of bonding in (Ni(CO),. Solution. Nickel atom is in zero oxidation state and its co-ordination number is 4. It ‘involves. sp*-hybridisation in formation of (NCO), and possesses tetrahedral eometsy ian four CO ligands are linked to Ni atom by usual four (signs) bonds. The single Ni~CO bonds are weaker covalent Denke Scanned with CamScanneria) atone a conc) Ol ul ‘oo pel Ul 7 tet ei psi) ad PEELE epee From four CO ligands four pine of i ed tall 8 0 in its structure, itis jred olectron in its st ‘As there is no unpai dinmagnetic. the core formulae for the following co-ordina- Write ee ch ,0 (oiolet, with 3 chloride ions/unit la) : Greiest,0 light green colour, with 2 chloride {ons [unit formula) (e001, 0 ark green colour, with 1 chloride lution i et coarinaton compounds are ‘The above three co-ordination comy 7 sense epi form of ionisation, called Hydrate Isomer- jam, Water can exst.as a part of co-ordination entity or a part cit sdethe wardnaton entity. ) ICH, 0 all three Cl ions are Pree outside the co-ordina- tion entity ) [CrC1GH,O)JCly HO: one CI ion is a part of , co-ordination entity and two are outside of it. two Cl-ions are a part of co-ordination entity and one outside of it. ____ The Cl- ion outside the co-ordination entity are inmisable and forms white precipitate with AgNO, while Cl- ions which are part of o-rdination entity are not fonisable. (6) [CrC1,1H,0)JCL2H,0 : What is understood by the generalization ‘magnetic err ofthe bond typ? Mlustrate your anatuer with suitable sxamples, Solution, The generalisation ‘magnetic eriteria of the bond ‘ype’ means that the geometry of co-ordination ent are a ‘edie its magoeticbehavour is known ie, whehon eg, For example: (NV(CN),)* ; spears tobe similar and neat totam again similar behaviour Corbibening and similar shape, But experin, [NWCN),)> is diamagnetic white mt , In order to explain and unders it is required that bonding ig unpaired electron in [NWCN), in [NiCl,)” entity Ie requires dsp®-hybridisating Similarly, INWCD,P equi bonding with four Cl tiga giving two unpaired electeons in yg, paramag and iy Mauch Pantin. tet Fahy “ ital, quare-planar geometry, tetrahedral geometry for (Nic) 00" X-ray studies. ave Using the valence bond appre ‘magnetic character of (Cr(CO),) Tae etic th 1, of ey Solution. In the complex, (Cx(Co), 7 mh oxidation state. } coin Grin zero ox. state (24) ad 4s ifafats}a Hybridised d’ sp’ orbitals in Cr (0) in presence of ligands ad aioe [] [cx(Co),)” 3d vfaofe ofey= La six pairs of elatrasing ix CO molly [CHCO),) is octahedral due to a°sp!-bybridsin central atom. Itis diamagnetic ast does not havean sin. [EER Using the valence bond approach, predict the shapead ‘magnetic character of [Fe(ON),}™ ion, (At no.ofFe=2#) Solution. The oxidation states of Fe is + 3 in [Fe(CN,l*ia ‘The outer electronic configuration of Fe* ions andnte formation of complex ion, (Fe(CN),]™ the Fe ion usd @sp*-hybridisation, Due to d°sp°-hybridisation, it bs octahedral shape (or geometry). Six hybrid orbitals reset pair of electrons each from six eyanide ions. The pres one unpaired 3d-electron in the complex ion mais Paramagnetic as shown below: Scanned with CamScannereon of F (20) ad 1] 1] for coordination «the valence bord approach, predict p uate of (CINE. At no of on Stepeand Bee ere number of Co i827 and iti in ag Sto ine complex and has 38 pola 43 state of Sn gn scheme 38 as follows: tration, The wa fe as ; ial » Po OQ ® LT] A lala | aa a + lands approach central atm, rears _ Ai getectrons take place due to energy changes and buble six vacant orbitals which hybridise to fa pecomles oe fp api rita of Co lel d'sp*-hybridisation dsp?-hybridisation ‘There is no unpaired electron in the complex, it should vediamagnetic. Due to d?sp*-hybridisation, complex is ‘wtahedral. NH, As this complex is formed by use of 3d-orbitals with 45 2 pip, it is called inner orbital complex. This t¥Pe of or vill complex in either diamagnetic Or ‘unpaired electrons and is a8 © are param faetatmaedeal Ni (1D) compleses OP PGi Patarenre planar Ni(ticompleses wr (wong transition metals are MO complexe. involve 8? ecmlee al Nill) compleze® iO ore Liybridiation during their formation and 1 see the em Ta ora tr eta of Ni in wich makes lex paramagnetic. Ni" Gin tetenhesteal comple) Bd 4s 2 corns 0 CLD cp ghetination Square planar Ni (11) complexes involve dsp" hybridisation dub their formation and there areno unpaired electrons lef in the complexes of this type and thus they ore diamagnetic. [Ni Gin square planar complex) dap -aybridisation (Gi) r-complexes are the compounds of transition metals with ligands of the type earbon monoxide, allenes, allynes, benzene and other ring systems like pyridine ete. In such compounds metal-carbon bond arises from interaetion between scelectron cloud of ligand (unsaturated-hydrocarbon) and partially filled d-orbitals which are present on metal atoms oF their ions see bonding of metal carbonyls (section 9.19). Since the transition metal atoms or their ions have partially led orbitals these can form bond with unsaturated ligands. Draw the structures of- (a) Cis-dichlorotetracyano-chromate (aD () Mer-triamminetri chlorocobalt (mp (c) Fac- +triaquatrinitro-N-cobalt (mb. Solution. The structures of given ‘co-ordination entities are: cr @ | ® cr CN cis-dischlorotetracyano Mer-triammine trichloro ‘chromate (I) cobalt (11) Scanned with CamScanner1 enn of ie ftom Pert of etre iain? reg Pett or tend cle nl ce fen equnre iNWCN YF poo she wag earth tec Rs ae pntt at bipyramidal Mane nl 7 aa) iiayare shown : se it ioe oe dap'-hybrid orbitals dsp*-hybrid co “ap? hybrid orbitals (inner orbital complex) or apse nthcaebats Coster ‘orbital complex) both have cciahedral shape with bond angle 90°. Examples are {Gri and (CotNH)” are inner orbital complex while {CoFe,)*-and [FeF,)* are outer orbital complex. ; (d) sp? -hybrid orbitals have tetrahedral geometry with bond angle 109°28'. Examples are: (Zn(NH,),)** and [FeCl }~. sp? dbybrid orbitals sp*-hybrid orbitals (octahedral shape) (Tetrahedral shape) MEW Explain on the basis of valence bond theory, the experimental findings that [Ni(CN),]ion with a square-planar structure is diamagnetic and the (NiCl,F- ion with tetrahedral geometry is paramagnetic, Solution, Valence bond theory, extended to co-ordination com- ounds in 1931 by Linus Pauling, ioaefll eoleee ta amagnetic nature of [Ni(CN),|* as follows: = COMPNC Cine y tn presences of stron field a ’ 76] err CI fire +[+[1] EE 4 pecnct It in square planar compe, hybridisation. The complex is dian, unpaired electrons. On other hand, Cl- is weak eta no pairing of 3d electrons takes place in art rule is obeyed). It is represented as follon "3 ts o OU elle) | four soasbri oma, four pairs of electrons from CI in sp bbe, ‘Thus, [NiCl,]*- has two unpaired electrons and tan’ is paramagnetic Mnetie "8 Atomic orbitals of Ni’ ion (3d") ad V/V} r}1)4 sp*-hybridised orbitals of Ni” Vivi o] 141 HR Explain with examples geometric and optical isn Solution. (a) Geometrical isomerism: Two entities (or complex ions) are said to be geometrical iam when they differ in the arrangement of their liganésia This type of isomerism is of importance in 51 planar, [Ma,b,] and octahedral [Ma,p,] co-ordination at g., [PtCl,(NH,).] and [CoCl,(NH,),}* ete. Scanned with CamScanner