After stuctytng this Unit, you will be able (0 * appreciate the postulates of Wemer's theory of coordination compounds; + Ruow the meaning of the terms: coontination entity, central atom/ ton, tygand, coordination number, coordination sphere, coordination polyhedron, oxidation number, homoleptic and heteroleptic: Jearn the rules of nomenclature of coordination compounds; write the formulas and names of mononuclear coordination compounds: define different types of isomerism in coordination compounds; understand the nature of bonding in coordination compounds in terms of the Valence Bond and Crystal Field. theories; appreciate the importance and applications of coordination compounds in our day to day life, OTE COT Compounds are the backbone of modern inorgant 4 Compouril andl chemical netusery, In the previous Unit we learnt that the transition metal form a large number of complex compounds in whic] the metal atoms are bound to a number of anions neutral molecules by sharing of electrons. In moder, terminology such compounds are called coordinatios compounds, The chemistry of coordination compound is an important and challenging area of modert inorganic chemistry. New concepts of chemical bondiny and molecular structure have provided insights inti the functioning of these compounds as vital component) of biological systems, Chlorophyll, haemoglobin an¢ vitamin B,, are coordination compounds of magne iron and cobalt respectively. Variety of metallu processes, industrial catalysts and analytical reagent involve ‘the use of coordination compounds Coordination compounds also find many applications 1n electroplating, textile dyeing and medicinal chemistry Alfred Werner (1866-1919), a Swiss chemist was the first to formulatt Qt Werner's Theory ‘of his ideas about the structures of coordination compounds. He preparet ry Of and characterised a large number of coordination compounds an¢ Coordination studied their physical and chemical behaviour by simple experimenta Compounds _ techniques. Werner proposed the concept of a primary valence an¢ a secondary valence for a metal ion. at primary 2 and 2 respectively in a serles of compounds of cobalt(III) chloride with ammonia, it wat found that some of the chloride ions could be precipitated as AgCl of dang excess silver nitrate solution in cold but some remained it solution,- 2 a ee 8 1mol Cocl,.6nn, (Yellow) CoCh.5NH, (Purpte) i a SoChANH, iGreen) gave 1 intl AgCl hese been MMe gave 1 mol AECL . mateiurenionte: Te uons: together with the results of conductivity either ehloride tons or won ca" be explained If (i) ste groups in all, the cobalt ion durin {™™Oonla molecules or both, remain bonded to fas shown in Tables “eacton and (i) the compounds are formulated form a single Ge L, Where the atoms within the square brackets conditions. giana’ gwilch does not dissociate under the reaction r of groups bound ae the term secondary valence for the rectly to the metal ion; in each of these Soe aed ce fave — 3 mot Agcl gave 2 mol AgCl 1 mol mateo; Tormulation of CobaltiIn) Chforide-Ammonta Complexes feesnis hoe Petter aid {CotNH)_I*3cr [Coctontis)s"" 1 [CoCl(NH,),)"Cr a ge [Coc,(NH,),'er ; " Note that the last two compounds in Table 9.1 have identical empirical formula, CoCl,.4NH,, but distinct properties. Such compounds are termed as isomers. (Werner in 1898, propounded his. theory of coo! is: The main postulates are: i »1, In coordination compounds metals show two types of linkages a (valences)-primary and secondary. , and are satisfied by negative ions. le further postulated that octahedral, tetrahedral and square planar \ geometrical shapes are more common in coordination compounds of transition metals. Thus, [Co(NHg)e”, {CoCl(NH,)3|” and (CoCl,(NH,),! are octahedral entities, while [Ni(CO),] and [PtCl,|” are tetrahedral and square planar, respectively. 1245; Coordination Compounds 7On the basis of the following observations made with aqueous solutions, Example g) 9- assign secondary valences to metals in the following compounds: OCC m oe ceca Come the compounds with excess AgNo, Poe () PACI,.ANHy, (i) NICL,.GHO (tit) PECL,.2HCI (tv) CoCh.ANHs (W) PtCl,.2NHy (i) Secondary 4 (i) Secondary 6 Solution (411) Secondary 6 (iv) Secondary 6 (¥) Secondary 4 Difference between.a double salt and a complex Both double salts as well as complexes are formed by the combinatior of two or more stable compounds in stoichiometric ratio. However, the ced CN to ‘Wemer was born on December 12, 1866, in Mulhouse, a small community in the French province of Alsace. His study of chemistry ‘began in Karlsruhe (Germany) and continued in Zurich (Switzerland), where in his doctoral thesis in 1890, he explained the difference in F properties of certain nitrogen containing organic (1866-1919) substances on the basis of isomerism. He extended vant, Hof's theory of tetrahedral carbon atom and modified it for nitrogen. Werner showed optical and electrical differences between complex compounds based on physical measurements. In fact, Werner was the first to discover optical activity in certain coordination compounds. He, at the age of 29 years became a full professor at Technische Hochschule in Zurich in 1895, Alfred Werner'was a chemist and educationist. His accomplishments included the development of the theory of coordination compounds. This theory, in which Werner proposed revolutionary ideas about how atoms and molecules are linked together, was formulated in a span of only three years, from 1890 to 1893. The remainder of his career was spent gathering the experimental support required to validate his new ideas, Werner became the first Swiss chemist to win the Nobel Prize in 1913 for his work on the linkage of atoms and the coordination theory. Chemistry 246,z Sa itions of (4) Coordination 2 Defimt™ f x ih entity Some to.a fixed numbee 2, onstitutes a central metal atom of ion borided [mportant 1s a coontination Ot tons or motecutes. For cxample, [COCHIN Jl three ammonia mons, Which the cobalt jon is surrounded bY Te are INICO}. Perec ileS atid three chloride fons. Other igo cntead nN LACHINH.. tRetcNn (CoN). @oordination it atomyion In a coordi Of lons/ groups RULY. the atom/ton to which a fixed number ind in a definit i nt around it, is cal inite geometrical arrangeme! central atom /r 4, te central atom or ton. For example, the Compounds {CoCl(NH,)./* and irc the coordination entities: [NiCI,(H,0).J. ‘These central at g (c) Ligands cearts OF Molecules bound to the central atom/ion tn the IFe(CN)I* are Ni*, Co” and Fe". respectively. ‘oms/ions are also referred to as Lewis acids. entity are called ligands. These may be simple fons such 2s eral Molecules such as H.O or NH, larger such as proteins ant OF NICHLCHNE,) or even io he I ed 7 CH.COO Bec —N~cH,coo™ a | yp ORCOT ne —cH,coo™ Ze Optical tsomers (d and I of cts- en en [PtCl{er),F* dextro mirror 7 Chemistry 252, ieee tetrahedral complexes f unidentate ligands coordini ligands attached to the central cl cl Gt Pt ‘This type of isomerism alge arises when didentate ligand, LoL fe. NH, CH) CH, NE, feny) are present in complexes of formula IMX,(L-~ Lh) (Fig. 9.4. ated with | isomerism because other. Optical isomers are mirror images that cannot be superimposed on one another. These are called as enantiomers. The molecules or tons that cannot be superimposed are called chiral. The two forms are called dextro (d) and laevo (l) depending upon the direction they rotate the plane of polarised light in a polarimeter (d rotates to the right, | to the left), Optical isomerism is common in octahedral complexes involving didentate ligands (Fig. 9.6). In a coordination 2+ entity of the type x] [PtCl,{en),]". only the cis-isomer shows optical en _ activity (Fig. 9.7). c™ laevoNH, a NH, z new | Pa new | Se! ne“ Son not New cN we =a trans .6 Out of the following two coordination entities which 1s chiral (optically active)? (@) cts-[Crcl(ow* (b) trans-{CrCl,(ox).J” Solution ‘The two entities are represented as ox gare C) yet i ei a ‘ ox @) cis—[CrClow,J” —_(b) trans [CrCl,(ex).” Out of the two, (a) cis - {CrC1,(ox),]* is chiral (optically active). 9.4.3! Linkage isomerism arises in a coordination compound containing simple example is provided by complexes ranate ligand, NCS", which may bind through the nitrogen to give M-NCS or through sulphur to give M-SCN. Jorgensen. discovered such behaviour in the complex [Co(NH,)s(NO,}|Cl, Which is obtained as the red form, in which the nitrite ligand is bound through oxygen (-ONO), and as the yellow form, in which the nitrite ligand is bound through nitrogen (-NO,). 94.4 ‘This type of isomerism arises from ‘hea tween ———— cationic and anionic entities of different ions present in a complex. An example is provided by [Co(NH,)gI[Cr(CN}d]. in, which the NH, ligands are bound to Co” and the CN’ ligands to Cr™. In its coordination isomer [Cr(NH,}gl[Co{CN).], the NH, ligands-are bound to Cr and the CN ligands to Co”. ‘This form of isomerism arises when the which can then e counter ion. An example is pune by the ionisation somers [Co(NH,),(SO,)]Br and [Co(NH)sBr]SO, ;283,_Coordination Compounds94 ‘This form of isomerisin is known as ‘hydrate isomerism’ in case where water fs involved as a solvent. This is similar to lonisation isomerism, in the crystal lattice. example is provide the aqu; complex [Cr(H,0),ICl, (violet) and its solvate isomer [Cr(H,0)-CIICl,.H,0 (grey-green). Intext_ QQuestions 9.3 Indicate the types of isomerism exhibited by the following complexes and | draw the structures for these isomers: (@ KICT(H,O),(C,0.2 Gi) (Cofen)3JCl, iti) [Co(NH;),(NO)I(NO3. (iv) [PtNH)(H,0)CL} 9.4 Give evidence that [Co(NH,),ClISO, and [Co(NH,),(SO,)ICI are ionisation isomers. 9.5 Bonding in Werner was the first to describe the bonding features in coordination @oordination compounds. But his theory could not answer basic questions like: Compounds Why only certain elements possess the remarkable property of ae OO. forming coordination compounds? (i) Why the bonds in coordination compounds have directional properties? (iW) Why coordination compounds have characteristic magnetic and optical properties? Many approaches have been put forth to explain the nature of bonding in coordination compounds viz. Valence Bond Theory (VBT), Crystal Field Theory (CFT), Ligand Field Theory (LFT) and Molecular Orbital Theory (MOT). We shall focus our attention on elementary treatment of the application of VBT and CFT to coordination compounds. 9.5.1 Valence Bond Theory Dee eat | Corer eet Tetrahedral Square planar ‘Trigonal bipyramidal Octahedral Octahedral Pieters cry ptrore. m. = yl aqyoeiaiset grco"ion 20 tas co” Rec ee owe me TN % x I _ tO al oF on complex) Tes usual Porstble (9 predet. the eometry of a complex from the knowledge of its ttt TF] oO Ean Magnetic behaviour on 3d rry ap the basis of the valence bond theory, La a In the diamagnetic octahedral complex. C9 hybrid (COIN), the cobalt ion is In +3 oxidation state Tei ein Tiffa[t] @nd has the electronic Six pairs of electrons COMMguration 3d*, The from abe NHS hybridisation scheme is as molecules shown in diagram. Stx pairs of e1 lectrons, one fj hybrid orbitals. Thus, the camples feet molecule socty aad OF le can ectUse ofthe absence of unpanea eee formation plex, the inner d orbital (3d) is used in iybridisation the complex, [Co(NH)l"" is called an paired « The orbital or low 2 edseliet 2 ban Paramagnetic octahedral complex, (Cord woes qpialsofcovion «= [tM] tt] 7] + a 3d ea ap aa fe wridised gin ttlt [ty] + O rT} £0) 3a spd hybrid ad (cor J” fouter orbital or tut[rlt[t ae LT] high spin complex) 3a ‘Six pairs of electrons ad a from six F ions In tetrahedral complexes votasofneion [tre] a] + CI aiigedtoe Gee 3d. 4s 4p equivalent orbitals oriented hybridised tetrahedrally. This - + thials of Ni purrs] +] | ustraled bella Be INL 3d sp" hybrid Here nickel is in +2 = wor oxidation state and the ion. bghspincompiey (tY{te[ry]t [+] [repra[rsry] has the —_ electronic Four pairs of electrons configuration 3d°. The from 4 Cr Each CI ion donates a pair of electrons. The compound is paramagnetic since it contains two unpaired electrons. Similarly, [Ni(CO),] has tetrahedral geometry but is diamagnetic since nickel is in zero oxidation state and contains no unpaired electron. 12884, Coordination Compounds.A! cavern] ?- ner i 9.5.2 Magnetic Properties of Compounds Canc 2 9D Fen? 21 Chemistry 256, in ¢, aa SO« "y fd 5 In the square planar comy complexes, the hybridisation involved is . sample is [NI(CN),’, Here nickel is in +2 oxidation state mnie q ‘clronic configuration 3d”. The hybridisation scheme is a8 shown, in diagram: Orbitals of Ne“ion [ti] ta[tap t [+ =| 3d 4s 4p dsp’ hybridised orbitals of Ni” PN At [ 3d ‘dsp? hydrid 4p foweee compten [elte]relty afr eft apts 3d Four pairs of electrons 4p cyanide ion. The compound is diamagn from 4 CN groups Each of the hybridised orbitals receives a pair of electrons from a of unpaired electron. It is important to note that the hybrid orbitals do not actually exist In fact, hybridisation is a mathematical manipulation of wave equation for the atomic orbitals involved. ‘The magnetic moment of coordination compounds can be measured 9-4 the magnetic susceptibility experiments. The results can be used to by obtain information about th Coordination and hence structures adopted by metal complexes. . and [Co{C,0,)sI” are 1° Loft, the former two complexes are pé etic as evident from the absence e number of unpaired electrons (page 228) ‘A critical study of the magnetic data of coordination compounds of metals of the first transition series reveals some complications. For metal ions with upto three electrons in the d orbitals, like Ti” (d'); (@); Cr* (@); two vacant d orbitals are available for octahedral hybridisation with 4s and 4p orbitals. The magnetic behaviour of these ‘with co tio with species containing d' and +> p)vut: has magnetic moment of two re ilal ‘consequence of is not: i Thus, for d' (Cr“, Mn"), d (Mn™, Fe”), d (Fe, Co”) cases, a vacant pair of d orbitals results only by pairing of 3d electrons vle-which leaves two, one and zero unpaired electrons, respectively. "ions there are complications. [Mn{CN)_™ unpaired electrons while [MnCl,|” has a .etic moment of four unpaired electrons. [Fe(CN).)" has magnetic moment of a single unpaired electron while [FeF;|” has a paramagnetic moment of five unpaired electrons. [CoF,]* is paramagnetic with four unpaired electrons while [Co{C,OJs]” is diamagnetic. This. aj is i ‘ ct formetion of ed by valence outer orbital: inner orbit theory in terms entities. [Mn{CN).I*. [Fe(CN)” {tal comp! involving cf sp” hybridisation, etic and the latter diamagnetic. On the other hand, [MnCIJ°, [FeFl” and [CoF,]” are outer orbital { “a {uly complexes involving sp’ corresponding to four, five and four unpaired electrons. As hybridisation and are paramagnetic 4EL ware. BE. Tos tpn eal hemes (imaged 5 BM. Predict the | gromety ofthe semper eto MAB \ Since the coordinat a teenies will be either canatlon number of Mn ton in the complex tase | planar Bioidieation). But the rend, the pct mcrae \ Solution magnetic moment of the complex BM, it should be tetrahedral presence of five ___ Planar because of the, pimitations While the VB {heory, toa larger extent, explains the formatlo from oss of Vulemoe the utustlc behaviour af coudinatios sompeceae # outers Bont a i qheory @ Itinvoives a i number of assumptions. (i) It does not give quantitative Snterpretation of magnetic data. ww Tf does not explain the colour exhibited by coordination {dees not give a quantitative interpretation of the thermodynal : or Kinetic stabilities of coordination compounds. aral ©) Tt does not make exact, regarding the t = fauare planar structures of 4-coordinate complexes. (0) It does not di ‘stinguish between weak and strong ligands. gs Crystal Field ‘The crystal feta % : a point charges in case of arlons of point Sines ores of neatral Bine otne mete als i an nated ioe meta tor ion ve sr they are coal bei egune chars " fara atom/ lot Hower anions or the negative ends of dipolar molecules depends 2nd 1.0) in a complex: tt becomes asymmetrical and the field. Let us explain this splitting in different crystal. " (@) Crystal field splitting in octahedral coordination entities In an octahedral coordinatios the metal atom/ion, ' @S%\ Coordination Compounds ‘ adegenerate levels due to the 2 & presence of ligands in = L A 1. definite geometry is termed ay S-(O)~ A Ee aeeng i u L separa aad L pil subscript 0 is fop Pe iran (Fig 9 8) Thus the 2 d, ’ of the two ¢, orbital t wy ot” Tra, MT creme by (/5ha, and S ote ; that of the three 4, ~~, me ty 4d, , ¢ et w ss. J2/5a, a d, dd.) tie Metal, orbitals 7 d, dd, Average energy Splitting of d orbitals of the d orbitals in in octahedral Free mietal ion spherical crystal field —_erystal fleld Fig.9.8: d orbital splitting in an octahedral crystal field In general, ligands can be arranged in a series in the order of field strength as given below: I
P; it becomes more energetically favourable for the fourth electron to occupy a ty orbital with L tage,” a which produce this effect are known as strong. and form low spin complexes, are more Calculations show q sabieter strong field as compared to weak field cases. Chemistry 9258v SR ON ® Srvmtal ott splitting in fetranedrat coordination entities Tietttahedral coordination entity formation. the d orbital » fitting (Fig. 9.9) ‘gman to the werePlitting. For the same metal, the same Mgands and mMetal-ligand distances, it can be shown tha (9) Ay. Consequently, the orbital splitting energies are not l toa Fotis Average, le Suffletently large for forcin; pairing and, ieee TRESTRAO units erefore, low epin configurations ore fare Srnaigad hc pa ved: The 2! gia sping ‘a tetrahedral crystat pers ' f mialuit: we learnt ‘that one of the moet di colours. rordination Properties of metal omiplenes et thelr wide Tange fe 2 Compor wee that some of the visible spectrum is being re som w ar Passes through the eerie ene rte at anger White, The colons at that which 18 absorbed, ‘n 4s not used with energy levels. ysscolourin In the previoy is means v the complex is complementary to ¢ complementary colour is the colour » it appears red. Table 9.3 Gifferent wavelength absorbed avs the ¥ Co a ae Colour of light crag pas Rc) Der [CoClNH}5)"" ICo(NH)s(H0)]* | [Cott Blue | [CofCNl™ = Ultraviolet N°* St visible Red [cu(tt,0),1*" 600 mtH.0)." { 498 Blue Green SR ‘The colour in the coordination compounds can be k . in terms of the Crystal fleld theory. Consider, for example, the complex MT(H,0)_1", which is violet in colour. This is an octahedral complex fisre the single electron (It is a Sd system) in the metal d coun in the fc level in the ground state ofthe comilex. The next higher ctate ' available for the electron is the empty ; level. If ight corresponding to the energy of blue-green region is abs sorbed by the complex, it excite the electron from ty level ta the @, level (t,'¢,° tag ee > tag ey). Consequently, | sgrales Spears viclet in colour (Fig: 9.10): The crystal field yr tes the colour’ of the coordination sere stots (8% Coordination CompoundsIt Is tmportant to note that -- + $= hence ror a ma example, removal of Water ae be. from [THH,O}ICh on heating : bn renders tt. colourless, Similarly, anhydrous CuSO, 9 white, but CuSO,.5HLO fe influence Fig.9.10: ‘Transition af an electron in {TUH,O)," blue in colour. The sed of the ligand on the colour , sidering the [N(H,O)l”” complex, dissolved in water. If the rogressively added tn the series of reactions and ground atate of a complex may be illustrated by con: which forms when nickel({I) chloride 1s didentate ligand, ethane-1,2 diamine(en) {6 pt molar ratios en:Ni, 1:1, 2:1, 3:1, the following their associated colour changes occur: INI(H,O)I" (aq) = ten (aq) = (NiG,0)(en)I"(aq) + 2H,0 pale blue green IN1(H,O), (en)}*"(aq) + en (aq) = INWH,O),(en),1"(aq) + 2420 blue/purple + 2H,0 [NIGH,O),(en),f"(aq) + en (aq) = INifen)s!""Caq) violet ‘This sequence is shown in Fig. 9.11. = seEE ‘on bag | Fig.9.11 i iil j a ‘Aqueous solitons af I. La Hf complexes i ee ricket wth an seo)" aq) _ |p Fa " g IMilenk* faq) increasing number of ethane-1, 2-diamine ligands, INi(H,0),en]" (aq) [NI(E,0),en,]” (aq) Colour of Some Gem Stones ‘The colours produced by electronic transitions within the d orbitals of a transition metal fon occur frequently in everyday life. Ruby [Fig.9.12(a)] is aluminium oxide (Al,0,) containing about 0.5-1% Cr” tons (4°), which are randomly distributed in positions normally occupied by Al’. We may view these chromium(III) species as octahedral chromium(II) complexes incorporated into the alumina lattice; d-d transitions at these centres give rise to the colour. Chemistry 260)yr AY \ jn emerald [Fig.9.12(b)}, cr jons occupy octahedral sites in the mineral beryl (Be,AlS!:0.e). The absorption bands seen in the ruby shift to longer wavelength, namely nd in yellowsred and blue, causing 9.9.13: (a) Ruby: this gemstone was fou emerald to transmit light in marble from Mogok, Myanmar: () the green region. )) Emerald: this gemstone was found in Muzo, Cotumbia, ° uipteaiont The crystal fel of Crystal ld model i the formation, i a Is successful in explaining aoe Pe nds field to.a large extent. Howmen senate Properties of coordination compounds, Theory verre uargeS/ Xt follows that anionic ligands should exert the greatest ae gands actually are found at the low end Sa ae we OE and ‘molecular resent study. i a SS Intext_CQuestions 9.5 Explain on the basis of valence bond theory that [NI(CN),|* ion with square planar structure is diamagnetic and the INiCL}* ion with tetrahedral geometry is paramagnetic, 9.6 {NiCl,J” is paramagnetic while {Ni(CO),] is diamagnetic though both are tetrahedral. Why? 9.7 [Fe(H;0)¢l” ts strongly paramagnetic whereas [Fe(CN)J* is weakly paramagnetic. Explain, 9.8 Explain [Co(NH,J!” is an inner orbital complex whereas (NI(NH,),]" 1s an outer orbital complex. 9.9 Predict the number of unpaired electrons in the Square planar [Pt(CN),]” ion. 9.10 The hexaquo manganese(I) ion contains five unpaired electrons, while the hexacyanoton contains only one unpaired electron. Explain using Crystal Field Theory. field | orbital theory which are beyond the scope of the p: 6 Bonding in The homoleptic carbonyls (compounds containing carbonyl ligands Metal only) are formed by most of the transition metals. These carbonyls Carbonyl have simple, well defined structures. Tetracarbonylnickel(0) is roomy ls tetrahedral, pentacarbonyliron(0) i s trigonalbipyramidal while hexacarbonyl chromium(0) is octahedral, Decacarbonyldimanganese(0) is made up Mn(CO), units joined by a Mn - Mn bo: has a Co - Co bond bridged by two C of two square pyramidal nd. Octacarbonyldicobalt(0) 0 groups (Fig.9.13). : 281, Coordination CompoundsTT 00 co \ on, 1 Ht e €O oc~ | co oe co d 8 NICO), Fe(CO), of Z co ‘Tetrahedral ‘Triqonal bipyramidal = OG & co oc” § co Cl oe) CO; co. r co f co co oh Rig. 919 +p ‘ {c0(COV, Structures af nome aeons 06 fff ifn CO representative cor co co co homoleptic metal ‘0 0 - carbonyls, Cr(CO), Ootahedral Min,(COd) Ps Yo 2 jee-8 ‘Synergic bonding Fig. 9.14:Example of synergic bonding interactions (n a carbonyl complex. 9.7 Importance ‘The coordination compounds are of great importance, ‘These compounds a are widely present in the mineral, plant and animal worlds and are fal Known to play many important functions in the area of analytical __ Applications chemistry, metallurgy, biological systems, industry and medicine, ‘These o are described below: ordination * Coordination compounds find use tn many qualitative and Gompound quantitative chemical analysis. The familiar colour reactions given pOUnas. by metal ions with a number of ligands (especially chelating ligands), as a result of formation of coordination entities, form the basts for thelr detection and estimation by classical and instrumental methods of analysis. Examples of such reagents include EDTA, DMG (dimethylglyoxime), a-nitroso-p-naphthol, cupron, etc. «Hardness of water is estimated by simple titration with Na,EDTA. The Ca” and Mg” ions form stable complexes with EDTA. The selective estimation of these fons can be done due to difference in the stability constants of calclum and magnesium complexes. * Some important extraction processes of metals, like those of silver: gold, make use of complex formation. Gold, for example, combines wit cyanide in the presence of oxygen and water to form the coordination entity [Au(CN),J in aqueous solution. Gold can be separated in metallic form from this solution by the addition of zine (Unit 6). * Similarly, purification of metals can be achieved through formation and subsequent decomposition of their coordination compounds. Chemistry 926% — —_—rong For exaniple, Impure nickel ts converted (0 ANC decomposed to yield pure nickel. * Coordinat (ion. compount f eatnce_ise tae at mone cai aac enani e e. Vitamin By. cyanocobalam nt c fa factor, 1s a coordination comPor Among the nm tance witl other compounds of biological impor ae coordinated metal tons are the enzymes like, © and carbonic anhydrase (catalysts of biological ayer) eu * Coordination compounds are used as catalysts: for many SEH. *~ processes. Examples include rhodium « Ueal “Wilkinson catalyst, is used for the hydrogenation 2 nore Articles can be electroplated with silver and gol ee AgiCNDT smoothly and evenly from solutions of the complexe: Es and [AU(CN),T than from a solution of simple metal lon®- si In black and white photography, the developed film 1 — washing with hypo solution which dissolves the undec’ AgBr to form a complex ion, [Ag(S.03:1"- ; There is ng interest in the use of chelate therapy medicinal chemistry. An example is the treatment of problems caused by the presence of metals in toxic proportior ns in plant/animal systems. ‘Thus, excess of copper and iron are es D-penicillamine and desferrioxime B via the formation of coordination compounds. EDTA is used in the treatment of lead poisoning. Somme coordination compounds of platinum eff fectively inhibit the growth of tumours. Examples are: cis-platin and related compounds. years, advarites in this area, have provided development of new concepts. and models of bonding and ‘the chemistry of coordination compounds is an important and challenging area of modern inorganic chemistry. During the last fifty molecular structure, novel breakthroughs in chemical industry and vital insights into the functioning of critical components of bielogical systems. ‘The first systematic attempt at explaining the formation, reactions, structure and bonding of a coordination compound was made by A. Werner. His theory postulated the use of two types of linkages (primary and secondary) by a metal atom/ion in a coordination compound, In the modern language of chemistry these linkages are recognised as the lontsable (tonic)"and non-ionisable (covalent) | bonds, respectively: Using the ‘property of isomerism, Werner predicted the | geometrical shapes of a large number of coordination. entities. | the Valence Bond Theory (VBT) explains. with reasonable success, the j formation, magnetic behaviour and geometrical shapes of coordination compounds. . however, fails to provide a quantitative interpretation of magnetic behaviour | and has nothing to say about the optical properties of these compounds. a { The Crystal Field Theory (CFT) to coordination compounds is based on } the effect of different crystal flelds (provided by the ligands taken as point charges), BA, Coordination Compoundscon the degeneracy of d orbital energles of the central metal atom/ion The splitting of the d orbitals provides different electronic arrangements in strong fand weak crystal elds, The treatment provides for quantitative estimations of orbital separation energies, magnetic moments and spectral and stability parameters, However, the assumption that ligands consititute point charges creates many theoretical difficulties. “The metal-carbon bond in metal carbonyls possesses both o and ® character ‘The ligand to metal is ¢ bond and metal to ligand is x bond. This unique eyner#ie bonding provides stability to metal carbonyls. Coordination compounds are of great importance. These compounds provide critical Insights into the functioning and structures of vital ‘components of biological systems, Coordination compounds also find extensive applications in metallurgical processes, analytical and medicinal chemistry. € XUICISES 9.1 Explain the bonding in coordination compounds in terms of Werner's postulates: 9.2 FeSO, solution mixed with (NHJ.SO, solution in 1:1 molar ratlo gives the eee te re” fon but CuSO, solution mixed with aqueous ammonia in 1:4 molar ratio does not give the test of Cu” ion. Explain why? 9.3. Explain with two examples each of the following: coordination entity. ligand, Conraination number, coordination polyhedron, homoleptic and heteroleptic. 0.4 What is meant by unidentate, didentate and ambidentate ligands? Give two examples for each. 9.5. Specify the oxidation numbers of the metals in the following coordination entities: ( [CofF,ONCNI(en}.I” (i) [PLC () ICrINH)sCh} (i) [CoBra(en)al” (v) KylFe(CNel 9.6 Using IUPAC norms write the formulas for the following: ( Tetrahydroxidozincate(ll) (vt) Hexaamminecobalt{Il!) sulphate (i) Potassium tetrachloridopalladate(t) (vii) Potassium tr(oxalato)chromate(II) (ii) Diamminedichloridoplatinum(tt) (viii) Hexaammineplatinum(1V) iv) Potassium tetracyanidonickelate(t!) (ix) Tetrabromidocuprate(tt) (v) Pentaamminenitrito-O-cobalt(IIl) —() Pentaamminenitrito-N-cobalt(I]) 9.7. Using IUPAC norms write the systematic names of the following: (© [Co(NH ICL, iv) [Co(NH),CI(NOJICI (vit) IN(NEAICL, (8) [PUNE),CIINE,CH3)ICI_—_(¥) [Mn(H,0)e!”” (wilt) [Cofen)3)” (ui) TU0H,O)” (wi) INICLI* (9 [NICO] 9.8 List varlous types of isomerism possible for coordination compounds, giving an example of each. 9.9 How many geometrical isomers are possible in the following coordination entities? © [Cx(C,0y)* (i) [Co(NH),Cla] Chemistry 264,9.30 gil 9.12 9.13 9.34 9.15 9.16 9.17 9.18 9.19 9.20 g.21 9.22 9.23 9.24 9.25 9.26 9.27 praw the structures of optical isomers oe ) ICrC,003) W) tPtCIyfen), " Draw all the isomers (geometrical and iecid oft ee CoCl,{en),]" » @ [Coch (tt) [Co(NH,)ci(en),1" (wy (cowry, chien write all the geometrical isomers of (Pte will exhibit optical isomers? s}(Br\(CI(py)} and how many of these Aqueous copper sulphate solution (blue t in colour) gives: @a Peat precipitate with aqueous Potassium fluoride and (ii) a green solution q experimental results, with aqueous potassium chloride. Explain these int. i the coordination entity formed when excess of aqueous KCN 1s ad Uther Solution of copper sulphate? Why is it that no precipitate of copper sulphide ts obtained when H,S(g) is passed through this solution? Discuss ‘the nature of bonding in basis of valence bond theory: the following coordination entities on the oa TEENA GD Tere” i) (CofC0yaI” tv) [CORA Draw figure to show the splitting of d orbitals in an octahedral crystal field. What is spectrochemical field ligand and a aa a fad iene the difference between a weak What Is crystal fleld splitting energy? How does the magnitude of A, decide the actual configuration of d orbitals in a coordination entity? (Cr(NH,).)" 1s paramagnetic while [Ni(CN),)* is diamagnetic. Explain why? A solution of [Ni(H,O),]" is green but a solution of INi(CN),|> is. colourless. Explain. [Fe(CN)I and [Fe(H,0),]” are of different colours in dilute solutions, Why? Discuss the nature of bonding in metal carbonyls. Give the oxidation state, d orbital occupation and coordination number of the central metal ion in the following complexes: : (i) KslCo(C.0,)s] (til) (NH),[CoF,] (ti) cis-[CrCl,(en),}C1 = (iv) IMnqH,0).JS0, Write down the IUPAC name for each of the following complexes and indicate the oxidation state, electronic configuration and coordination number. Also give stereochemistry and magnetic moment of the complex: () KICr(H,0)}(C20,)2].3H,0 (i) [CrCly(py)a] (v) K,[Mn(CN)¢] (i) [Co(NH,)sCLIC, Gv) Cs[FeCh] Explain the violet colour of the complex [Ti(H,0)** on the basis of crystal field theory. What is meant by the chelate effect? Give an example. Discuss briefly giving an example in each case the role of coordination compounds in: W biological systems (ii) analytical chemistry (i) medicinal chemistry and (iv) extraction/metallurgy of metals.9.29 9.31 How many tons are produced from the complek Co(NH,j,Cl, in solution? ws (4 wu 3 (i) 2 Amongst the following ions which one has the highest magnetic moment value? (@ [Crt4,0})" —_() [Fe(HH,O)6F"* (tu) (Zn1H1,0)6F” Amongst the following, the most stable complex 1s (tv) fFeCls” () (FeO) * (11) [Fe(N Hse” it) IFe(C,O05I” What will be the correct order for the wavelengths of absorption in region for the following: INUINO,)I*. [NKINH),}". [NICH,O}” 2 the visible Answers to Some Intext Questions (iv) [PUNH,JBrCl(NODT 9.1 (i) [CofNFi,),(H,0),)Cl, (i) KaINS(CN)4) (v) [PtCl{en,I(NO): (ii) [Crfen)sICl, (vi) FedFe(CN)els 9.2 (i) Hexaamminecobalt(il!) chloride (i) Pentaamminechloridocobalt(lI} chloride (i) Potassium hexacyanidoferrate(IIl) (iv) Potassium trioxalatoferrate({tI) (v) Potasstum tetrachloridopalladate(tl) (vi) Diamminechlorido(methanamine)platinum({l!) chloride 9.3 (i) Both geometrical (cis-, trans-) and optical isomers for cis can exist. (4) Two optical isomers can exist. (itl) There are 10 possible isomers. (Hint: There are geometrical, onisation ‘and linkage isomers possible). (iv) Geometrical (cis, trans-) isomers can exist. 9.4 The ionisation isomers dissolve in water to yield different ions and thus react differently to various reagents: {Co(NH,);BrjSO, + Ba” + BaSO, (s) [Co(NH,,SO,JBr + Ba” > No reaction ICo(NH,)sBr]SO, + Ag’ No reaction [Co(NH,),SOJBr + Ag’—> AgBr (3) 9.6 In Ni(CO),, Ni is in zero oxidation state whereas in NiCl,*, it is in +2 oxidation state. In the presence of CO ligand, the unpaired d electrons of Ni pair up but CI being a weak ligand is unable to pair up the unpaired electrons. 9.7 In presence of CN’, (a strong ligand) the 3d electrons pair up leaving only one unpaired electron. The hybridisation is 'sp* forming inner orbital complex. In the presence of H,O, (a weak ligand), 3d electrons do not pair up. The hybridisation is sp*d* forming an outer orbital complex containing five unpaired electrons, tt is strongly paramagnetic. 9.8 In the presence of NH, the 3d electrons pair up leaving two d orbitals empty to be involved in d’sp* hybridisation forming inner orbital complex in case of (Co(NHs)d™.tn NIE)", Ni is in 42 oxidation state and Ine comers” the hybridisation involved is sp’d’ forming outer orbital jex. 9.9 For square planar shape, the hybridisation 1s dsp’. Hence ie unpaired electrons in 5d orbital pair up to ™ ined “sect empty for dsp* hybridisation. Thus there 1s no BP