oh Ae es RN. ; & “atemeersm GK 5 / 0p ——— (N COORLINATION ConmpouNLs GF — —* ‘ corns Olt fiett: Hare pra Sime ChLmi AL Rien Gk Kove Aibh ertut Sfructurras edrarge- y ete oF ee eh ord (00 fhe (n. ahord Cone boats ‘ Me C6 EM LOLI IN OF pra atom fn Sposa) ore Cnttenk formers anal ne = % a e ALO %D Ona Qt Veto i TSS PO [S0m ers is Cptied “isomer/bm. # | @ Type: LTre Bomeriém oF Lodrolimation comp ounglt : ney 66 cane’ ted jnfo A> porns ippee — i Ud Structural bomenitm ; ‘Sfrovturot [$amepitm ire fr ar om ore Lorpounds ohVA Kame enyorient Brromutla Ao Ler im atom tinting § to (bart a Commectivits es). 7r2 4 akko exhledl cfrtfurrk /50- a ere fm. . 2 no Le» Shirevlo mentem: | Pn Thi th fre Comps Aart sre fame bmpri Cah termarta ancl SRA Sams “ator fo atom Aink Sepwirtt, bet Dif tren’ gar agsen ent OF ppL alt’ im Spat: ne main ty ees yr ( emi Cotegory mre” A bE pI Vai Wek eA piles ~ < A bs r LD tons: pr tronak 1807 eadn ", it two CI- ions are placed cis to each other or at 1-2 positions, it is named as cis-dichloro bromoiodo palladium (I) ion or 1,2-dichloro bormoiodo palladium (11) fon. On the other, if two CI ions are placed trans to each other or at 1-3 positions, it js named as trans-dichlorobromoiodo palladium {Il} ion ot 1, 3-dichlorobromoiodopalladium (11) ion (See Fig. 4.2) Here we shall consider geometrical isomerism in square planar complexes of [May], (Maxb], [Mab,], [Mab], [Mazbc], [Mabcd] and ([M(AB)2] type in which M is the central metal atom; a, b,c and d are monodentate ligands and (AB) is an unsymmetrical bidentate ligand, since it has wo different donor atoms namely A and B. 1. [May], [Ma3b] and [Mab] type complexes. Square planar complexes of this type donot show geometrical isomerism, since all the possible spatial arrangement of four ligands round the central metal atom is the same.Aaveneed OH nang WY a » sys | a we el 90 | f pt /) 8} fp We / | ol NS } i “ Vo i \al af h og i by rraneichlora brometerta patter. ~ 1) fon oF f _ year aghiowns Rermoncchs foarladionn (1 bi tore tre ~ at espana tees ae Seer mmmrayndy , r a square . Aarure of geometrical (cti-and (rant) WOMEr? ° 19408 planer come, eS in examples of square planar complexes og 2. [Majby} (pe compleres, ins [? etc. These complexes ex } . MINH) (NO3)2 5 Cm HARCHP. UU EHP. [MONTE i! r te Se eas ot (PRNID AChE are shown in Fig. 4.3. In (a) since bom, cvs to each other, it ix called cis-ixomer. On the molecules ant tath Ch fone ar wy ona are trans with fespect to exch at BE in QB) since Kh NH, molecules and both called mansisomer. trans-isomer Fig. 43. cis-and trans-isomers of [PP*(NH3),C1,P. 3. [Mabed] type compelxes. Square planar complexes of this type exist in three is forms. For example (PU*(NH)(py(CI)(BN) exists in three isomeric forms shown below is 4.4. These isomeric forms can be obtained by selecting one ligand, say NH, and then the remaining three ligands, one by onc, trans to NH). NH, x Fig. 4.4. Three isomeric forms of. [PENH Gy)(CDBN) [PE*(NO2)y)(NH,)(NHOH)]* and [Pe CH. es of planar complexes which exist in three toner tone San als Tre existence of three isomeric forms that these complexes have square planar geon 4. [Ma,bc} type complexes. Sq isomerism. For example (Pd?* Beas: xample [Pd*Cl,BrI} case of the complexes mentioned above i metry. ware planar complexes of this type also” show a i: + = low! ion exists in cis and trans-isomers as shown Pla Br / - oR f pa ~ f a mt cletoomer tronetenene Me. 45, Clean rane tsomers of {CK HAP on [PEPYANHCH! ix another example of equ: eo oat type whic! exists in ciand franvisomers Bi fens Stereo toore} erence §. [M(AT),1 type complexes. Here Mis the central meta ‘ pe central I ion and [AB unsymmetrical bidentate ligand in which A and Ib are two ditterere criseuseteg Ooty tases ‘Square planar Sop leie of this type also exist in cis-and trans-isomners. For cxample IP(gtyb} -exists in cis-and trans. isomers as shown below in Fig. 4.6. Here gly represents the inate ligand, NH,.CH;COO™ which has N and © atoms as its donor sorta bere =N ates oO). Hy, trans-isomer Fig. 4.6. cis- and trans-isomers of [PE*(gly):)- [Cu**(gly),]° is also an example of square planar complex of [M(AA))] type. This complex " also exhibits cis-trans-isomerism. Geometrical isomerism in 6-coordinated complexes : Octahedral complexes We know .that a complex compound having central atom with coordination number equal to 6 is octahedral in shape. Before discussing the geometrical isomerism exhibited by various types of octahedral complexes, we should know how cis- and trans- isomers of an octahedral complex are named. In an octahedral complex, if two similar ligands are placed on any of the twelve edges of the octahedron, they are said to be in cis position. On the other hand,. if two similar ligands are lying on a straight line which passes through the Centre (where the metal ion is placed), they are said to be in trans position. Thus in an octahedral complex, thé two ligands at positions 1-6, 2-4 and 3-5 are trans to each other and the two ligands occupying positions 1-2, 1-3, 2-3, 3-6, 6-4 etc. are cis to each other, (See Fig. 4.7) * :OR 2. Numbering of six ligands in a regular octahedral complex round the Fig. 4.7. numbering system of ligands. can be Oa by Considering the isomers of [Co™(NH,),Cl)]* ion whic san octahedral comple, of cis- and fren wo CI ions are cis to cach other is also called 7, 9.0% ion of this ion ng (see Fig. 4.8 (a)]. Similarly, trans-isomer of this ion in whic copa a iene other is also called 1, -dichlorotetrammine coban cm sh tog A Central The above are trans 1) ion, Oo) Here we shall discuss the geometrical isomerism in octahedral Complexes Of the hy type: exhibit geometrical isomerism. 2 [Ma,b;] type complexes. Important examples of octahedral complexes of 4: [Co™¢NH,)Cl,]*. [Co'(NHs),(NO,)2]* etc. These complexes exist in cis and i Oe These isomers of [Co**(NH3),Cl2]* ion are shown in Fig. 4.8. In cis-isomer two rh the adjacent (ie. 1 and 2) positions of the octahedron while in trans-isomer these the opposite (ie.. 1 and 6) position. Cis-isomer of [Co™(NH,), (NOj ones Wes inns while trans-form is yellow in colour. 304 (NO2)a}* ion is yeton “1. {Mag}, [Magb] and [M(AA)3] type complexes. Octahedral complexes of 1, i om a) 7+ i a. 6) ca OR ) (2) cis-isoy “ (@) cis-isomer (1 en (©) trans-isomer cobalt (III) ion), (ellow-browny @) trans lomet fe Salone col ion), (yellow) Fig. 4.8, cis. comy i. [Maybe] type conmteres cnn ea of [Co**(NH,) CLP ion, Plex of [Ma,be °8. [Co ade CHONG FIO se a Fig. 4.9. In cintor pe This ion has cist ae 1)?* ion is an important example o ite s frans-isomers whose structures afe give! ese ligands (i... two NH, ne fave cls positions to each other and in Ua IRhpy nega) Pe complexes, cenrs MVE ARs positions woh sen -Y)sCl3], (RuCH.O) E15) Teta ACH ICONE OD, [Cr(H,0);Fs}; Icey ac s)3Br3}*, [Pt(NH)sIs]* etc. are inoe, — — )- aye § Gn ot | ne 1 yn, 2 { om, a nit } 0D) te ener ‘ om, 2 Fee 4B. Bereientene a ete eet prem 0 caneuanes Serres ot it ow enOO ~ examples of notuhedrst cempitenee of (ite) NCTE esunatans i premedomen AL nh rr minpfle ink eps Beet ae aa 410. om termes foe IW ENTEeP eee a ne ~ me ae Tig a Rx a . ty n o | A nye, * es ~ i aw ; < ey <<. ~_ yl s NH, _— ©) a - = {@) cisisomer [1 2. 34somer or facial o . {Jac} isomer} Aaomer [2 emma erent h e Pas 410. cis. and trans-isomers of [Co™(NH Oy) may be seen the figure that in cts-tomer + coc ot On eidigher face of tir cctabcdron sad srelbrolngte ig rnoc al py pe ore cK of the opposite tnangular face of the octabedron Thus i= ee ee occupy 1, 2 and 3 positions and hence tus isomer is also called TL aon isomer. In trans-isomer the three CI” sons are lying around one edge of eo =e duce NH, molecules are lying around the opposite edge of the octahedron. Tass = T=meSa the three CI” ions occupy. 1. 2 and 6 positions and hence ranssomer = aiso cated L 26 isomer or meridional (mer) isomer. s.[Ma,b,ea] type complexes. [Pr**(NH,); (9)iCh> tn is an important exams St SATS complex of [Mazb3¢3] type. This ion can exist theoretically in five geomemcal acer tut have been shown in Fig. 4.11, but it is only three tsomers that have Deen actually sot 2 may be noted from the figure that (1) form 1s a cts-form Ss this form two aiconcal Rguads are occupying adjacent positions. Form (Il) ts cons form because in it the two Aienocal Rgead are placed at opposite positions. 6. [Mabcdef] type complexes. Octahedral complexes which have Giffereat woeodentatt - ligands have been prepared for PulV) [Pt ry XH XNOAXCIXBERD! =e Sols complies of this type of complexce. Theoretically 15 geometrical isomers are possibile for he complies compound, In fact only three geometrical isomers have been isolated.86 2+ <2 av) Fig. 4.11. All possible five geometrical isomers of [Pt**(NHs)2@y)2CLF* ion, trical bidentate 4 7 exes. Here (AA) represents a symmetrical te Tiga ea es ee * Jentival coordinating (donor) atoms. (CofenChl » [Colen)evi, which A a a caten)gChT", [CXC:0nsCHROT » He" (Cr0a)eCh] 2 are the exanph (Colen.MOnaT TN ons of (M(AA)aa2] type. Each of these complex ions exists in ci outahedral comples iets mple cfs and transisomers of [Co™*(en),Ch]” ion are shown jn ~ trans-isomers. 4.12. OR cis-isomerene 8, IM(AA)sab] type complexes. (Co™*(en), e ‘ zs a), (NH )CIP* is e7 oo Na Se Teco et Se Eee ee tomes i 1 ‘ NE and Cl occupy the a gnisomer these ligands occupy opposite (Le, rao seca tie. 1h poston while inane aso exis eam ee Fig, 4.13) (RU (CAs 2 = 5 NH, clelsomer Fig. 4.13. cis- and trans-isomers of [Co™(en),(NH (CP ion. 9, Octahedral complexes of [M(AA)ab1 t iS ; , y n ype. [Co™*(en)(NH: * on i aample of an octahedral complex ion of [M(AA)ajb} Gain Se on is ioe, BOL camPtoups and both Cir ions occupy the eis postions while in tans-isomer both these pairs NE Eine irans positions (see Fig. 4.14). NH; cis-isomer trans-isomer Fig, 4.14. cise and trans-isomers of (Co™(en)(NH3):Cla)" ion. [Co*(C,02) (NH)2 (NOz)aI" ion is another example of octahedral complex of [M(AA)a:ba} type. : 10. M(AB)s] type complexes. Here (AB) represents an unsymmetrical bidentate ligand in which A and B are two different coordinating (donor) atoms. Octahedral complexes of this type exist in cis- and trans-isomers. As an example the cis- and trans-isomers of (Cr*(gly)s} has been shown in Fig. 4.15. Each of these forms is optically active and hence each has a pair of optical isomers. In cis-isomer two N-atoms and two O-atoms of two gly ions are placed at cis-positions while in trans-isomer these atoms are ‘occupying trans-positions. TRE trans-isomert cis-isomer oe Fig, 4.15. cis- and trans-iscnurs of [ce“ely)s)-‘ 11, Octaledral compleren comtainingeegabently wetive MAdert ate Nyon, (0, Hipy Jon Ie An tinportent example af euih type of detabedenl conmplerre Were an way) diamine and 1, Jaianiw propane (alse called progfens al Oyo ny Ws Hynnde are bidentate Nynsde and thelr aiuctures mre given bedern: yh / 2 4 Cy Ch ~My CH, — NI, MWh MW, CH, — NU, . ” Hihylene diamine (4n) 4 asiriea 0 le a Nya nd hence optically samtive) onl haven typieatty were the liyands are bidentate Prom thelr structures it te evident that both : Cth donors viz, Nestoms and that en ty ayrmunetricnl and hence opnically inactive white gy jg ie, and hence optically active. ‘Tv differentiate, the two denen steams viz, Neatennn of been shown with onc und two uatetiske, (Coveny(on) ONOzy]* bom e258 an tong MO ” forms; two are cis and two are trans, (a) chr-isomer has been obtained by pra fy, NH, at 4 and 6 positions of the octahedron and in (b) cls-isomer thelt penition, reversed, (c) nnd (d) which are frans-ivomers have been obtained similarly (ree Fie aig “ ” Wans-isomers trans-isomers of [Co*(en) (pn) (NO;)3}° ion. é Fig. 4.16. Two cis-and two t Tt may be noted that both cis-isomers while both trans-isomers are are unsymmetrical and hence are optically symmetrical and hence are optically inactive.monsin Wy Vvuranmur CunpOUrES 59) (so 12, Dinuclear bridged octahedral com : cil att of TFeOHAHO),1" tyre ne samy paras Dany ing dinuclear t Fig. 1.53 (Chapt - ructure of this fon has already been ee oes aiructaTes 1). This ion shows geometrical i aves peat isomers We are Riven’ Fle 1s ne ep omer aid gives Chee geometrical Co (IM) f ? F 54. in Chapter 1. (b) Co ¢ i forms dinuclear bridged octahedral complex which contains NH; and jons as bridging ligands, This complex is formmutated as {Co} (en),(NH,)(NO i aes ua Co}'(en),(NH,\(NO,)I* whose structure has already been given at Fig. 1.45 in chapte has ftures of these isomers have been gi corel Rig eee ie eo clean en eos The LAG in chapter 1. EP | distinguish between cis- and trans-isomers ‘The following methods may be used to distingui io guish between cis- and trans-isomers. 1, Die eocenee oreo : nents. Jenscn has shown that the Pt (II) comics of (PH, type, where A= phosphine, arsine or stilbine such as (C)H,)sP, eo aes halogen fave ithate dipslomenietis (ay ci ate 2 (CoHs)sAs or (CzHs)3Sb Debye units. In the compounds with 1 = 0, the individual moments me Sealine nites oe Debye Uo caclcmers, The pompous aa See Dae ee ruc 2. X-ray crystal analysis. X-ray crystal analysis and dipole m¢ i eases f several PII complexes have confirmed the square planarity af the bonds around th el , Stal atom. This square planar arrangement has also been established for ‘ceo sted Pi om, ‘AgdD, Cudl) and Audi) complexes. Tetrahedral configurations have been asi ned 10 cud BI), AIGID, Zn), Cad), Hg) and Cod) in their coordinated compounds. Agd), Au@). ( eee metals such as Ni(II) appear to show either configuration for 4-coordination. MO A ie (e) civisomer (otras “cis-and trans-isomers of [Co™(NH,),Cla]” octahedral complex. ° ee ai TSN xe cl ok nd) / wn Pt f “cla, NH; i (a) trans-isomer (c) cis-isomer 2 ° : jsomers of [P" (NH,),Cla}’ square planar complex cis-and trans-iso’ [Pr 3)2Cla) aa rere of (CONHSACHT and Fig. 4.17.. Symmetrical Cl-metal-Cl ‘stretching vibrations of cis-an TPNH3)2Ch)” vrad Te Chomiy, f 3. Infra-red spectrascopie technique Ina rans octahedral complex sucha IcoMgy or in trane square planar complex like (PY"(NH,),Cla} the Cl-metal- Lem gy vibration produces no change in the dipole ipaorent ot ieee Pe. dy sponding to this vibration Is Win the inf tram Mee oh eek Be portal the symmetrical cic Votation [Fig 4 ae ‘as well the unsymmetrical stretching vibration produce apprecial 4 changes in the dipole 4 hence the infra-red spectrum of the cis-isomer will contain a large number of bangs? a -metal-C! stretching. P , 5 i hosiece e 4 high molar extinction coefficient (absorption) than the trans-isomer and sometimes the two isomers may differ significantly in their abs ti 5. The technique which consists of attempting to resolve the cis-isomer into the 10 pone optically active isomers is also commonly used to distinguish it from the trans.isomee 6. Grinberg’s Method. It is a chemical method and assumes that when a cheat, : having two donor atoms separated by two to four other atoms reacts with cis"and ae , ’ Ind fra donataloms coordinate athe central metal ion ofthe cis-form at two ae aides anattie or six membered ring, while in the trans-form they coordinate Ea Tetal jon at trans positions and thus the ligand acts as a@ ‘monodentate ligand, i, the tid eanaot form ting complex with rans form. Typical chelating igands used for the pune oxalic acid, (COOH), glycine (HzN—CH;—COOH) and ethylenediamine (uh CH,—NH,). The application of this method can by explained be considering the 27° oxalic acid and glycine with cis- and sransisomers of square planar compley a na (Pe*QNEE).Cl (Fig. 4.18). Quite obviously the cis- isomer gives a chelated comply vial the trans-isomer yields a non-chelated complex. q coor, — [HNN 4 F=0 Pt + 2HCI ce)” | HN” No—C=0 0 Chelated complex HN, cl pee HN” Nc cis-form +H,NCH,COOH racoon cl + Hel ‘Chelated complex 0 +2(COOH), HAN - 4 / O0C — COOH ancy Hooc—coo”"" \, mm ‘NH, FINA yl Non-cheloted complex a Na, transform Su icoon HN, _/NHyCH,COOH . 7 HOOCH,CHN“" \wH, / Non-chelated i Fig. 4.18. Reaction of oxalic acid, (COOH) 2 ae oat 4 square planar complex of Prt), >and 2Y°iNe, NH>.CHs,COOH with eis-and rrans-isom™a \ e Ae} 7.Kormakov's reaetion, Kurnakoy uilised the phenomenon of tans-effect in distinguish M6 ihe pairs of cis- and trans-isomers of square pl Pe Tiberi crea Daye mi fo quate planar complexes of (PtAyX,} type by. treating dy \ % ‘iby, Definition of some terms related with optical isomerism Ms A A ace Ie _ Before discussing the optical isomerism shown 63 i > hp, define some important terms related to this isomerism, Nai, types of, eomplenee we gil When the solutions of certain complex compounds are placed in the path o -polari iN directions are cut off), they rotate its plane through a certain angle which may be either to the Po, left ora he right. ae property of a complex of rotating the plane of polarised light is called eS its optical activity and the complex possessing this property is said to be optically active. Optically active complexes are said to exist in the following forms & (@) One which rotates the plane of polarised light towards right (i.e., in clockwise direction) t js said to be dextro-rotatory or d-form. d-form is also represented by placing (+) sign before cg, its name or formula. my @) One which rotates the plane of polarised light towards teft (ken in anti-clockwise ex! direction) is called levo-rotatory or t-form. I-form is also represented by putting (-) sign before its name or formula, (+), dextro, and (—), levo, refer to the sign of rotation of the optical isomer at the sodium D line wavelength. The d- and I-forms have the following characteristics: () Since d-and -forms are capable of rotating the plane of polarised light, these are said to be optically ‘active forms or optical isomers and this phenomenon is called optical activity or optical isomerism. ‘These two forms have exactly identical physical and chemical properties, although they differ in their action on polarised light. (ii) d-and /-forms are mirror images to cach other just as left hand is the mirror image of the right hand, Thus d- and /-forms can be superimposed on each other and hence d-and I-forms are also called mirror-image isomers. These optical isomers are also called optical antipods ot enantiomorphs (Latin: enantio = opposite; morphs = forms) or enantiomers. From this description it follows that optical isomerism can also be called mirror-image isomerism or enantiomorphism or enantiomerism. (c) The isomer which is not capable of rotating the plane of polarised light is called optically inactive, Such an isomer is called meso, racemic, dl-or (+) form. A racemic substance is composed of 50% d- and 50% [-form, The solution of a racemic (dl mixture) form in a solvent which contains equimolecular amounts of d- and /-form is symmetrical and hence optically inactive, because the rotation (of the plane of polarised light) produced by one isomer, say d-isomer, is balanced or compensated by equal but opposite rotation produced by the other (i.e., Lisomer), Optical inactivity produced in di-mixture is said to be due to external compensation. Conditions for a molecule to show optical isomerism A molecule in which the grouping of the atoms is asymmetric is called an asymmetric or dissymmetric molecule. An asymmetric molecule has the following features: (® An asymmetric molecule never has a plane of symmetry (also called mirror-image Plane) which is defined as an imaginary plane dividing the molecule in such a way that the Part of it on one side of the plane is the mirror image of that on the other side of the plane. The molecules possessing such a plane of symmetry are always inactive while those having no | Plane of symmetry are optically active and hence show optical isomerism. 3 Gi) An asymmetric molecule cannot be superimposed on its mirror image. =, __ Thus the most necessary and sufficient condition for a molecule to show optical Pas (ie, to exist in d-and L-forms) is that the moelcule should be asymmetric, (ie., tt should have Z| no plane of symmetry) and should not be superimposable on its mirror image.ted complexes: Tetrahedral Complexes i 4-coordina - Optical isomerism in isomerism in the following types of tte tal Here we shall discuss optical exes. 1. [Mag] and [Mab] type complexes: Turahets et (Mad ana iy are not able to show optical isomerism Oe duclen ements of 4 hen round the central metal ion, M are exactly equi : ig) tivichenicd ln, 2. [Mabed] type complexes. Since the central AO ee i Tal complexes ype f Ruaeanded by four different ligands, the tetahedral Complex of this type Mg to produce a pair of enantiomarphs, For example tA “(CHCA ISN CHa (tetrahedral) exists in two optical isomers as shown in Fig. 4.19. Mirror plane a= a ( t t t t Il ' t t I t t ' t t t ' ' Fig. 4.19, Optical isomers of tetrahedral complex ion, [As(CH)(C;H;)(S)(CH,C00);- Here it may be noted that 4 different groups round the central metal ion are not th; requirement to make the complex to show mirror-image isomerism. All that is requined jg) the molecule should be asymmetric (i. unsymmetrical), i., it should have no plane of symm so that it can exist in two mirror-image forms. 3. Tetrahedral complexes of Be(I), B(LI) and Zn(1I) with symmetrical bidentate lp have been made and resolved into optical isomers. Some examples of tetrahedral complae this type are bis (salicylaldehydato) boron (IMI) ion, [B**(CgHs.O.CHO),]* and bis (ten acetonato) beryllium (I), [Be* (CgH,CO.CH.CH,CO),]° whose micror-image i ( in Fig, 4.20 and 4.21 respectively. se inn Mirror plane levo form (Mirror-image) f ral bis (salicylaldchydato) boron (ID) #* 1BY(CgH.0.CHO),). ue Fig. 420. Mirror-image isomers of tetrahed:Mirror plane ‘dextro form levo form cores (Miror-iamge) “fai a Fig. 4.21. Mirror-image isomers of tetrahedral bis (benzoylacetonato) Abit 11) i [Be?*(C,HsCO.CH.CHCO),). a) Beeytans Sion erism in 4-coordinated complexes: Square planar complexes | isomerism rarely occurs in square planar complexes, since they have all the fd the central metal ion in the same plane and hence contain @ plane or mmetty: Thus these complexes are optically inactive, i.e, they cannot show rmerism even if all the four ligands are different. Although square planar complexes ‘ow optical isomerism, yet the following square planar complexes exhibit optical No-butylene diamine, NH,—CH,—C(CH,);—NH; (bidentate ligand) and meso-diphenyl “diamine (also called meso-stilbene diamine) (bidentate ligand), NH,—CH(CsHs) “react with [PtCl,|* and forms a square planar complex which is called “damine meso-stilbene diamine platinum (Il) ion, (PC* (NFy—CHz— C(CH;)—NH) i (C,H;)—NH2)* (See Fig. 4.22). NH, — CHCA NH, —CH(CH9) Meso-stilbene ‘diamine a a + ely” + Pt 7 N—CHC Hs) H, S—N FH diamine meso-stilbene diamine pattinum (1) ion- iso-butylene di ed the above complex into two optically active isomers amine meso-stilbene diamine platinum (M1) ion. omplex ion with Pd(I). In this id forms a square planar c tr gand. This complex ion = ifetraacetic acid acts as @ tetradentate liMirror plant : ' ' HH, H | c——N Nt i lhe Na Sern i | cH Pt GH, | eee Ny gen, ee || CH 2 ch, { \ ers (optically active isomers) of squate planar complex ign Fae 8 NT CH(CaH) CIKC«H,).NH,) (NH;.CH,.C(CH,),NH,)F* merism and hence exists as a pair of optical antipods as shown in CH,COO" CH,COO- “OOCCH, OOCCH, uty A fom on iia can be formulated as [Pd2*(EDTA)]*~ a . Mirror plane 9 tO a i a | a ee aa ' —n’ \n—c i powe \ $e] | Hy Ne af f Hy. fi, Hi, I { \ i Fig. 4.24. Pair of optical antipods of [Pd**(EDTA)]* ion. 3. The resolution of a complex of zinc with 8-hydroxy quinoline-S-sulphonic acid i optical antipods has been described by Liu and Bailor (1951). Optical isomerism in 6-coordinated complexes : Octahedral complexes Here We shall discuss the optical isomerism in octahedral complexes of the follo¥s type: 1. [Mayba] and [Ma3bs] type complexes. (a) We have already seen that octahedral compl of (Magbs} type exist in cis- and trans-isomers. Both these isomers are optically inactive ¢ to the presence of symmetry and hence donot show optical isomerisin, (b) We have already mentioned that octahedral ‘ exist in oi facial) and trans (or meridi complexes of (Masbs] type ional) isomers. Both these isomers are optically inactive 24 donot show optical isomerism. : _ 2. [Ma;b,2] type complexes. (Pt**(NH. + ion i tabed : 3)2(Py)2Cl]** ion is an important example of octah complex of (Mazbscal typer'We have already sated thar erin eae iat a 2 ‘ coer in Je Beometrical isomers, but only three have beon ‘icolated, In cis-som™ optical (1 roe nc ePy tne adjacent positions of the octahedron, ‘This ets. isomer exist Fans on graze) isomers which are mitror-image to ech’ oles ce chown in Fie i plex ion is symmetrical and hence is optically inactive form- 1650 form.Mirror plane 2+ cis-disomer cis-Lisomer (Object) (Mirror-image) Fig. 4.25. Mirror-image isomers of (Pt*(NH)),(py):ChI™ fon. 3. [Mabedef] type complexes. [Pt (py)(NH)(NO,)CIBrI)? is the only example of octahedral complex of this type. We have alrcady stated that, theoretically, this complex can exist in 15 geometrical isomers. Each of these 15 geometrical isomers exists in optically active d-and |-foms, giving a total ‘of 30 optically active isomers. d- and Lisomers for one of the 15 geometrical isomers are given in Fig. 4.26. Lisomer Fig, 4.26. Optical (d-and Lb) forms of [Pe*(py)(NHS)(NO)( CBO!’ 4, [M(AA)3] type complexes. Due to the absence of a plane or centre of symmetry, the ‘cctahedral complexes of this type are resolvable into dextro and levo forms. For example @- Mirror plane 1 t ' 1 1 i i i 1 i 1 1 1 1 ' ' 1 1 d-form Fiore Fig. 427. Optical isomers of [Co™*(en)s] }P* ion. These cannot be superimposed on each other.own in Fig. 4:27, Olber exarmples of ' Tal ¢ } t 3 3+ jon are shi ue n Penis on ad 1 F008 (ons (Co™ (pp xis at the complenes of IM(AA)s] type ean be resolved comm es etahedeal shape. Neither hexazonay inn, ye rise to activily. ton Po 1? omplex can gi exes. Here we can consider [co™(en),Ch)” fon, Wig fal isomerism and hence exists as cls. and pn have a | The cis-isomer does not have any planc or centre of symmetry and hence is ta ina 7 ie, isomer can be resolved into two optically active isomers (d- and Lisomers), on, oni hand the #ans-isomer has a plane of symmetry and hence opty inactive, ic bok , ymer is optical i i vie pt ly inactive (mey, tee pantesolved into optically active isomers. Thus érans- isome Conseque! ie has three optical isomers Wir. (a) Two optically sani ive ntly [Cocer):Cla]” , corresponding (0 Sjeconfiguration (i.e, and /-forms). One form is the mirror i ‘ other, (6) One optic form corresponding to trans-form (meso-form). Att ran te ally inactive “orms have been sho and [-forms of (Co of (M(AB)] type [Fe**(diph),]?* ete. The fact isomers confirms that these complex prismatic geometry of 6-coordinate ¢ 5, [M(AA)z#21 YPC complexes. stated that this ion shows geometric ¢ wn in Fig. 4:28, ~ Mirror plane ! A | Twit W-b--<5Cl | | / Ree \ ¥ on ‘ | 1 n&-- yl 1 1 1 1 1 oN trans-meso form (Symmetrical and hence | optically inactive form) | (Uasymsmetrisal and hence optically active forms) Fie 428, Optical jsomers of [Co(en);Chl* ion. - ‘ Giker exons or IniaA}er Ue octahedral complexes whose cis isomers exists in dere! and_ levo roo ares” [CO™*(en),CNOab2]" [r**(C20a2Cl PRY e Qav(EsoattOny” Ite (GO.nCh)- ee PRET BSE %. [M(AA),ab] type complexes. Here we shall consider [Co**(en),(NH)CI™* i ion. We bre already seen that this ion exists in cis and trans-isomers ae te Dene Mirror plane N en 2+ 4. (Unsymmetrical)tgomerism in Coordination Compounds o7 ence of plane or centre . abe resoved Into d and of sxmmey in es isomes, this isomer is opel active and hence a i ni 5] vn Hence opty ie pea aay ac aly oo ee a eRe ol A) ab] 4,29). nd /-forms is [Riv te of [MCAA} ab] Sype octahedral complexes whose ciisomer exist # , [M(AA)azbz] type us tat rag Be ica, Here we shall consider [Co™(en)(NHj),CloI* ion. We hehe gives'o is- and trans-isomers (geometrical isomers). Cis-isomer is ptically active d-and [-forms. On the other hand trans-isomer have Ss Iptically active an tically inactive and hence docs not give any optical active isomer. (See Fig. 4.30) Mirror plane ‘ t is opt NH, le BNeclenns trans-meso-isomer (Symmetsical) Unsymmetrical Fig. 4.30. Optical isomers of [Co™(en)(NHjChI" on. ),(NO,)2]" ion is another important example of| (M(AA)aybs] type octahedral ‘omer gives d-and isomers. complexes. We have seen that an octahedral complex of this type exists (geometrical isomers). Each of these forms is optically active Mirror plane [Co¥*(C,04)(NHs). complexes whose cis-is 8. [M(AB)s] type in cis- and trans-isomers Q Rd cis-Lisomer Oy { Le 5 hy 1 XA Ph 1 —— oO 1 ' t { N N ab trans-t-isomer comers of [Cr“¢elys]” as and | optical isomers.~ hy, 08 hence cach gives a pai pers (deand forms) shown in Fig. 4.31 for (¢ ory ex compound. Thy, 9 Octahedral complexes ontaining Ol ticnlly netive ligands. ICo™(enyp hi jon is an important examp) type Of emanedral complexes. Here en Rain thylene diamine end Ae: me respectively’ Both these are bidentar mn’ en is a symmetrical ar c sally inactive Tigard. on the other hand pr Buti % and is. therefore, opti dg. We have already seen that [Co(enyy ‘Pre, jon exists in four geometrical isonet: of these Nur geometrical isomers, Wo eno, and two are trans-isomers. since both cis-isomers HFC unsymmetrical and hence ar Hy petive, ic, each of the meGeomers can DE resovied 10 BIVE IW optical isomer cis-d-isomer and cis ‘hich have becn shown in Fig. 432. On the other te Na both rrans-isomers are symmetrical and hence are optically inactive, Le. nor Nd, tix can be resolved 10 give any optical isomers. ‘cis-d-isomer is om of g ve ihe is formulated as €4 [Co™Cen) (Londons) 0, i trans-isomers ‘pny(NO2)2}" and cis ture of the ligand, pn. ‘L indicate the ‘optically active na! Mirvor plane : o i N ' © = e { { } | ' e ! 1 © ! | and [-optical isomers of one cis-isomer } Mirror plane } ® ak a | (6) N£---- i poo Noe Z {@ o Fig. 432. d-and # @and Loptical isomers of other ¢ . de and optical isomers corre sponding to two cis-i s-isomers of [Co™*(en! : )(pn)(NOz)aI" ion 10. Octahedral ligand (polyel complexes containiny ee ah eaaie linen Uh ethyl ig polydentate ligands. C Sa cele Be eae ee Gamine rena Se Complex containing hexadenta is given as follows: lene diamine tetracetate ee ae ‘exists in two opti viated as EDTAY 0% )Isomorism In Goorainauon Compounds 99 fo} As. +O—C—H,C I = ® rN @ CH; —C~0 ee We ‘CHy—CH,—NC eo © |? cH,—c— 4) ° 2a speach fou ie Te as 3,4,5 mae) and two donor nitrogen n a ir 1S coordinat de a oe Goh cen unis On ES me at wig nitrogen atoms. (Co’(EDTA)]" ion has two optical isomers shown in 1 Mirror Plane — ' form Fig. 433. Optical isomers of [Co*(EDTA)} ion. ‘Two optical forms shown in Fig. 433 can also be shown in a simpler way as given in Fig. 4.34. Mirror Plane d-form (-form Fig. 434. d- and [-forms of (Co™(EDTA)} ion shown in simpler way-3 Ng? 39% cis-d-isomer | Opt mers for cis-isomer of [Co (en),Cl, Fig. 440. Geometrical and optical isomers of [Cofen),CI," jon The complex ion, [M (CN) (NO.) (HO) (NH is optically active. What is the Cs | geometry of the complex ion ? — 0 ‘Solution. Since each of the four ligands viz CN", NO,-, H,O and NH, is a monodentate | tigand, C.N. of M atom (central ‘metal atom) is 4. Thus the given complex ion has either square | planar or tetrahedral geometry. Since the given complex ion is optically active,it has tetrahedral geometry. Le The formula Co{NH,),CO,Br represents three isomers. (i) Draw their struc- tures (i) How would you distinguish these isomers ? the three isomers represented by the given formula are given nage) Solution. (i) The structures of z in Fig 4.41, In isomers (a) and (b), CO,” ion acts as a monodentate ligand but in isomer (c) this Vhatdy ion acts as a bidentate ligand. a rodents mors wo M wee ----“nt, (©) Ionic isomer 4 te CofNH).COBEisomerism in ,Goorainauon wormpounas o cis-isomer frans-isomer Fig. 4.44. cis and trans isomers of (Pt (gly),]- [Pt(P(C,H,),}C1,],- It is a bridged binuclear planar complex and exists in three isomeric iz cis, trans and unsymmetrical shown in Fig 4.45 cl. Cl cl N Sow . aA (CHOP ae f° So OS a?” . NRE, a” Pil! oon cis-isomet traas-isomer CN Lo\n Pein a Na~ Neer, ‘unsymmetrical isomer orms Vv’ (CoHs)sP’ Fig. 4.45 Three isomers of [Pt (P(C,H,)3!Clalp [Cr(VH,)(OH),CI,]” ion. This ion has three geometric isomers shown in Fig 4.46. 2 (b) C1- Cl trans, OH= OH cis a Fig. 4.46. Three geomeiric isomers of [ ,XOH),CL J ionot d-fo rid! 452: sxe 100 (07s Lik > Fm cl some a DT } Mis (ICT (Ney 1 com tahedra ical isomet ometri 4 4.53, Geom ee (B) is veaisomer (geometric ince ci s eT peis-isomer jets as d-cis-isomer exist hove discussion shows, that [Cr srical isome! five are geome! Br (@) cis-dibromodiaquadiammine chro (TIP ion (Geometrical isomer) NH, A Optical isom Np 34 Ps [co(ox),]} jon also does not have g Come re of ‘a w the er Te (iy fOr (er, Cll CHU) [9 (AA), theo \ aie ‘if Ll pe hy my) co), Br,] seca critter atic has five geometrical isomers viz (a), gy ‘are obtain are cis to each other. rs and two are O| + Lor ers of [Co (en),]°* ion of all the possible isomers of the Follow + jon, The given complex ion is of IM: a, bie i A F (a) is obtained when the ligands of eg, in| obtained when the ligands of each ty, hype) ‘ed when the ligands of one type are ae te Shag At isomer) shown at (4) of Fig. 4.53 is opg Me (optical isomers) shown in Fig. 4.54 Pay (NH,), (H,0), Br,]* ion has seven isomers, | ptical isomers. Ooty) Br } ‘| ZN] | Br (b) srans—dibromodiquadiammine chromium (IID) ion (Geometrical ison) HL, mium. NH, (©) cis-dibror iN rad Gh chromium (II) ion (aaa amine te @ aie ee trans boos, Some) 65 chromium (11D) ion (Geometrical ison) Fi rn ig. 4.53. Continued on the next page(©) cls-diamminediaqua transi 4 trans-dibrome chromi sesh ln Crm | ¢- 4.53. Five geometrical isomers of (Cr(MH,),(H,0),Br," ion , Mirror On, decis-isomer of [Cr(NH,), (H,0), Br,J* ion I-cis-isomer of (Cr(NH,), a a (optical isomer) ion (optical isomer Fig. 4.54. Optical isomers of ci? isomer of [C(NH,) (4,0), Br,]" fon (i) [Ce(en),C1,]CL. This compound contains [Cr (en), Cl,}* and CI” ions. Since {Ce(en), Cl,J* ion is an octahedral ion of (M (AA), a,] type it has wo geometrical isomers viz cis- Ieomer ind frans-isomer (See Fig. 4.55) Since cis-isomer has no plane of symmeuy, it is unsym- metrical and hence is optically active. Being optically active, cis-isomer has two optical isomers namely cis-d-isomer and cis-t-isomer (See Fi 14,56). Since trans-isomer has plane of symmetry, it is symmetrical and hence is optically inactive. Being optically inactive, trans-isomer has no optical isomers. f joomers of {Cr (€),C1,]" f° (geometrical isomers) Fig. 4.55. cis- and trans118 " Mirror \ cis-d-lsomer clt-bisomes Fig. 4.56. Optical Isomers of cis- isomer of [Cr(en),C1,}* jon, two geometrical isomers viz ¢j, (iii) [M(AA),B,) type complex. It has two gi CdS a4 tray Fig. 457 cis-isomer trans-isomer Fig. 4.57. cis and trans isomers of [M (AA), B,] (Geometrical isomers) Cis-isomer does not have any plane or centre of symmetry and hence is oplically x Being optically active, is-isomer can be resolved into two optical isomers which are cere and cis-l-isomer shown in Fig, 4.58. Mirror Aa i cis-d-isomer cis-l-isomer WIC Fig 4.58. 0, . v) Of + jon. exists in cioeand NOS) ‘on. The given complex ion is of [M (AA), 2 6) 1998 i 'somers (geometrical isomers) shown in Fig. 4.59. ptical isomers of cis-[M(AA),B,]a and cis-! isomers (optical isomers) shown in fomerism ' Gooraination Compounds N en 119 non cis-isomer et Fig. 4.59, Two geometrical isomers (cis and ou ; : trans) of (Co ce f Since eis-isomer does not have centre of syinmetry, iti oe CL MODT ton 1 i is 0 met ically active and hence has cis- Nien cis-d-isomer c ner cis-I-isome: Fig 4.60 cis-d and cis-1 isomers (optical isomers) of cis- [Co (en), Cl (NO, ion, |Give the structure of all the possible isomers of the follow y z (A) () EP (gly),} (ii) [Pt(NO,) (C,HN) (NH,) (NH,OH)]* yg Caner area (iit) [Cr (NH), CL]” (Delhi 1998) (B) [M (AA), B,] type complex. (Delhi 1999) (C) {Co (en), CL(NO,)[* (Delhi 2000) (D) {Co (ox), ion (ox = oxalate ion, C,07*) (Detht 2001) Solution. Do these problems yourself The complex cation, [Pt (NH,) (NH,OH) (NO,) (C,H.N)]* has been found to be optically active. What is the probable geometry of the complex cation ? Solution. In the given complex cation, since all the four ligands viz NH,, NH,OH, NO,”, C,H.N are monodentate ligands, the complex cation has either square planar (C.N. = 4) or tetrahe- dral (CN. = 4) geometry. Now since the complex cation is optically active, it cannot have square planar geometry, because square planar complexes have plane of symmetry. However, it can have tetrahedral geometry (See Fig. 4.61), since it has four different ligands and hence the mirror- images of the complex cation are not superimposable, é.e., it will show optical activity. Mi nr, 8 jirror NH, | oan, Pre } ms HOH,N 4 ss BCs gl “I \ ae Noy ! 1, ‘ Fig. 4.61 Tetrahedral geometry of [PUNH,) (NH,OH) (NO) (CH NDT