Coordination’ Compounds 5.1| DOUBLE SALTS AND COORDINATION COMPOUNDS Addition compounds are formed when stoichiometric amounts of two or more stable compounds join together. For example: KC1+MgCl, + 6H,O — KCI-MgCl, - 6H,O carnallite K.SO, + Al,(SO,), +24H,O ~ K,SO, -Al,(SO,), -24H,0 potassium alum CuSO, +4NH, +H,0 CuSO, -4NH, «HO tetrammine copper(II) sulphate monohydrate Fe(CN), +4KCN ~ Fe(CN), -4KCN potassium ferrocyanide Addition compounds are of two types: 1. Those which lose their identity in solution (double salts) 2. Those which retain their identity in solution (complexes) When crystals of carnallite are dissolved in water, the solution shows the properties of K’, Mg” and CI’ ions. In a similar way, 4 solution of potassium alum shows the properties of K’, Al ‘and SO? ions, These are both examples of double salts which ‘xist only in the crystalline state. : When the other two examples of coordination com- Pounds dissolve they do not form simple ions ~ Cu", or Fe’ and CN = but instead their complex ions remain intact, Thus the euproammonium ion [Cu(H,O)(NH),)” and the deg Shapes of d orbitals. Contents 51 5.2 5.3 54 55 5.6 57 5.8 59 5.10 5.11 5.12 5.13 5.14 5.15 5.16 5.17 Double Salts and Coordination Compounds Werner's Work More Recent Methods of Studying Complexes Classification of Ligands Effective Atomic Numbers Shapes of d Orbitals Bonding in Transition Metal Complexes Valence Bond Theory Crystal Field Theory Effects of Crystal Field Splitting Tetragonal Distortion of Octahedral Complexes ahn-Teller Distortion) Square Planar Arrangements Tetrahedral Complexes Magnetism Extension of the Crystal Field Theory to Allow for ‘Some Covalency Nomenclature of Coordination Compounds Isomerismda sal ie yy a Os 5 Meeentotayntooe KEE BIT pers cinco ye od and I” Completion, [Wb 5 Numba osm ps sin SS an Conn ee tnd termi FAO ats CO il Mero cota ett Pedant som ot (CHOI Gur Ri tego Ilion npr. ns ab aed 10 this STution. he amir. poeM ‘ q 7 T (ror tober a : dae aed esi ss) yy : : : ‘2 apemmonomin ose ose 0 ne : : 7 feats. +88 Ces eater athe cen, 3 sabia etn. a8 EN ‘Tse reukt song aged at . Not hatin anton a Sys roo! wot absolute prooG sims vag Oxy om 'S WORK jt posible thatthe comet experimental XTX 5:2 | WERNER'S WO! cena eine alt Sra ag, 1 Pe tat es ade Hi ‘Werner's coordination theay in 1883 was the BT TT as put forward before the electron had bees lithe isomers More recently the X-ray struc. l Onesie ese me emenered tt HSMN PN yen fale Theo nd a ae ave been determined and hn » copeetam ‘Secovered by 11 Therpeon ia 18% 04 BIO OTE pet Pie for Chemistry in 191, Tuntat the shape is octahedral Figure 52), "SY Z Segoe taking work over te next 29 years woo Ales any bnowlede of Ponds oF srt Fy ‘Moe recently, with a bidentate and { Conplees mst ve Ben 2 OnE ND ypu of stable moles of 3 compo socharetieneamine(2dannscthne, - example why des a abe sake COCK OT ca, SNH, and CoC, ANH. ? What are thes Sto opticaly active isomers of exabedral Stare previo cmp C2 su Ni ogres ie pope tbo of determing erates scr A hat ie Xm it ead ay ofthe mdr suena i, sigue anda hs stubes were ade ngs eaioa che ice ‘Benpexes have been found (Figure 83}, ae cmp wih ee NN) ra me fa i Spon) Teco TIE cnn dle TUlnitkespecmébeciberniiel Sky oer Tryin necpememiaestonponiiegCeciinmatieisiraas naar enrages (HZ Set ‘oespond to the ales ow known 35 xin state) of te 1 odie tho ferent somers for these compere, { Soa nam es it of iy ly Bement noe = ‘cies corresponds tothe number of charges on the central form, but a square planar complex can exist Se etnies tambo a ASMP Fg 52 Yona cad copie 15 [CINE and SCL Tus the pinay wane is plexes ate squae planar rather than tetahe- a mi cain ineeetennuo ee pean nese ae . oe ~ mR 2 Seam: Tse esi tei Spm ey Cas eC) ty _ oa, eee et « Foon pe er A f a, odnedwienel Tisserant Saber Lp ae ame pte ch DZ x 2s CT or neal ales ch at, Les ommoal, a NJ lands maybe psi on uh aN Ech metal resem oom sh a «al cde eat se - Tot} the tres Cr are hel by prmay rae ‘es Tae NH, roups are held by eon lenis, ee sonnet 4 ners seca a Las shapes of the complexes. 2 ‘The a arrangements of si groups eal a cae i 5.3 | MORE RECENT METHODS OF STUDYING COMPLEXES ae 8 planar exago, tignal prism and an octahedron eri Smee dec Ne Taser nua svi i rer 1. The concemraton of sole ese 2. The mumber of hago he ces wih formed en lation : core torte ‘Pion tremas a ee = | AGE cms corsaman core? ae she sl om Wan me es conducts SURE the gy nrciexperments cin os reve Condesa eh wena (rarer 4eeo) coc, 8H eto modem and Werner stvetres ‘able 5.3 Number of hoses ee pi ciines Secondary valency a a ond 2 4 SNH, +10-=6 famporse : tinier ce “seooemneypen 2 werd when a cherizal subtance is dissolved init Cryoscopic mes a Sn a a chi cig point were. The depression of teeing pi per opr measurements can be wed to ind fa Shane depends on ie umber of pares presen. COOP aid pends 0 he OED fe fanned a merle sociales into two fons it wil pie lec dn ae arrange pari te fons are formed tis wil give thre times te apes depresion Ts “Te recrng posto 2 ld La tr +O" panics [chara] MgCl = Me= 2c (panies) | charges) LG, + La 2301 capris) [(ocharges) “Tee numberof pars formed trom a complex molecule determines the size ofthe depression of freeing pot Noe ta th number of paris formed may beeen from the otal numberof hares ttuch can he ebined from conducts easements These fwo types of information can Be used Topstertoetash he stare (Tbe 5) ‘ible 5.4 Extablching the structure of complones Formas Coenope resend Wal conhaiy SR ©, 0 pee ‘aun Teena 36 cra, a, 2s sets {coos "201 cc ‘pace — Iconnin.e41° Cr CANO.,ANO-2NH, pe cage ieoest) C4) {o0¥0, 2880, 8 Span 2edaaes [costo eNO 3KNO, apace sae 2x (Co 80.) Setar 3K [CNOA === $4 Cutan of garde sigur pan (hm ad wm occ of ra caenoonsed eon onperetle™ ‘cri het mp rnc sd a Dah easas SatOy S rsh mon tobi pa cain ee one sd ane complex (PUN), CI] i sqate planar and can et anc mae forse Tae apse women OS te Sri metallia bonds nee out nthe vans conguraion Hoacrcr 2 fase wipe moment elon pee (UV tf sho pond vate noraion ce tosh ioe! some By mens so dasa aan ene nace) nite tePanl wha hae vantoncs ees enon poe eed pert rminin lvl racre Ts provie juli On sapeandetodiepis busses secs ies nformaton about the numberof unpaired ito Jee how the cecroes ae arraneed and he conples can he deduced ftom ts For e% 5.4 | CLASSIFICATION OF LIGANDS “Tere are several ways to easy igands and thee ace dct olow 1, Based upon charges fa Neutral ligands: H,0, NO. CO, CH, 2 bh Positive ligands: NO and 8 : Negative ligands C.NO:.CN OF 2 Based upon dentcty of he ligand ‘The number of donations accepted by a ental atom fom partes esas ‘fhe ligand Ligands may be casiied as flows Based oa ex dest Monedentate: Only one donation is asceted from the Bpind For euplc. H.O. NO. CO. NH. CoP. Crete by Bideetate Two donations are accepted fromthe gant For ramp (enretiylenediamine {i pe propylenediamine a. ye i Ve (Gy ts trimetnylenediamine (o)bocbuntesediamine <2 (©) ox? soxalate (on acacaseacetonate 5A ay aN ° o ‘ ii ‘ OS, 0% ‘0% ae San Tay: See eae eet - | ARG css ccm cope sete f Mennenae Si donations sep +cat nee (i dng simeteosite o EDTA’ ctlylentamineemecae mM Me MN For example ea TN Sma 7 Oe ay Hey I we are ne Noon orn onpnantroine fo ~— ee Vv ne en (3) NN Diethyioeartamate ion (si Saialdchy9® ® For example, ‘scaled Rexdentate pan s. ot 2 wg> OOS op xi §.Hydroguinoiol ion one) () @Phenlenebisdimethylrsin (arsine) os : os CO nica” AMCONBE P. es 2. Chelating: ligand that an form rng structure wit the emt pte een Avett nt toca bes aem aes an r i) md iinodiacetate ee Oiendeasetanse (Dimi {cated compet ae mare sate tn sna eens wi = en" “ou, ofthe complex involves breaking two bonds rather thn one nse H¥ands 8 dissociation we8PN, Prom Hower tn at ee i thn Fey yb 44. Tetradentate Four donasons sre scepe rom he ga, For example, wenswietplenetetaamine (8) NTA*zntibotiacctate aa ory 7 whe tobe pr NO Nn a Na oN Pentadenate Five donations re aceped EDTA” ciylnedimie tice hem Forexampe, pray, IO. cue NY io fo Se! AS RL RP . eai: spon ura atom utes scent en % Aas pon bong Iran beter mre a om came Sete si 8 ernst or ah ena elon cal iki fk donton sxample,C0, CN, NO. 1) Tc NGiteclhscoycu fem hele A, " Lim ta the #* orbital of central atom Jor molecu al her. Be cee sna lakes lice in these ype a he ume concn ce an or the bon ode (4) meas of PR, the ack donation maybe dete a (1) Ince of hhc donation maybe depicted wing he example of Za sal ithe Bosal hatheR* orbital of C~ C bond, Hence the bond order o molabnd eth ineeass as compared to free C4, meleasie oa "lanai. Similarly,C,H, molecule loses ts Hncary ‘0 buckbonding. CH, molesle oars ot the planar, 5.5 | EFFECTIVE ATOMIC NUMBER (EAN) [hvcally EAN spits the umber of econ ailable around a central Ing the electrons accepted tom ligens tom within 3 complex, ned ‘His mathematically defined ws follow, COMPlex= Atomic numberof the en 5 foidation numberof the + (oumiber of electron col tral atom (2) central atom with sign) lected from the ligand). oe Table 5.5 Elloctvn atomic nunbors Tabla 5.5 | hee am Aon Cagle oF e mB eacoy fe % tween re 2 recon a - & 2 (cant ‘ = Ni 2% INKeoy) _ o fewer " 6 iran n 7% jray" t ™ re 2 raceme si 2% wma “ * ra 46 wacat ’ 2 n muy * “ 2 ime-Gnyur-eanyy “ “ fe 6 trate-ciy ' : fe 2% fracOnOr) * = * © 2 fexcons : y 2B iweout Sldgwick EAN rule i ee te a rar atsean valor and Fs of hi pice Siew se carbom exit 908 caren 1. Toe wwe f CO motel scan be predicted For Camp g apace) ==" ecm rns mee > tc fem shy Sarees E* steol TeCui St Say Suse EAN IE sua enable 2s cofzraton and ence obCY Sidgvick 4.1Ma(CO).7 enderposinenzasion 1 3 5.6 | SHAPES OF d ORBITALS ten usd in orion complexes its important 1 sy their shapes and Site nas ren ed een andes ay be divided nt wo ets The he axea ty and z-The two e, orbitals have tre orbits have tena! shape an pla betwee te axes and . Raa ee on soag he ans (igure 53). allematve names for, and e, are de and dy 2! ob ob elo “1 ON 9 9 Fie SS Shapes of corbitls = 5.7 |BONDING IN TRANSITION METAL COMPLEXES wre noc te M metal olipand bonding complexes a yatence bond theory fective an empty obi ef abe ects maa for on see ht pF ae se meld theory. However. itis ofiterest for study as akon crane tones a compen tons in which ligands ors nd the etal crystal field theory ‘pistbeory 885 proposed by Bethe and van Vleck The stactionhetweca central metal and igands in plex s considered tobe purely clectosiaie Thus boodine isthe ceanpies may be onin at7ac- ih getncen postive and negate ion such x Co" and CT) Alernatvely ioe pe atractons at fue to boning (the ligands neutral mocsle ac se Nt er CO) NH. was cole moment with Pi earge on N and $+ charges on. Tus in [Co(NTL) the 8 charge the N atom of each NH. fein towards the CO". This theory simple It ha bee eomahaly occ io caplaming the lee- Rone spectra sod egotism of transton meal compicas partealaty when lowes made fr the ily of some covalent nteraconbeeneen the aria oo te sland ligand When som= lO {fee sma for covalecy.he theory ies renamed abe Head eld theory Tare typeset meracon - ‘eposble:coverlap of orbitals overlap of erbxtal or dv ponding back Nonding) dee to [ria orbitals on the metal with empty p orbitals on the bps verse Molecular orbital theory ‘Both covalent and ionic contribution are fully llowed for inthis dheory.Thoush this theory i probably ‘he mos insportant approach to chemical bonding it has got displaced the other theories This Because the quantitative calculations involved are dffcult and length. imclving the uae of exisasive computer time. Much ofthe qualitative description can be obtained by other approaches wsing SmetY and sTOUP theory 5.8 | VALENCE BOND THEORY ‘Te formation of s complex may be considered as series of hypothetial steps Fist the appropriate metal jon s taken, eg. Co”. A Co atom has the outer cletonie structure 34s" Thus a Co” on wil have the Suture andthe eletrons willbe aransed: {Whi on forms a complex with sx ligands then sx empty atomic orbitals are requited on the metal ion ‘oreccive the coordinated lone pits of clevtrons Te obits used are the 4g three 4p and two 4. These. Sschybaned ove att osu uso he bas A and oa com stetettons forme coordinate bond ing alone pair te bond by overlapping sith an empty hybrid orbital onthe metal ion. tn this ‘aya bond is formed with each ligand The dorital used are the 4, "eston pairs feom the ligands are shown a ve and 4d. Inthe diagrams below, se acess EgyI tn ea Th ey 29 coratroy KE ™ of Inthe crystal ie mms OCCUPY the ory sigan tt a theory the following as furthest epee sumptions ac # proach of 1, Liga “J 9 Point chatgeg , = = | HOMME oes nnn cop “ isa Sis te out ai ae wed ‘rts gut hh oat he eee SS ee) nthe fee atom. Howevet, hese nba Lethe orale now eral doallhae the same enc orbital complet. Thee ao ey ot favedifeent ergs ends he bile. The magnetic Moment depends and are termed degenerate m8 Metal ion. the five smu number of unpired eens 8 hy a danse a phekagee eeh e oed degen ld 2M fed fr ‘umber of anped cers The $e 8 OTe comple. Am alierative son Fa sion between the fl andthe sg OME Be neyo aE OURS het rangene so seme oe RT ert shown flo, a orf ands sondern th alc furangement poste wen he e085 | tne fel rodedby ana ee tr een elem hr Tone pis om he igus stv caval Oy the gard eld *phcealy syanineal avn doles} a) CUT ‘Octahedral complexes. 1 octahedral complex, the nat cal isat the ene of Te ston» and point tes aga const znd ae athe corner can ne obil complet SUh Sealy for clecrons to occupy the spre acy rc Tas it will be mors favours spireetrons. In similar way.suong field ands sch ar CN" cause re pling 8. Inti ease ques les enerey pac the lectons and for sown complex ee Tales oy ‘Similar arguments apply to high- and low-spin complexes of metal ions with d’. d° and d’ config == joe These ae summarized in TableSTL ae ew Figure 5.19 Relation ofa tetrahedron % Figure 5.20 Oriantaon of d orbitals relative to 2 cube. toocube, ‘The direction of approach ofthe ligands doesnot coincide exactly with either the ¢, oF the 1, orbit- sis The angle between an e, orbital, the central metal and the ligand 1s half the tetvahedral angle 109°28'/2=54°44". The angle between a1, orbital, the central metal and the Bgand i 35°16. Thus the # ital are nearer tothe direction ofthe ligands than thee orbitals (Alterasvely the «orbitals are bal the ide ofthe cube away from the approach ofthe ligands whist thee, orbitals are haf the diagonal of the cube away.) The approach ofthe ligands raises the energy ofboth ts of orbitals The energy of the, orbitals is raised most because they ae closest othe ligands This crystal eld spiting the opposite ay round to that in octahedral eomplees (Figure 521), "The orbitals are 04a, above the weighted average eneray ofthe two groups (the Bar centre) and the «,obitals are 0:6, below the average (Figure 522). r+ i fo ‘L — , erage i= ic Set 5 _ a \ | 7 \ 25a, \t Irene edn soe” tema a i igure 522 Enel or aba in Figure 5, epiting of ene -21 Crystal field splitting of energy a tetrahedral field. levels ina tetrahedral fi—_— ~~ y ou en CE 151 Coordin compres? snpleesiscOmSHETI eth cr he een configuration of he hater 5 Coo nemo hoe, a wer ne cnFront cet meld. tere no CFSE “re magic athe ens fe third the ier Ca ear a. CFSE Smal cha anda here losin CFSE O13 ord and where esti ae ae oe pao PE thin th ha furans sohien jy aston metal chlorides bromides an ides orm take cn ee om ee senna me nds TSIM yy ws hedral structures nace oes oteinc GNETISM 2 Teeth tia d= 1S a= 14 | MA aaron, ap aunain abel . vane sr esspting 8 M28 a HAE Weak He iene magnetic moment canbe measured using Go oment ‘os betevaeia esl SE re MM etaea pliig By Ths ees epaed cn a2 Cou aac Ine mane hat he magnetic moment 4 Soe ed ind as 5 ys al cMplXES Fe High spin, _ ons of unpaired eet in then th spn ony formal cn be Wad to ete oyever tetrad 8 8 anda be suber on ons. This pres tesonable agement fr complexe of the tro 0 tai808 Fiera oe reve energetic favour esebsonoit rb it nd ser eng « era (Once the number of unpaired electrons is knows ether the valence bond or he xsl ld theory fans specs oled ed pe Ce ee | EOS can bed 10 Work: out he shape of the compen, the atone of he Sead. nahh m0 Seecron faerie Smplenes beter nero outer dorba sewed For cule Coll) toon soy complete ah Soro Seng on cup 7 Soecrosmncl a saan Stan ate ooh Mot of tem are dampaci fu [CaF]. eprom nh an omeoned ote se moment of 53 BM. Crystal eld theory expan ts Ege 52) ry 4 wil ‘Co{+11) forms both tetrahedral and square planar four coordinate complexes These can bedistinguished * S _ 2 bymenee metaeens gue $28) _ “7 Oa Hower ori anguar momentum ao cnet eater o leer dec othe magni ok * | rome For the second and third row tanstonclemeas stony is cction seneant. ut - “a 09-08 as {pe ott coupling may ert Because ofthis the spin oly ppvxsnauon sc longer vad ah ere ¢ mov * ‘Foxensive emperatre- dependent paramagaeisn Ths the srpc ryan of manetic moments / fH fo caiees 08 os interns ofthe numberof unpaired cerns ano be eveoed rence oe of aon cements ‘ cb ‘to the second and third rows. The temperature dependence is explained by the spin orbit coupling. iE 4 12+ B= -04 os 6-16 ‘This removes the degeneracy from the lowest energy level in the ground statz. Thermal energy then allows a ! we * variety of levels to be populated. © ED Ga 2 ara co ono oo 20 «GTR ww -ueos -077 424 ete nwntnn te ¢ Ge GO ow awe a os 6 GR) TET -atsase-os —-036 12 6. ec compe i rng ade : & Wy -a4eane-ae 08-06-08 - ome 24240 09a ) came ncone ql 7 ‘Strong fe ligands. g [COCSH CFSE in bath stata ad taba aioe ven in Table 5.16. This shows tha oF sent sounder Sed endd argent CIS inh thea an cael compet al aie tome aomevct t ene me CFSE a the octahedral CFSE i greater thon the tte Ce Oren 3 in i] = 1. Where theigands are ag nd bu Weak cen (FI NOs, ‘configurationsare Nabe important. For iral structures d°, df, a, d’ anc a ™ 7 RARE Som cotcaeoantcneenaaee tO IMO eng eT figure £24 Co" in tetahal ad gure NOP G ANRPO Teer Gr era a MOO comlnt on comple 2 Westen sea g MCO"CAP (and za" CI eat, Figure 5.23 Co in high-spin and low-spin complexes. Pl eee sn os in CFSE ths es important aw eiion onsale This reduces the musnitude of A. aaa3: THEORY 5.15 | EXTENSION OF THE CRYSTAL FIELY TO ALLOW FOR SOME COVALENCY “The crystal ek hoor based om prey elect aration, AL ih this sec tly successful explaining tno')f0 BS 8 imprabetie mmion esemncles the beoy remark sees exaining ihe ag, Plexex their spectra and ter magnet properties Caen ca quite sing po Sivanans oe earn eee ht some coven! Doing Ses cacy The tanston met smpeses 1. Compoundsin the eg osiaion sae suchas nee earboratTNPICOD.NO mo lec tion Betnce the mctl an the gan Ts th boning must bs covalent tte ms cae ert cry imc SS ee cian oie ce Seeeeesee 5.16 | NOMENCLATURE OF COORDINATION COMPOUNDS “The rules for systematic naming of ordination compounds re dscused as fllows Broun, the 1. The name ofthe cationic pat is writen fst followed by the anionic part 2. The name ofthe ligand i sted before the name(s) ofthe central atoms) 3 No space et hetween the names hat relr tothe same coordination entity, 4. Ligand names ar listed ia the alphabetical order (multipicative prefixes indicating Vigands are not considered ia determining that ore). ‘8 When there are several igands ofthe sume king, refines ke ttt, before the name of the gan odie their number. 3, When the name of the igandicades terms ike tttr et. then prefixes like bis, ti enki, Pentakis ct. are writen before the marc of the lgand, and the ligand name i kep win beet, fo avoid ambiguity For example, © (NH,)ediammine (i) Me,NHdimethylamine (id) (60); (ethylenediamine) (iv) (NH, Me)is (methylamine) (Go make it distinct rom dimety laine) «There is no deletion of vowels or use of hyphen For example, (NH, tetraammine (The names of cationic ligands are ended with ium: For example, ( NO:ntrosyium Gi) NH, NH hyarainiom 7. The neutal ligand names have no () HO-aqua (ii) NH gammine (ii) CO-earbonyt ii) NOssitecsy i the number o ena, hexa, et. ate wed special endings For example, —r™rrrrsre=—=s—— Cd i Meconty, (©) MeNtismehanere (i) MePHt,-meay (a) MeO SONG G) Me,O-dimetiy ca @) Mes: dime ety G9 Catebensene IPhone “doppia © NO site EME Heche te (i) CO* seabonatg (i) MeCO}: seca ory ) ac06Aeciyacetonag 1s Ligand names ening 1) 50% apna He ae canes os i) CO;esox Gi) OCrbypochtrcg G9) NO} niito « Litand names ending wt FE Mody nn Me Meshes (0) Cheha (i) CN snide (iv) HE tirido (©) OFF :hydronido (i) NHamido (i) D":dewerdo oe PH) nyo womiste donor som are no ended wih For example, (CH: meh oot mtn) (i) CHC CHa (i) Ph pheyt (9) B:eytprnyt (6) CH, =CHt vy! « Forth dono th prfiie woe whe ines xin denon andi SS thchapty ois Wade he mnerctancsoetea eae eae (© x-C,Aien = epdopestatey or petsapogdopentatier (i) n= Cattg af = bomen orheaopobezee (i) eC HL: —atyLoewtapayt * Ambidentt ian ate ame ows () EN: ganido or gio -C INC inp eerie -N {8 NO; igo oro ONO: ait or visio -O G8) GOCN: ans oeeyamto-O E:NCO: isoeyanato or eynato-Na soon ons (oy Sewer ora 00 pe 1 gncosito(0-07 o) Se Seat Ae f , souncewn! (Atoms :Atuine (i) Paina Pine (Gi) Moybenuo =Mosbiae (60) Zine ica (G) Nickel =Nikelte (i) Cova Cobatate (i) on Ferte oe _— Cn Can ame TSA ecm Ane “Seng gence es eae enn Sura ih he eee eH appizable) thou the itervention of + space Forexample, erate within racket ater the (PC), potas bexaeyanioterate (1) tr pti bexscyanioterate (+) or etrapoaesam heraryanioterrate (i) KOC. paso pentachoridoniridoosmate 2-) ‘br potasiam pesaclorionitioosmate (VD) (G8) [CuO.J0= CNH, Plies (urea copper (1) (i) [COCKNH,), JO. pentamminecsoidoestlt (I) chloride or pestaminetlrdocoblt (2) chloride 1. tthe any wate of cysalizto. st included inthe name. For example, [C1t,0),C,}1-2H,0:seranqdlrdo chromium (Il) chloride -2-water or ‘eragundihorido chromium (I) chloride diye “These rues ar sate bythe flowing examples Complex nis [cats 1% cai feraumnineebalHl) chloride =. Fentaamminechlridocabalt(Il}) ion leon No, “Tetaamminesulpatocobat(I}) nitrate ee ayy Eien [eaves ‘Tismminechloridocysnonitrocobal (I TebiogantoNainc) a feasen.l ‘Complex cations “Teteathioeyanato-S cad) van Soren ecm, Wee ovo Tanita pron cron orm mete ‘etrapyridinepatinum(t) teteachloridoplainate() dor Tes(etylenediamine)chromsmi Il) chionde feuCh(CHNH),) Dichlordobisimethslamine eoppet 5.17 |ISOMERISM ‘compos nds that have the sme chemical formula diferent strata artangements ar ale omnes aon of he complicate formule af many eaiotoncompounae ie eric ot ha pes and ‘ember of shapes possible. many diferent types of tomers cesar Werner's classiest ino pols ionization yaks soil srdowton po and pase a ten omens water erally sees polymerization isomerism isnot trueisomerismbecawseitoccusbetween compounds ving la butdiferent Thi spoundshavingthesameempirialformt spolecular weights Thus [PUNFL,Cl), [PUNK IPC}, (PASH) [PUN CL] and [PUSH CTPA) pent coma) mafeet™Seasm} |) jou Figure 5.25 Polymerization tomers. allhave the same empirical form, Polymerization isomerism may be due to different number of mice in ‘he complex as shown in Figure 525, lonization isomerism “This type of isomerism is due tothe exchange of groups between the complex jon and the fons outside it [Co(N Be]SO, i red-vilet An aqueous solution gives a white precipitate of BaSO, with Ba selution, ‘has confirming the presence of ree SO, ions In contrat {Co(NH,) SO, Bris ted. sohuton of this complex doesnot give a positive sulphate et wih Ba. does gve acream coloured precipitate of ABBr with ASNO,- ‘hus confirming the presente of ree Br ions Note tha the sulphate son occupies only one coordination por ‘ion even though i has two negative ‘Other examples of ionization tomers are [PANTECH and [PUNE JBe,JC, and [Colen}.NO,-CISCN, [Co(en).NO, - SCNIC1 and [Coten).Cl-SCNINO. Hydrate isomerism ‘Tis ype of isomerism is shown by compounds havin the same formula but differing only in the number of water molecules of exyatalization, Moe broadly. t can aso be called solvent somerism to include ter arent lo ike Nor et Hans) pent nla manne Some examples of Hodate eis are as follows 1. CiC1,.611,0 can exis in following forms: {CrCH,0), }C1,: violet (three chloride tons)ee o BE scorns one cpnieie) ; 140: uM feat, 010,08 one ac aoe ET aioe : ron pit. Thus this Linkage jon win cs enn tn eT es i ther Nor O some cat sr tn ne ot. on ene Cetin gts ss a, Teer oes CONF NO, Sampara ee eh poy = SAT cone The be cpl PEE prepared. cc oie Be T= ONO and compound. The two materny ‘genanelbn,Soger eee ei eet rane on Ierepesetedin Fe 525 wo)” fo NA Ly PN a,| fax 1S ma, Ni senen ng Spm Faure 5.26 Nite adit comple isp otsmern ao coun witless SCN”, OCNS,0,°,CN, (0.8? (tool on Fc exam, (OS, NOand [o-¥-RavowO1n = [N-0-RuNO) OF | ‘oem Namen A é SA pel Penney LAA AMS POXA ASS | AN NAS. Coordination isomerism emer oer mg rnc Intermediate types between example ns isomerism may be caused bythe interchane these etems tal (cogu an (cM reese RE MTCENN [Cx JICol eee ea Peter (Cots FetN0, (Peas yep : ns, (cuciy (NOH) etc, 0y,f [Neo PetC,0,)) coordination position isomerism csr compl a ine wae af Mots en 1 fn sonst An came sec oman se pond conf No J Figure 8.27 Cocrination position isomers Geometrical isomerism and optical isomerism In dsubsitued complexes the subsite groups maybe adjacent or oppost fe to geometric somerism. This type of isomers s observed in completes with, four five and six ‘fa molecule is esymmetricit cannot be superimpoted on ts miro image Te molecule ands ror ‘age bave the type of symmery a shown by the It an ik bands and ae called an cnantiomorphic fait The wo forms are optical tomers Tey at ell either dexo or leo (often shortened tod. pending on the direction in which the rotate the plane of palarza kt ina polarimeter (drtates 10 the ight othe left) Optical isomerism common a oraedral compet nvoving bidentate 0p ‘The seometial and optical omerism fr complexes having coordination numbers four five and sx ‘edited a follows. each other This sites ordination neh 1. For coordination number 6 “Tae compleres with cooristion number can exis in octaheal gsometry.Ths following cass may arise in complexes with octahedral eometry 4 Al igands are monodentate bingo cra centre The varius srstures posible ae sted ‘elon Here M isthe mel in anda, ang 7 ed he | iq Ke ; (iy tfuasymetical idea ignds are resa.then the compound wil be optically activ. For Me xe we INI Ne ie og cmp re opel eee Orie Opty acre BeSpug] aa, oS ae a C ve re (i) The complexes with Me’ x! ne Me eal N wate ” Spears t oma Ma, Ma, IM(AA),T°,[M(AAJa,J*and[M(AB) sie = seaman amt nace po oy MT an MCAD op Benno al npg e Tea ident Hgand and AB isan unsymmet) once respectively. ae Ww" Ns! x ae ph ae re 5.40 Geometrical isomers of Petbe) F Figure 5.29 Geometrical isomers for complexes of the te [M/AB) ab) (i) The complexes ofthe type [M(AA),I= can show geometrical isomerism if the ligand AA has 8 chiral conte For example, consider the gsometrial ames st [Pu(ba), |” (Figure 5.40) whet ving no chiral ceter are present, then the complexes are bbn:CH, -CH(NH,)-CH(NH,)-CH,,_ urs crt comet sonoma omtiay |, +e er nae ta SN Co) ese cl ce se A im cee ve Mg, - we ote, aoa it ee tee ~~ nai Pro ™ oman - te Mt 7 loc? er aCe: i PSone Sy “peyote (no mnt) Figue S41 1 nomer are posible for quae aM (tt). Geomeria : [rh pn) ee 32) LN L° Om ne Ne? Na mw Ne 1 f1PaINH, ‘Georeicl vores of Pl CHICH,)- Conf. x binuclear complexes of the type, DLA Figure 542 Geometsl somes of Fd Cl(Phy: Etech ake eleceaae keene 1. Whi of the owing come at nen IUPAC mame nd cnples? (A) Hora pacttf00 onde im) [Be,1CH,COO)) (@)eamiedecurminasa eae fost Contents 60), (c)Femasemunslonoplstia aoe pemclodopate( I) 0) fray) (0) Msg etude IV) ai HS) 2 Wh fe olin op pen te aun sae of Co and Cn the ven comple? Icom. 034m yh eee Ce meee ome mec, Simon? Binet fare ease, esr mmae 28 coms match? (OVARY 4, < P-Diamagoedc (oy reef 4, can—an}] (Dr[PICyCenI (a) Lana (Bp ttronly whi (SKCO), clsmapneicand sp ybrecs | Which of the folowing chem specs a0 a8. yy (ry (3) Geomes cae oe Sy ompound V hace counter ine ne {i Four onadenatewnnepane bends ae com (A FICO). NAC, oyTin compound proces twotamnitsaqcows ——(e} ref) SO} Nae (Oyo Mantes of cleo temins the szne__ (P) THEOW) (MONO. whit of {5} Comples [CWCN}, i paramapnctc snd Ce fom ai” hyd. (@y[MubiF ons paraagneteand yp tbs [QWaskavenayantharm encore eas, (©) ANC atoms are agastat rom Fe" ho, magnetic andl on ep hybidecd 10) Spee teg thes ps nese Become Cor nN aE NNO owls gal)? wee a (MD sieraie. Which of the following Ware charsterisic of (B) 1 Diaminopropancdiamminesallvenhalt (a) cope ac do oo Seurepatmar © Sree tt cen Oircmpieanante cad ©) RRC NSemprt {b) thos meta-carbon bond. ‘Which of the folowing chemi species ire ah magnetic as well x coloured? (A) Hesaforidoterrate( on (@) Permangnate ion (©) Brown ang complex (©) chromate ton Incase of M(H (A) relation in between and Pit.

: [ Oh Ne TENSION TYPE QUESTIONS, Se Passage 1: For Questions 1-2 Dena rae trea eae ante conning Baa Eceeataiciesesant tice ies oo "hc ems nkag heron or ambiente so senate sed orcs aig oh ems hese ian “. Which of te following ately matched eens ‘eet an a ec te Sires ore ‘Sinn oem Be eeemmeaeare seponrs tarred Soccernet epee aecenincn en taaes One ae ee aren Passage 2: For Questions 3-5 Fis maxi men re comps emp! io ‘Te cpa OM stalconpley, (a) [SKH,O)(NO,),)-4NH,: eras (@) [NUH ),(NO,),-2H,0: tetrahedra (©) [NH 10, 28,0: square planer (0) [N(NH,),(9,0),}°NO,); octahedra 5. Which ofthe flowing statements are tue for the second complex? (i) thas the EAN value of. {B) Ican show optical isomers (6) Heannot show geometrical isomerism {(D) produces tre fldreeing poi depron. Passage 3: For Questions 6-8 Same gas not only donate thet lone pat the ct ‘ra metal atom but also aceapt the elton cloud fo cena meta stom. This is known as synergic bondi 4 Inwicho the folowing eases isthe bond ener of C=O bond minimum? (A) Free CO molec. (0) Temina! CO group inn comples. (©) Doubly bridging CO in complex. () ipl bridging CO in a complex. 7 Sect the coret order forthe stretching eater (1 C-O bond the following compounds foc MoCO}PE), feeMtCO,(Pery, on re Mitac MC (PMe feted )'t>usin (8) Sno (0) trata, aac eee feuweont (B)V(CO),| pesenon Restoring Tp Questions os, 13 Wich ofthe foloing fas hipher mile od Passage 6: For Questions 14-16 passage 4: For Questions 9-11 Be Spoinsoltion aptly orn aad rhc val of the tal andy of Fo eptek asim? me wt o2 m3 so. for wich valve of wl te comple st show Fe caiomerie? a 2 63 () Atotties anor which value 0€ te cmpes wil how Facing pint presion?” ” we 3 62 oi Passage 5: For Questions 12-13 syeri bondi typ of bak one 42, Which of tbe following has higher stretching fe ne for C=O bond? i imiconPe) {@) {Nico),P3te91 Bom nove equal sechng teguen: {D) None ofthese C= [Coes 9) NH icon sores be odes (©) compan abo (oa os) ors Solara ane Then (A) USeecraipe (B) 1: 2etewoine {@ Lteearope () 5:teceratne 16, Doe tothe presence of ambiente ligands coor aston coopoands show omens. palladium Geant of te ype [PAGANS] and ipa eiscs) a (A) taka isomes. {B) ceordinaon women. (6) joomsoe Somers (D) omer bomen. Fie ee ee nthe folowing set of questions Statement 1 sten {nd corresponding Sateen liven below it Mark The correct answer a: (A) It both Statement 1 and Statement Tare Woe fod: Statement I isthe comeetexplaaarion of Statement (8) Ie both Statement 1 and Sttemest Tk ae tue bt Statement Il is not the comest xplnation £¢ Satomet is tue but Staterent ae. i fae but Statement Ist eas with ole ot the an 1 Statement ts Only eis PUNE): ‘cid (H,C,0,) 10 form [PCI tomer, Statement Mt The oxlae fon sa bidentate Het hich oeupiesajacent positions es 2. Statement Under the strong eld ligand only the Skgeneracy ofthe orbital ost Statement Afr spliting of the dorbitals also Hands ale aot lated anywhere 2, Statement ENO is Sedonor. Satemest I:The antibonding electron of NO is ery ‘hoch auscpine ta donate spar from is lone pat. “4 Statement Dithiooslate is bidentate ambidentate Vigan Statement Ata time either 140 S atoms or to O tome acta Jona sams 5. Statcmeat LPF, s weakest donor aswell as weakest ‘Septor somporcd to PMc, in synergic bonding. Statement :Me group is having +7 effect while atom haing feet.coc (eH 01 Samar - a acc oT ees st le eo mension net meester re mer ca fe fot sc he nebo dana sw perro RP momar OL Ren gja wet citer. renin in Fite nusterof rh * peo ose sooo site pr. Ica fon FeO (Femou ee 2: Suppo ere: ie sae sah ricoh tes eet ae onan seid rani tae! Of (Sderot er of ora anon oon wk cea he Svat Da (i) Neate, errs Ah Neat eens UvpNumberotderoiones (0) Nami of emetic (ueaNeaue 4. Te numberof conta pater (oT, (oro, c.PUoNJ8_——— (olFant reco (arty Pee0 Fi 7 > met BAK SSM co sce sa stent st Seay come te a i some ait Both tHe 109 POKES he agg oe — eae nce ey 6: a a a [coven)ipnNO.):] Leger PERE uaepe by 38 28 8 rpc Hy and for Rh 1 le" eae or ee er I wih open me oes scrips fe i and ing cons ay = & etCO, 4. Te coordination numberof the cet atom in [CaN 50,]N0, 40, The umber of opal active isomers or the com seca frmula[Ma 11 Tee umber of unpaired electrons inthe se of tals complex [CotH0) is ‘2. Thenumberof empire electrons present in [NB 12. The sumo stereoisomers of complex compler and complex in flowing reaction inet cums. Ina A comp Ta it one of emer eo aap 2B me ») BtComplec) aa In cach of efor gusion Foetaeesteneen seen ‘ments in Coluesn | noe einige hoe in Colm I ae abled a P)(Q). RS) ‘nd Any ven statement in Coma fan av "st mtchig wih one ormor statements in Coli 4. mani peses other epecnehadeti gannt “Cah Goel Chapsi eaten} emetic OFRAEDTANT +) Change ts emer freer ‘dereumen rs CR) EAN asd et (Ofpiono) ene : DCLG» (Charen santero feattoncsiio "set wae (Canpeis naps teiest —— yc be etl ample pe wih he apr Tonal oe ‘ine|__toveg_ Ta IMAARET ) Algoma eames i, meena ce (@) [MAB (0) Treader of Stcosonen fo. 1R) Tee paar of peometreal (OMAR < (D)iMavase (9) Thesmader oes Se compe cmponnt wih he RET wy (rot @) [ero Omar ® FAO “Match he posses cared ot withthe changes cbered Calor (a) (MAB AT AMAR AT ©) DMCABDHT =A IMABRA I — (@ (0) (ape? Naat ® (0) [M(AA I AMAA AT 5. Match the comple compounds withthe proper, depicted by them. Celina ‘Cour TAIFACO)]” Hybridization sa (@) [CNH,),C,] (0) Hybridization. (©) [rm,f* (Eats geomet @){za(ey),!——_) Lowspincveee. (1) Esti opiat ee ‘atc he pir of complex ompouns th e rn tes that are diferent in them. Galena Goma (A) [Ma(NH,), 50, (P) Hybridization. ‘and {Co(H,0),]Ch, (8) (NH,),{MCL) (Q) Magnetic momest and K,[NiCL.] bce (©) KFe(CN),0,) {(R) Magnetic bebaviout, 2d KCN] (9) lesa cond> The gamber of gometial Som prods fox: Toe saber of seremeoen is ineesed 0 othl of (be orga xr deseaed to taf tbe ong 7.Mach the pair of complex compounds with the ‘properties tat arame them. camel Corn (ANTHGLOL!" (PY Hybridization sas]MoNH A @ Acar (@) Magnetic moment value and (PECL (©) (FADMG,T (RY) EAN vale, aad N(DNG).T (@)[FACOLP ans (8) Shape. [Nicout 1, Mat the coordination compler withthe number of toner formed ‘court ‘Caunait DOMABY 7) Conplextovng wo opal ative mers B)MapeI — (Q) Complerdaving ourS aie —_ BRET essen : omar sneer oat ge Oa oh = rng Om ia (e600 "igh-spincompley, ——~ CODUAAAT Come vaio (a) tot © tevin conn pe ener Ofte comer. ooo ° Paarup haar m ational wai _) @ep'tybritzaio, smsscomacnierrenmiat yO ao) LA) oo ‘6.(0) 23. (A) 30. (B) 28 eae : 2) 3. ( 30) 10.00) ae . +0) ey 20) 5.14) 2@ oo! ba an 1 ee ee «x0 7A) 148) oe ans sp ome dee tt 0.0 eanerix) RAO) HAO) 17. (AD) oO pom woe) a(ay(cnd) — 71A)B sn (ayouD) AEM) Apia Ce) ted OS) Compe ye eit +0) +o) ‘wy 8 20) tm mM +0 20 no 8 @) “0 +o 2 8 eit pe “o 70) + no 20) * inca 6A) 81) 10. (D) Integer Anomer Type Questions a tipene4 oo ewnwe anms 96 tu 20 56 ta) 10.4 13.7 m2 20) ari aT Ose PCO) .(7) 1) NLD. 90.09). (yarn cniBen a0) (yao (amon wo wr KR) (1.10) (ARNON) 9, ca) (0,48. er.) t (Ch =1P.10.08) (Aracmennisycr) (01-0). OO. ee @219) wo O45) ee