‘Types of ligands a 93. Terms used in coordination chemistry i 9.4 Classification of complexes 9:5 IUPAC nomenclature of coordination | 9.10 compounds ie Qu. Explain the following terms: a i Coordination compouna i Ligan fii, Central metal atom or ion ix. Coordinate bond Ans: i © Ceardination compound: Coordination compound is a compound in which a central metal at is surrounded by atoms or molecules ©. A chemotherapy drug. cisplatin, PENH)):Cl, is 2 coordination compound in which the ea jon, platinum s surrounded by two ammonia molecules and two chloride ions, Ligand: In coordination compound. the species surrounding. the central metal atom oF i ligands The ligands serveas cleciron donors €-8 In cisplatin, Pu(NHs),Cl, two ammonia molccules and two chloride ions are ligands, ML Central metal atom orion: dt coordination compound, the central metal atom or lon usualy deficit species aid accepts on clecton pir from ligands. Coordination compounds having & ts the centre are common ©-8, In cisplatin, PUNH):Chs, PALI) ion isa central metal ion Je. Coordinate bond: The bonds through which ligands are directly linked to central metal gun bond omstn of oad Ase The ct charge residing on the complex on iss chaye man ie metal ian and the ligands, [tis algebraic sum of the ch eg. The complex Pe(CN)]* has charge number of —4. 0.14. Calculate the oxidation state of iron (Fe) in [F¢ if a eal Ans: The hiraeon complexion (F(CN) hia, CNMI = * (OS. of Fe + charge on ligands) =—4 (OS. of Fe+ 6 x charge of CN” ion) ~—4 ii Q A Identify coordination sphere and counter ions. Bee aonQUIK. Can you tell? (Textbook Page Na 194) pein PENODANHDT? What isthe coordination number of: up ; Coin CoCtfenbal’, ie Aein [Ir(C000 in ie hee ds and 0 moony ri - jamaine (2) Hea toms in n Wee eee elds uocaaar comin THe = fi, In fIn'C,0,,C1)" two bidentate ¢, 0% ligands come Al Atoms are attached to irciom ion. There are six ee... number of iP” im in the complex is six avi Tiga ae ai In {P(NO: S(NEL hf, two nitro: (NO; Jand two eran “iam ‘There are four dosot SOM these are monodentate snes each has only one donor atom. TPS ‘Therefore, the coordination number af Pr ion in the comp! ictal ion in the complex [Ft “0.18, What the cordinton number and oxidation state of meta i ‘Ans: In complex [PH(NID JCI.) the coordination mumaber of me te chloride ions, that is, tor he complex. Therefor, th at is, total six diganels: In APHINEICKT- one ammonia motecule Or Sn ee ae A ees Scala rah ocr aon) me conde the complex. Therefore, the coordination number of The oxidation state of metal ian is calculated as follows The charge on complex ig —F (OS of Pr + charge om ligands) ~ 1 (OS of Pt +) * charge of NH, + $= charge of CE ian) =—F {OS of Pr=1 4K). + [Fe(CNy i ‘Counter oa Complex ton KAF(CN is a complex. Feay *2N1Y 4-250fi, Neutral sphere complexes: 4 coordination complex which 0.35. Give reaw a i fi, Ky[Fe(CN} is am anionic complex because it has 0.36. Give chemical formuta of one neutral complex, Ans: [PuNH3):Cle} =: Q37. Use your brain power (Textbook Page No, 193) Ans: 4 ip fi, Anionic complex cent with excess of co is 6) jon reacts with NHs)CLICE - ‘treatm on ‘ofa green coloured comples 0 EN, of C0 Amole of AgCl What the formula of he comPler’ Cat one Cl ‘Ans: One mole of the complex gives 1 mole of AgCl. Tt NOTE pier is [Cs ‘complex has oe jonisuble CI fon, Thus, the formula of os 0.30, What is the shape of a caimplex im winich the ane ‘Aas: A complex with coordination mumber six has oct yrdination Q.31 What is the shape of x complex in whiel the coordina N08 T i remaphacwil coe lee umber four has tetrahedral o¢ 'Q.32, How are coordination complexes classified om the Bases aie atm": eral atom oF on ‘Ams: On the bases of type of ligands attached to central m classified as: pound to only ane iype ef Hgande, L — Homoleptic complexes: The complecer in which metal son ts hou homolepiie complexes ieee eg. In[CoxNiikt, only ane type of tan, NEL surrounds the Co” JO oa ay ii ii, —_Hetroleptic complexes: The complexes in which metal jon is surrouns are called heieraleptic complexes, type of ligands attached to. the coordination. nd Cl attached to Com ton, in eat, In complex [Co(NH Cl» there are two types of ligands, NH, ind Cl attached to 33. Use your brain power (Tertbouk Page No. 128) . Classify the complexes as homoleptic and heteroleptic (Co(Eh xCHSO,, (ColONOY NH Ih [CoCMNHjem):I” and [Cats . Ans: i,” Homoleptic complexes: (Cu(C:O4h] 3 ii, Hetroleptie eompteres: [Co( NH, jC1IS0y, [Co(ONOYNIL). JCI: (CoCIONHL Ken): ‘ Q34, What are cationic, anionic and neutral complexes? (ive one example of each, mE: On th basis of charge on complex ion coordination complex is classified as Cationic compler: positively charged! coordination sphere or a coordination compound v positively charged coordination sphere is called complex or cationie sphere co: eg. (Z0(NH,),]" ee au — negatively charged coordination sphere or a coordiation compound aa charged coordinavion sphere is called antonie complex or anionie sphere oo eg [FaCN}l™ : eo does nos possess cate fi neutral complecesov-neuieal sphere complexes, silted chit eg: [Ni(COh) ICo(NHy):C1ISO, bs # atlonic complex while K\{FACN),| is an anionic {[CoONH:CHS0, i «cationic complex because it has coordination if counter ion nd makes the complex neutral overall TS (CONE CIP. ions are-ountcrjons and make the complex neutral vera nao" Sphere TFe(CN MP Classify the complexes as cationic, anionic ™ NayfFe(CN}), CONE, Ch, CAMON COI.” Preheny, and COO) Y Cations complexes: CNH iC, a Anionic complexes: NaFs(CNb), CHB:O}(C,0,),° iii, Neutral complenes: PuCh(ens, Cr(CO},.metal a altate() eee jinae(HID) Rota wot ‘Fetraamminecopper(It) io a [I1) fon b [Pet O}(NeS)P ea ncraeteccente optimum) a ere A TBE Be tarsermsadromopitund ier [Co(NHy},COsICL ‘Pentaammir arbonatecobalt(II1) » [ek KN Pentaammineaquacobalt(Ilt) iodide ___ live ci [2 (CowO MIE} | TriammintinitvocobalUll) b Fe(CO), Rentacibonytion() a | |e [RbINH,)SCN},) | Triameinetrithiaeyanatorhodium(T!!) QA, Try this... Texibook Page No. 197) ite the tation of i Auta aaah jon ii, Sodium hexacyanoferrate(IID) BLY Petiinn, becacrco crete ix. Aquachlorobis(ethylenediamin \. Tetranquadichlorochromiam(IM chloride vi,_-Dlamminedichloroplatinum(I) Ans: 1. ‘Trearbonatocobaltateth ion’ [Co(€O, fi Sodium hexacyanoferrate(II): Nas[Fe(CN)e] iil, Potassium hexsevanoferrate(II): KelFe(CN},] an iv. Aquachlorobis{ ethylenediamine obal(IIf): [Co(HsO)CKen):} ¥Tetraaquadichlorechromium(Il} chloride: [Ci1sO),C',]C1 Vi Diamminedichloroplatinum(l!): [PUNHs}:Cl,] Qut1. Write the forma forthe following coordination compounds: i Tetraammineaquachlorocobalt(IID chloride 1, Potassium tetrahyd lil, Dichlorabis(ethylenediammine)cobalt(ll1) fe Warseiae eke) i [Co(NH)(H,O)CIICL, i Ks[ZOH), [Cocigen),} iv DsiCOn] : QA2. Write the formulae a following coordination compounds; J i ‘Tetraamminediaquacol alt(1N) chloride it {tl Tris(ethylenediammine)chromium(lll) chloride iy, ae cnegkamonieketate(t) \. _Dichlorobistethvlencdiammine)ptatinam(V) wierare ‘bromochlorenitritopag Ve Tron(Itty ‘hexacyanoferrate(IT) i [CoPNH,)6(H,0),)C1, i ih, Kati ix. [PRENEL)BrCKONO) 3 eee, ye Q.43. Write the formulae of th g k Cusine ¢ following complexes: i Tris(ethylenediammine)cobalGtt) sulphate . Catteni) (CofenixS0,) age ene fortmulae for these conn naires) 1 settfamminechlarocobaltate(F) cho nateeperyencdiawaee patina sya (o8ODA a (Cots, 4 i UNO: ung IUPAC norms, write the formulae ofthe ma ENTE of Terahydroxocineate(tD) i eae ANCERI reminedichloroplatinusn(1) Pe eee 5 s+ Petanaminenitritocabal(1 Lee retnstum triexatatochromate(IIt) Vill, Hexaammineplatin mo yeirabromocupratett) x Pentaanialatiocaa i) ie : anit ii Kyfpac a5 {PAC} iii. [PuNHs)Ch een] ¥. [CONH)CONO wt eat aasto0, xCiG00] viii, [PANE ix [CuBr Ca(NHs}(NO2)) pa og. Write formulae of the following complexes Foassiam amininetrichloroplatinate(IT) il, Dicyanoaurate(t) on wt XP(NH}CH ii, [AMCN IT oat Write the formula for tetraammineplatinamilt) chloride, fs: (PONT) JCI 8 Cassi following complexes as homoleptc and beter POE {Cu(NHL)ISO% {Cate (HO)C1P™ [FetHOMNCSIE + ‘etraamminezine(I}) nitrate, [Cu(NH, 1802, tetrmamminerinett) nitrate. Homoleptic complexes: (HLO}CI, [Fe(HOMNCS Hetroleptie eomplexes: [Cuten) mic number (EAN) Tale ie veffztive atomic number (EAN) ls. eee pairs till it ain rimues 19 (9. State and explain: Effective ato! lag Sidgwick who proposed an empincal EAN rule states that “a metal im cont configuration of the next noble Bas ntl en int orl EAN equals total number of electron" — Ay EAN ries obs EAN cs tl sg (ad 36 CO) SE 3 .N can be calculated with the following. ofetectrons donated by Hears veut oe TAN] Neer of electrons of metal npmber cra es he om 8) Name a Oe of mel Cee alias gands (> aleetrons donated by tl Z=K4¥ i && Consider, (CoH Oxidation state of Co #6 2=97,K=3,¥ 22 EAN of Co =Z-X 42 fa7-34 12 =%(Onidation state of Za is +2 and ligands donate 8 elocirons. Z=30,X=2,¥=8 cx EAN of Zn” =Z—X4¥ il =30-248 26 © SS rec EA ‘Oxidation state of Fe 1s +2/and Wigands donate 17 cleteoes 2-26,.X=2 Y=12 EAN ofFe™ = 2+. ni =26—2+ 12 Mi oe a S Q.52. Calculate the EAN ofthe following complexes and identify which obey FAN rule and z [Re{CN)e 1" CrtCOee [Fe(CNIe I [CUNEL) a [FeCCNie Onidation state of Fe is +3 and ligands donate 12 electrons. M 2-26, X-3, vr # EAN of Fo" -Z-X+¥ 0 =26-3+12 3 d 35 I [Fe(CN} 1° does not obey effective atomic number (EAN) rule: ; fi, Cr{CO}e F . ‘Oxidation state of Cr is 0 and ligands donate 12 electrons. i] Z-14,X=0.¥=12 ork ; EAN ofCr=Z-X+¥ " 24-0412 3 =e iE ‘€x{CO}, obeys effective atomic number (EAN) rule. r ‘ih, (Fe(CN J . Oxidation state of Fe is +2 and ligands donate 12 electrons. ; 2-26, X=2,¥=12 EAN of Fe’ ahnt Ans: 26-2412 =36 IFe(CN), J" obeys effective atomic number (EAN) rule. } x, (CuONt) | Oxidation state of Cu is +2 and ligands donate 8 electrons, Z=2,X-2.-8 EAN of Cu =2-X+¥ =29-2+8 =35. [Cu(NH,}4}°* does not effective atornic number (EAN) rule, (CO), and s Mog Ne TCC shey the BAN mle white 1Fe(CN, and | aisomers Optical isomers or ‘enantiomers fonization isomers Sol Linkage isomers Coordination isomers isomers. Q.S7, What are stcreeisomers? Name the two types of stereoisome! - ansptuent atoms tie different 1 Sterenisomers are the isomers having the sake inks eros atoms im space ii, Twotypes of stereoisomers: ' ae a Geometric homers dtersieomer tb Enantiomers or optical isomers Q.S8. Explain the term geometric isomers. Aus: Geomettical isomers: : 1 Geometric iseiners are nonsuperinsposable mirror image isomers. ! ii, These are possible in heteroleptic complexes Til Im these isomers, there:aré cis and trans tyes of arrangements of ligands, 8, Cis-isomers: Identical ligands occupy adjacent positions. b. _Trans-isomer: Identical ligands occupy the opposite positions. Cis and wans isomers have different properties. Cis trans isomerism is observed in. square pi octahedral complexes. : Note: Geometric isomers are also called as distercoisomers Q.59. Explain cls-trans isomers in square planner complexes, ‘OR Explain geometrical isomerism in square planner complexes. ‘Ans: The square planar-complexes of MA;By and MA2BC typcs exist as cis and trans isomers, where, r are monadentatc ligands, Mis metal i Cisctrans isomerism in MA;B; {ype complex: d eg [P(NH,)Ci,) Ch aN Ce NH; : Pi Pt ac SN; a7 Sg ; ‘Gener Timskicomer a The cis isomer is more soluble in water than the trans isomer latin is an anticancer nace vt SP anticancer drug while the trans’ isomer is & ‘The eis isomer is polar with non-zero dipole men ‘ as. aresult ofthe two opporte PI Cland two PUNE, heer 289 Homer has moments, which cancel eagh th Cistrams isomerism in MA:IC type complex: nn ee eg [PUNK WHO)Ch} oy eto Gas HO Pt cn, HN Sc Cis isomer ‘Trans iscener Note: EE cottons real Seg D nc watmacunrahe co rit ( ‘Tho andndiomer tat otses the plane aise) is called ine wiles rt te pa oe ail ) ‘Vi. Optical isomers in octahedral eg (Coren) st FY: 8 |[[gs é Poem: ier is vik, Octahedral complexes existing as both geametric and optical som" sme [PiCh(enp) 4 4. Cis isomer of the complex show optical isomerism, ae Cc) cd alee en) | aA i al ne a Trans isomer-of fPtCljgen)s}*” dees not show optical isomerism as it has a plane of # 1 ala ee wih Square planar complexes do not show enantiomers since they have mirror plane and axis of "Note: Our hands are nonsuperimposable mirror irsages. When you hold your left hand upto a : Jooks like right hand tiomers of [Cr(ox)3)~ Praw nantiomers and cle and trans isomers of ICrCH,O}(oxh” (where ox = cota it Optical isomers ot (Croxt™: 2 “bis | | | St Hk Enantiomers of [CWH.O)sox)]- ies f a , HOw Bo) ie ] p<, s fon, ; ‘Horan. *a a[> af> i b. Enantiomers of fPi(en;)CIB1]™ 2m en torn ‘The complex [Crlen}(H.O)2]" is chiral ‘Structures of enantiomers Q.68, What are structural (or constitutional) isomers? How are they classified? Am ‘Structural or constitutional isomers possess different linkages among their cotstituent atoms but h same chemical formula, ‘They are cla a. Linkage isomers Ionization isomers © Coonination isomers | Selvate isomers 2.69. Explain linkage isomers giving one example, An inkage isomers are formed when the ligand has two different ‘Tt coordinates to the metal via different donor atoms. os The nitrite ion (NO; ) having two donor atoms shows isomers as: (eoNHanon and [ean 4ono) € nitro complex has Co-N bond and the nitrita 2 eu cer complex is linked through CoQ Q.70. Can you tell? (Textbook Page No, 199) ‘Write linkage iomers of Fe(H0)SSCN". Write thelr TUPAC Finkage isomer of the given complex is [Fe(@h,O)(NCS-y° 4 [Fe(H:0)SCNJ": Pentaaguathiocyanatoirond it) Fe(HO),(NCS }]' Pentaaquasothivcyenarcie ot Qn. Ans: t Ionization isomers involve ‘exchange of ligands ‘between ce (Const sour sndiCotH B80, :CMEN| K= 2.0107 Co! 4 6H) —+[ColNH, a} K = 5:0 10" “Among the abave equilibrium constant data, [C' because [Co(NHs)}’” has higher value of equilibrium: : #079. Name the factors governin the equilibrium constants of the £00! Ans: Stability of 0 complex or equitbriwm constant is goverMe PY re i. Charge to size ratio of the metal ion = Q.80, Explain the factors which affect the stability ‘Ans: The factors which affeet the stability of coordination com i ‘Charge to size ratio of the metal jon: &. Higher the charge to size ratio, greater is the stability. Irving William order. b. The stability oder of divalent metal ion complexes V8 ene Cut > Ni"> Co" > Fe" > Mn” > Cd” 1 pha cc nthe list, both Cu and Cé have the charge +2, however, the tone in CoP" is 97 pm. The charge ty size ratio of Cut" 1s grestet than that of stable complexes than Cd" Nature of the figand: Fe abit of coordination complex depends upon the basicity of the Ligand, tanita figand can donate its lone pair of electrons to the central metal jon. tb, The ligands those are stronger hases tend to form more stable compl afeoordination compounds: ypounds are! exes. |. Use your brain power. (Fex/so0k Fage No. 20) ‘The stability constant K of the [Ag(CNisls §.5 * 10" while that for the corresponding [ 1.6 *10", Explain why [Ag(CN}:|” is more sta The value of stability constant determines the stability of the complex. The stability constant [Ag(CNb is higher than stability constant of [AgiCN))’ . Hence, [Ag(CN); mere stable of the: rela For the reaction, M+ 4L. = Mls, larger the stability constant, the hi Ci : Y © higher the proportis the solution. Free metal ions hardly exist in the solution as they are cared 6) Dien e which will compete with the ligand molecules. By ignorin , Q i ere es ee ignoring these solvent molecules, we can write fo M+ L = ML ‘ Ki = [ML}/ [M] [L] MLS b= Ml; 0) Ke=[MLal/ [MLL] Mi; #L—=Mb;; Ki=[MLil/ (MLa} {L) Miy +L —==Miy i} Ky= [MLq]/ (ML) [L] where, K., Ka, Ks, Kuare stepwise stability constants, ‘The overall stability constant (f) is given by, M+ 4b === MLy ; Pe=[MLs]/{M] [L]* ‘The stepwise and overall stability constants can be related as folla f fam Kin Kx Kak, id General constant is known as the instability, ‘onstunt or the‘can you recall? (Textbook Page No 201 wh re vale bond theory andthe concept of ybidiaton? * yatence bond theory is chemical bending. i og theory based on the concept of'wave mechanics I explains that beng Rocen Iv afm Bappens seul of overipof half filled ate obs ofthe valence sell ‘uring bonding in the mofecule stich as CH,, NH, etc mixin : is NH i und recasting of the valence orbitals of central som takes place forming equal number of new equiv 295 arms 0 form Bond. Tas ica ee anne! Cir) oral whch ovray wih oa ‘The bobridized state is « theoretical step that describes how complenes are formed. VBT is based on the concept of hybridization. ‘The hybrid orbitals neither exist nor can be detected spectroscapically. These orbitals, however, help us to desctibe structure af coordination compounds, ‘Write the steps involved in describing bonding in coordination compounds using the VBT. The steps involved in describing bonding in coordination compounds using the VBT are: Metal ion provides vacant d orbitals for formation of coordinate bonds with ligands ‘The vacant d orbitals slong with s and p orbitals of the metal ion take part in hybridisation, ‘The number of vacant hybrid orbitals formed is equal to the number of ligand deaor atams surrounding the riatal fon which equals the coordination number of metal ‘Overlap between the vacant hybrid orbitals of the metal and filled orbitals of the ligand leads to formation of the metal ligand coordinate bonds, ‘The hybrid orbitals used by the metal ion point in the direction ofthe ligand The (n-I}d or nd orbitals used in hybridisation allow the complexes to be classified as a Outer orbital complexes b. Inner orbital complexes Forhybridisation in the outer orbital complex nd orbitals are used, whereas inthe inner orbital complexes (te1 orbitals are used. 084. State whether TRUE or FALSE. If False, rewrite the correct statement, Valence bond theory (VBT) and Crystal field theory (CET) describe metal-ligand bonding, When the hybridisation is d’sp’, the structure of complex is tetrahedr: Tole ii False 2 When the hybridisation is dsp’, the structure af complex is setahedeal Note; Type of hybridisation decides the structure of the complex 55, Complete the missing entries.See whether the complex is low spin or high sri"- cleetronic ¥ Write the electronic ssntion ana tbe ype or nye it ‘vi. Identity the orbitals of metal ion available for hybrid (ibe oap ul ‘ik Show fitting of orbitals afer complex formato. ace behaviour & vill, Determine the number of unpaired electrons ane! pred eR 0.87. Eaplain the structure of actahedral low spin complex, [CA ’ Ans: : below: i. Oxidation state of cobalt is +3. ea diagram as shown ii, Valence shill electronic configuration of Co” i represented in PO* ‘ vii, EC as a Phra) CO saa Number of ammine ligands is 6, ‘Therefore, the mumber of vaca with ligands must be six 2 Complex is low spin, so pairing of clectrons will take place prior 1° Electronic configuration after pairing would be x 4% 4p [elale pele| Six orbitals available for hy id ybridisation. jon are two 3d, ones, three 4p orbitals 9 itis ae ae ements Po are decided from the number of ammine ligands which is six. Here, (n-1)d ofbitals participate in hybridization since it is the low spin complex. c Electronic configuration after complex formation 3d 4s SS ttf tpn perp sty [ety [et ett | ea Asall electrons are paired, the complex is diamagnetic Structure of the complex [Co{NHs)«]": ‘The orbitals for hybridiz rei # NH HN | -NHb 6 HN | Ni NH, Explain the structure of octahedral high spin complex, [CaF ‘Oxidation state of central metal Co is +3, Valence shell electronic configuration of as “it aie (ils Sc facie iia Co" is represented: bidi ig In hybridisation for this, Sevan bd ators Coal te complex is octahedral and has four he austure of the complex is: “unpsired electrons and hence, paramagnetic 3 qi. Explain the structure of tetcahedral complex: qNicul As: i i onidation state of nickel is +2 ‘Valence shell electronic configuration of Ni as ip es alee Tigands i 4. Therefore, the mumber of vacant metal fon ‘orbitals required for bonding with four, « hybridisation are one 4s, three tp, The complex 's tetrahedral, 1 fe J ipands are derived frora the sp’ hybridization, # swith CT ti at fo four orbitals of CI tons. ‘The four metal ion orbit di Four vacant sp’ hybrid orbital of Ni overlap ‘it Configuration after complex formation cies i 3d = ae The complex has two unpaired sfecans Thestructure of [NICHD #8 2 a a a) Cl cl- 7 ~ soxz [NCND “Q490, Explain the structure af square planar comptes: [Ni “Ams: +; Oxidation state of nickel is +2, ii, ‘Valence shell electronic configuration of Ni” ET 4 *” psa jtats required for he mumber of yacane metal 10". oF Lite] ty t | iii Number oF CN tigands is 4, s0, ‘would be four, Ei iv. Complex is square planar, ion uses dsp v,3delectrons ate paired pri hybridisation a4 ao hybrid orbitals. ‘and electron Com! anseno dpi ve tte orbitals of CN” ions to form: rafter] rl Onbitals available for hybridisation are one 4d, one 48 Four vacant dsp’ hybrid orbitals. of Ni** overlap with fou Contguration afer the complex formation becames, i as one ta]te| te taf re) [er] [or ] viii. The complex has no unpaired electrons and hence, diamagnetic The structure of the complex is Q.91. Try this. (Fexihook Page No. 202) ___ GREYBT deseripton of bonding in each of fotloing complexes. Predict their magnetic b ik ac (square planar) i Hot O Mt (high spin) [cr(NHeAP" + ICOCLY” (tetrahedral ‘Ans: i encus 3, Oxidation state of zinc is #2 b. Valence shell electronic configuration of Zn? ia (ele [etays Number of Cr ligands is with ligands must be four, Four:The complex has no » The suture oFZACI te em ae Benes, diamagnetic [ q a] acy et Lech 4 [CotH:OX)" high spin) ‘Oxidation state of cobalt is +2 Valence shell electronic configuration of Co” ad te tn tlt [tit (inl Number of H0 ligands is 6. Ther f 7 Nar eapes: 156. Therefore mumber of vacant metal ion orbitals required for bonding wath ad ps spin, that means pairing of electrons will not take place prior to hybridisation. oe eas selfs Be ee eee Sis ita tal available for hybridisation are one 45, three 4p and two 4a. The complex 1s 3a 4 4p | te[t | spit ‘The six metal fon orbitals For bonding wth CN" ligands are derived tam te ad hybridization She vacant sp'd: hybrid orbitals of Ca" overlap with six orbitals SECN fons ‘Configuration after eamplex formation would be 3d 4s 4p + aie) (eT (psa ea gift Jd électrons and hence, paramagnetic 4 The complex has 1! The structure of (C2& h [CoCh|* (tetrahedral) b. d. f eB ion orbitals apt fads Tete i with ligands must be four, Jdisation and electronie Sd clecirons are paired priot to the hy-bridisati Sd oe ee Co ae i ye $d one Four orbitals on metal available for hybeidisation are oP ‘square planner. a © sa Th] td | tL] tL (el jzes) dp? rived from the dsp" hyb ‘The four metal ion orbitals for bonding with CN a en oe Four vacant dsp" hybrid orbitals of Pr overlap with four ‘Configuration after complex formation would be St as * ta] [ra] rafts] [re] [e Jes] | = ee ee ep! ‘The complex has no unpaired electrons and henee, diamagnetic. The structure of [PUCN)e]is = = aN Pt an en Oxidation state of cobalt is +2 Valence shell electronic configuration of Co” sd # te alle [e ft Eley | Number of Cl Tigands is 4, Therefor with ligands must be four. Four orbitals on metal available for hybridisation are ong 3d as 4p ele iets fe) nese * he for metal on orbital for bonding with C1 gana Fou vacant "hybrid rbitals of Co” gyerlap wine ecg en the sp hy Configuration after complex formation woul be ‘srbitals OF Cr ions, HM Nin] t]t nN ve, the number of vacant metal ion orbitals required for bo 45 and three 4pb . Try this, (Fextbook Page Ne 204) Based on the VBT predict "The comp lois Enceiegan ‘Toe russ of See — jeri” Oxidation state of chromium is +3 ‘Valence sbell electronic configuration of Cr Hs a Tal Number of NH ligands wih hand meee Six orbitals on metal available : ahs lable for hybridisation are two 3d, one 45, three 4p and. The complex is is 6, Therefore, the number of vacant metal ion orbitals required for bonding: ad ft: The four metal ion orbitals for bonding with NH; ligands arc derived fiom the asp" hybridization. Six vacant d’sp" hybrid orbitals of Cr” overlap with six orbitals of ‘NH; molecules. Configuration after complex formation would be 3a 4p title tee ‘The complex has three unpaired electrons ant enc paramagnetic The structure of {CNHs 18 = [ NH Hawn. | ANB « ls Hy { NE; NE structure and magnetic behaviour of the [Ni(NTH}6L" complex: Oxidation state of nickel 8 +3. nse Valence shell electraniéwhist ‘Vi Orbitals available for hybridisation are one ds, three 4p, two 44, ¢ NE vii Six vacant sp'd? hybrid orbitals of Ni!" overlap with six orbitals ‘coordinate bonds. (Configuration after the complex formation becomes, Pe 3a 4s 4p : ntl ay [et we ‘Hl The complex has one unpaired electron ard hence, paramagnetic: The stucture of the complex is a NH; Nu | Ni, nur" SNH; Ni, “Q.93. Give valence bond description for the bonding in the complex [VCl|~ Draw box @ metal ion, Which hybrid orbitals are used by the metal? State the number of unpaired Ans: 4, ‘Oxidation state of vanadium is +3 ‘Valence shell electronic configuration af free metal ion, V"* 3a fn PeLEOI Ci ft ta ‘Number of CI ligands is 4. Therefore, the number of vacant metal jon orbitals required for ligands must be four, Four orbitals on meta available for by isation are one sand thice 4p. The complex is tetrahedral 4 2 Je) Fis four metal ion orbitals for bonding wih CI” ligands are derived from the sp hybridiza Four vacant sp’ hybrid orbitals of ¥"” overlap with four orbitals CT ions. bi ‘Configuration after complex formation would be id 4s * PT TT) fal ee hal The complex has two \npaired electrons. The structure of [VC] is r a7] a‘ne dp and three 4p orbitals participate in hybr atch the following. oe [NWCNM} | a | Ni(COW [MnFel* jw. [FeACNI we id b ill a6 Write the limitations of valence bond theory. As | tides not explain the high spin or fow spin nature of the complexes. In other words, strong and weak field nature of ligands cannot be distinguished. Irdoes not provide any explanation for the colour of coordination compounds, The structure of the complexes predicted from the VBT would nt always match nccessarily with those etermined from the experiments What are the assumptions of crystal field theory? (CET is based on following assumptions: ; The ligands are treated as point charges. The jnteraction between metal jon and ligand! is purely electrostatic ot there are ne orbital interactions: between metal and ligand. lian isolated gaseous metal ion the five d orb poe dv de Seca te se snr it they me degenerate, When ligands approach the tbe degeneracy of the d orbital eracy ig destroyed. The d orbitals (4, j.4,,) called as ey, These (9° ae mi energies of these two sets of d orbitals jg the ceystal field splitting parameter, This 4s noted by Oy ( ctahedral). The .\, depends on strength of larger spliting of & orbitals and pain? cial i they create rystul-Geld around the etal fon. If were symm Salk ay inact, Usually, the fictd tented i¢ noe symmetrical ni Mus epic into to sets namely, (Boy dye da) usually referred srt ot orhitals nov have diffvent energies. A separation of has CN’, NCS, CO, NH. ete, cause the ligands, Stone Oe ey These ligands tend to form Tow spin 1g of electrons is «cea hme bore: comers mma es fa 2S as ‘Weak field ligands such pin complexes electrons; hence, these ligands form high ie, ip a8) Note: increasing ont c= Huo C x bond. This is also called back donation or back bonding, ‘The metal to ligand bonding creates a synergic effect which strengthens the bond between CO and the metal. Structure of some of the metal carbonyl complexes: 1 I ! ! I I ! 1 1 I t |wy. Write in brief the oe In biology: Several biologically im, ole in a number of processes de complex of Mg. Haemoglobin a Ptcomplex, cisplatin is used in, treatment of cancer EDTA i ated for here rie ae ro estimate har ae in ata ae oir ane i th ets fC” The ero: aly site coat cai a Seen eda ns en, ion dissociate to suall extent snd furnish .g.110. Mention two applications of esordinat ee Relr 0.108 ‘Seerclnmion somtpoint: | Purification of metals: Puritieatios nea beni Zaconipodton of ine coocinatna Cxepee al 000 le ain a eg. Impure nickel gets converted into [Ni(CO)}, which on decomposition gives pure nickel In photography: In black and white photography, the developed film is fixed by washing with solution. This process dissolves the undecomposed silver bromide (gl) to form a complex ion. [Aa{S:03)) In Industrial processes: Coordination compounds finds important application 2s catalysts for many industrial processes, Examples inckide shodium complex, [(PhsP)RhCl}, a Wilkinsoe catalyst, is used for the hydrogenation of alkenes. fn Im analytical chemistry: The ability of metal ions to farm coloured coordination complexes: with | number of ligands (especially chelating ligands). fori the basis for thelr detection, and estimation by Gaccieal and instrumental methods of analysis. Examples of such reagents inclode EDTA, DMG (Gimethylglyoxime), «-nitroso-f>-naphthol, eupron, ef *Q.111. Activity: (Textbook Page No 209) if The roe ‘of chromium metal with H;SO, im the absence of air gives blue solution of chromium ion, + 2H) + Gry, + Haw Ce farms octahedral complex with HO ligands Writeformula of the comBIEN, cy and VET: Deserihe bonding in the complex us! = Draw crystal field splitting and valence hond orbital diagra al complex with water Higa, tbe formula of comple [eon Since chromium forms actahedr nearyt Bonding in [Cr(HO)d sing ears chnges and hie is sles interaction jee The metal ion Cr” and ligand Hi @ rate crystal field around the metal ion andthe desenerssy Te) oral experiencing age sepulsion ans reset am el oping overs A is sale the pine vpfa Bonding in (Cr(H,0)|""using VAT theory: Orcidation state of ehroenium is #2 Valence shell electronic configuration of CP" ul ‘i * | ais 3. Number of 1,0 ligands is 6, Therefore, the number of vacant metal 100 orbit wired ‘with ligands must be six : 4 HAO is weak field figand and hence, complex iv high spin Be $. Six orbitals on metal available for hybridisation are wo 3d, oe du and thse Ap The complex is ot Md as 4 thn pie The six metal ion orbitals for borsting with H:O ligands are derived from sp’ ‘vacant sp'd* hybrid orbitals of Cr” ow erlap with six orbitals of HzO molecules. 7. Configuration afer complex formation sould be id 4 4p “4 reali te ee ey Te Hepat tty LL = op 8. ‘The complex has four impaired electrons and hence, paramagnetic ‘The sthictire of (Cr(H,O) [is 10 HON | 1,0 #07 | 10 HO (Textbook Page No, 209) Reaction of complex [Co{NHs)s(NO;),] with HCI gives a'com plex {Co(NHs)H30CI,]" in which two chloride ligands are trans te one another, 1 Draw possible stereoisomers of starting materi a iL =~ Assuming that NH, groups remain im place, which of tw saint ‘0 starting isomers would give the Stereoisomer of starting material [Co(NHy)(NO3)sk: eat eee AE bhi FE | Ni, Nos ee a 0 no |’ ett | fst f Naas NO, NG, iy Isoener rani teen‘Types of Ligands: ‘The species surrounding, | ee cr o1rcN Monodentate | Ambidentate mmgle donor atom | |'® Two ormore donor atoms | |= Use any one of two denon ee, Bidentate | © Two donor atoms | 28 Ettylenediamine,c,0; | atoms to form Me |__ Hexadentate + Six donor atoms [eedprayt | #. Me SCN or9.4 Classification of complexes 11, Classify following complenes as homeleptic and Iter ion compounds. ICHMT) CSOs, comedy gh 69,74, 74, 76; {Co(ONOXNH, JCI [COCKNTL Hen)” and | ame: Ref [eucsoyn)" 9,9 Stability of coordination Ams: Refer 0.33 explain stability of coordination Sompdands, 12, What are cationic, anionic and neutral | 24, Explain st E 2 Refer 27 complexes? Give one exumpte of each Ansi size ratio of the meta Ans: Refer 0.34 25, How does charge to size ratio neta jon i i ct stability of coordination cor 18, [€o(NH)).Cl/S0, is a etionic compiler while affect stability of ‘ : 70-0) Ka[Fef(CN),] is am anionic complex, Why? ‘Ans: Refer Q. a Hush Fete 29. 26. How ture of ligands fects atl ap 14. Is the complex [CoF;] gationie or anionic if the soordination compounds’ oxidation state of eobult don is +3? Ans: Refer O80. (id) Ans: Rejer 0.35 9.9. Theories of bonding In complexes ares SeraCme yearns | err compounds — ~~ spin complex, [CotNHs}el Ans: Refer O87 15, Write the formulae of the following ‘coordination compounds. 28, Explain the structure of square planar : i. Tetraamminediaquacobali(IM chloride 2A. Eagle die serie oF aE complet Potassium tetracy anonicketat( I!) Nien" Trisfethylenediammine)ehromjurn(ITT) chloride | Ams: Refer 0.90 of 29, Based_on the VBT predict stricture and 3 i [CNH JMHLOICL ii, RANI(CND) magnetic behaviour of the —[Ni(NHj) fe iii, [Grten)s}Ch peupe zt 16. Write IUPAC name of the following complexes: | Ans: Refer 0.92. i ee isi 36. Explain the structure of [VCL] “O(NFT, ONO} Ans: 0.93 [Cog }a](80.)s oa 31, What are strong field and weak field ligands? Potassium letracyanonickelatell) Ams: Refer 0.99 S Hasasutncctalul spec 32. 1s the complex Fe(CN).J* diamagnetic at 9.6 Effective Atomie Number (EAN) rule Paramagnetic? Is it coloured? Explain with & Orbital splitting diagram in octahedral eormpler. 17, Calculate the effeetive atomic number (can) of Ans: Refer 0.107. ‘copper in [CufNH)),]°'. [Z of Cu 9 910 Application [Reb 20) | 7l¢. APpllcation of soordination compounds Ans: Refer 0.52. (iv) 3 Slate applications of coordination compounds, Aust Refer 0.109, ' 3.7 _Tsomerism in coordination compounds, 18. Comment on geometric isomers. Anns Refer 0.58 19. Explain geometrical isomerism in complexes Tagine i UR igands ina comp are ‘with coordination number of 4, (A) ‘ions tinked by Ans: Refer 0.59 'y coordinate Bonds-to @ central metal emioe igh en ee fons linked by coordinate’ bonds (0 it ie 20, Draw geometric isomers of [Fe(NH;)(CN)e) Ans: Refer 0.61 Central ctl ato eseasall : (Chavonti wile ire : 2. Se isomerism in octahedral Donde a cena by. sgordinate ‘Ans: heer 0.63 (D)" ions’ ot molecules: linked beetedas! _ bonds to central atom he Jalil2 Which of the following will show isomers? ? cay (zac By [CoN (©) [CnC:04h) {D(C ‘Which ofthe following complexes are chiral” Eo [eoteniChy M fPaenCh TH. (CACO) WW. [CaN Ch! (A) Lands (B) Zand 3 (Ch tands (D) Banda Which ie following ic NOT platy active? KAY [Cofends}"" greater is HS 8 {B) [Criowp)? Greater the charge on the central metal ig tC) cix[CoCh(en).] sreaicr ithe stability ofthe complet, . {D)tans{CoCenp Greater isthe basie character of the. ; Tigand, the greater is the stability of the “The number of geometrical and optical isomers o Aaa ain @ 3 8 > G0 @ 4 pt aa epeicagrem a ond ued the Reamet of complex ion ‘Cisplat (A) co-ordination (10) tinkage qu (©) sonization (BD) optical (A) malaria (B) cancer AIDS” ‘yellow Sevet [CNH CAEN nd [EMEA CHIH (A) linkage isomers (B) ionization isomers (€) coordinate isomers (D) solute isomers On the basis of CFT. predict the number of iunpaited electrons in [CrFg]™ is wr oz © @ 4 A strong tigand gives a complex which is ‘generally called (A) high spin (B) highenergy {©} low spin (D) stable “Bee ogee ‘What isthe correct electronic configuration of the central atom in K,[Fe(C tal file, -[Fe(CN),) based on erys theory? (a) hye? B) t.°e,! @ ay oh aos Hint: Fe" = [ar] 34° In presence of strong field ligand (CN), all six electrons 8 will be placed in Electronic configuration = &, c! Bese ew soen ig oe Ke(Fe(CNe i low spin complex which contains no unpaired electron in oblate. ‘The Crystal Field Stabilization Energy (CFSE) for [CoCle]* is : 8000 cm”. The CFSE for ee ‘) (A) 8000.em"t (B) 6000 em" ef INEET (UG) (C) 16000 em (y 18000 cens +d i om fi. GAN of cial metal wom in 2CCIMT = aos (B) 4 ks |W. Ationg the following, the mos! stable complex is WAY [RF e(HLOM” (By iraecNh Q2. Answer the following: ination compound. {Nate the fntors goveming the equilbvuim constans ofthe coordina Classify the follosring us homoleptie wn earl cmp ‘(NH a [Fe(EbOM ‘Write the TUPAC name of (Rin NHG)(SCN)} i iat ence of eralia Ceesde = ye) (retal” hod) Attempt any Four: ean example ‘ O35. Whatis difference between a double salt and a complex? Givean cxampl Q44. Give reason: [Co(NTH))4CH]S0«is cationic complex while K,{Fe(CN}] is an anionic: complex: Q5. Define the following terms Cation coanplexes ii, Neutral complexes 26, Write all possible isomers oF [Crén, iB)" Q.7. What are strong and weak field ligands? 6 What are the limitations of valence bond theory? 9. Explain geometrical isomerisin in square planner complexes, 2.10. Explain the formation of octahedra! complexes using crystal feld theory : Q.11. Write a note on colours in coandination compounds. aq (O:12 Explain the structure of octahedral high spin complex, [CoF|* O13 i ii Attempt any One: What factors atfeet crystal field splitting energy? 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