Ligand Substitution Reactions in Octahedral Complexes what are Substitution Reactions in Coordination Compounds? Substitution reactions in coordination, compounds are the reactions in yhich a ligand present in the coordination sphere of the complex compound is \ Nhlaced (substituted) by another ligand (nueleophile) or the metalin a complex compound is replaced of another metal (electrophile). Substitution reactions’ are also called exchange reactions or replacement reactions or displace- pent reactions. Classification of Substitution Reactions in Complexes Depending on whether a ligand is'exchanged by another ligand or a metal is, placed by another metal, substitution reactions of coordination compounds have heen classified into the following categories. 1; Nucleophile (or ligand) substi these reactions a ligand present in the coo | igand (nucleophile For example: ‘ F ma,{e) + E > MASEL. 0, Nucleophile ja ln this reaction the ligand,‘L (leaving group)-present in complex (MA, L) le replaced by another ligand E (entering group). E is called nucleophile, since 2s electron pair donor (Lewis base). CNs, of the new complex (MA, E) and the | inal complex (MA, L) are the same (= 6). In this reaction Lis the leaving | Itutgoing) group. — = \ act Electrophile (or metal) substitution reaction (S;, reaction). In these | ®tions the metal present in a complex is replaced by another metal (electrophile). ‘ot example; v “MMA, Ls @ > M’A,L+M?* \ . ‘Electréphile In this reaction the metal (M?) present in the complex, M'A, 1 is replaced eee ie metal M?. M? metal is called electrophile, since it is electron pair Beseg (Lewis acid). C.Ns. of the two complexes (M1A,.L) and (MA, L) are © (=6). In this reaction M! is the leaving (outgoing) metal and M? is the Metal, 1 this cha 2 ahegyei® chapter we shall discuss sucleophile (ligand) substituts roti P itution reas i "aq pcletmplexes oly, since these reactions proceed so slowly that ese lowed easily by conventional techniques. . 4 L rn mm reactions (Sy reactions). In mn sphere is replaced by anotherTe B94 , ‘ Je Selected Topies in Inorgany, lech ‘ x Qucleophitic (Ligand) Substitutfon Reactions in my ctahedral Complexes. Nucleophilic substitution reaction in an octahedral complex j . plex Which one of the ligands present sts octahedral complex is replaced cetton ligand. For example the reaction, by anotie MA, L + Octahedral complex Entering ligand _ (ON. =6) (Nucleophile) is a nucleophilic substitution reaction in which the ligand L. present in octa complex (MA, L) is replaced by another ligand B. Thus Bis the entering i hear Lis the leaving ligand. Since all the ligands are nucleophiles (electron on or Lewis bases), these reactions are called nucleophile substitution reactions lechanism to Explain the Nucleophilic (Ligand) Substitution Reactions in Octahedral Complexes. Let us consider the following nucleophilic (ligand) substitution reaction iy octahedral complex, MA; L BE > MAE + 1 MA,L Me E> MA,E + L @ Octahedral complex Nucleophile Leaving (C.N. = 6) (Entering group) group Here MA, Lis an octahedral complex in which Lis the leaving group, ie. Lis replaced by E. Thus E is the entering group (nucleophile), ‘There are two mechanisms toexplain the occurrence of the above ligand substitution reaction (i). 1. Unimolecular nucleophilic substitution or dissociative Sx mecha nism. According to this mechanism.the ligand substitution reaction (i) proceeds through the following steps: (a) Dissociative step (D): Loss of leaving group a “< oup Siow step () Mag fe A fahedral complex Square pyramidal (C.N.=6) intermediate (C.N.=5) (b) Associative step: Addition of entering group Addition of entering group by association (+1 MA;E MA, +E Fant step Square pyramidal intermodiate (C.N. = 5) ates t0 In divsociative step (a) the octahedral complex (MA, L) dissociates “C, reaviny diosp (L) and forms square pyramidal Rntermediate (MAg) With to 8 thi Bnd fond prosent m MA, L molecule is broken Hen ale ‘Thus in this ster ‘Thus 50 be calleq bond brealring step. In associative ste (p), the query ass intermediate formed in step (a) adds the entering group (nucleophile) by i" n edforms the octahedral complex, MA, er Since the dissociation step [step (a)] is a slow-step, it is the rate re iy ot ing step. The reaction of this slow step is unimolecular, ‘since it involves—_— gona Substitution Reaction in Octahedral Complex 895 | acting species viz MAg L. The rate of this reaction depends on the concentration MA; L only, i.e. the rate law of this reaction is represented as: Rate (r) = k[MA, L] ; = kMnitial complex) Since the rate of reaction (r) depenids on the concentration of one species only vizcomplex (MA; L), Sk mechanism is also called unimolecular Sy mechanism vr $y mechanism. , ‘fn this mechanism, since the octahedral complex MA, L dissociates in rate de- 0 of termining step (slow step), the mechanism is called dissociative ‘S} mechanism. ‘Above discussion shows that the rate of reaction (i) is directly proportional to con- entation of MA, L and is independent of the concentration of the entering group E Both the steps.of dissociative S}, mechanism can be combined together and can be represented as: Dissociation (-L) Pl an MA, L Slow 0 =. MAs Laid Octahedvat . Square pyramidal (CN. =6)) . intermediate (C.N. = 5) Fast | Association MA, E GE) Octahedral (O.N, = 6) : Ina simplified way the above steps of dissociative Sy mechanism can also be shown aa: ; (was, tenga, yay Sane Ma 2 WA Rate (r) = & (MA, L] = & [Complex] /Simolecular nucleophilic substitution or associative Sy mechanism. - According to this mechanism the ligand substitution reaction (i) proceeds through the following steps: (@) Associative step (A) t —~ Addition of entering group (Wale e by association CHE) MA,LE 1h ets ~~ Stow do T-coordinated ctahodral intermediate (C.N. = 7) complex (C.N. = 6): . ®) Dissociative step : by diavocaten CD eee MA,LE ee MAE +L ‘7-coordinated intermediate ® Octahedral complex (C.N =7) (C.N =6) eng associative step (a) the nucleophile (entering group), E attacks the octahedral M, AL (MA, L) and gets associated with it to form a 7- coordinated intermediate wage E). Thus in this step a new bond (M_E bond) is formed to produce '. Hence this step can also be called bond making step. In dissociative step (b),aos Selected Topics in 'norganie gp, a Tawordinated intermediate (MA, LE) formed in step (2) breaks up ang yy, igand (1) is ejected. oa " _ Since step (a) is slow step, itis the rate determining step. The roq, ion ™ Step is bimolecular, since it involves two species diz MA, L and E. The rate ly reaction depends on the concentration of the complex (MA, L) as well as on tn ar tration of the eiitering ligand (E) i. the rate law for this reaction is represen Rate (x)= RIM A LI JE = eda = [Complex] [Entering group] Since the rate of reaction depends on the concentration of the com, and the éntering group or nucleophile (B), this mechanism is also called imo! Sy mechanism or 8 mechanisra. | In this mechanism, sirice the entering group (E) gets associated with the plex (MA, L) in rate determining step (slow step) to form 7 coordinated Mie ~P intermedige this mechanism is also called associative Sx mechanism. : Both the steps of associative 8 mechanism can be shown as: antic E) MA,L+E gee, u MALE Octahedral (C.N, = 6) : ‘T-coordinated intermediate Dissociation (-L) 5 MA, E+L ‘ Fust Octahedrai (C.N, = 6) in a simplified way both the above steps of associative 8,3 mechanism can alsp be shown as: 48ntoring'group (H) ~Leaving gréup (L) MAS ed? MAS LE, Moving group), Mace Rate (r) = AIMA, Li {Bl = k (Complex) (Entering group] Comparison Between S,) and S2 Mechanisms. * Let us consider the following ligand substitution reaction MA,L+B>MA,E+L Sx mechanism MAL 1C.N. =6) aechanism . MA,L =e Ma,LE s ‘Slows KD ~ 8 ‘ast (CN. =6) (C.N.=7) (c. anid boo! (é) In Sy’ mechanism the rate determining step (slow step) ia metal —ligae4 (M—L bond) breaking step, since in this step MA L (C.N. = 8) 8 tp into MA, (C.N. = 5). Iti Sy" mechanism the rate determining this se ” step) is a metal — ligand bond (M—E bond) forming step, since #* MA, L (CN. = 6) is converted into MA, LE(C.N. = 7)e a ubattution Reaction in Octahedrat Complex , gf mechanism follows first ini i Gi) Sx mee , inst Order rate law. Thus rate determining step 16 unimolecular, ie. rate of reaction is first order w.r.t. MA, L Hence: Rate (r) of Sy mechanism = k, (MA, L] | =k, [Complex] Sa | { wv 2 mechanism follows second order rate law. ‘Thus the rate determining stop “ bimolecular ‘and the rate of reaction is first: order w.r.t to MA, L and first order rt B. Hence: 1 ° Rate (r).of Sy mechanism =.k, (MA, L] [E] £ y = kg [Complex] Entering group) ~~ >. jeaction Profile of Disbosiative (D) Mechanism 1 Reaction profile is a graphic representation of the energy a6 a reaction coordinate. Reaction coordinate represents the progress of a rei reattants to products Let us consider the following ligand substitution reaction — MX, function of the action from Here X is the leaving group and Y.is the entering group. The coordination amt cof the reacting complex, MX, and the formed complex, MX, ¥ is the same tay irthe above reaction proceeds through dissociative mechanism, them the con version of MX, into MX, , ¥ can be shown by the following steps: Mx, ay —Dissggiation 20, MK, +X4¥ : AO (CN.=n) ‘Transition state nat ie We AGN oD Yo k u Hie wba fe Sa MX, Yo 4K | a = CN=n-141 =n) Above mechanism shows that in the int step M-X bond is broken and. transi- state, MX,_, (intermediate) is obtained: fais the complex MX, should have activa: sguttetey required for the transition state shige MEX bond is broken to from Mass bagi has lower C.N. than MX, Once M-X. elit broken, the leaving group 00 leaves ing dination sphere of MX, to form the eqnediate (MIX, ,) which has a plateu 2s Ry ident from the reaction profile shown in ———Reattion coordinate ——~ 2271 Sino the leaving group OO leaves Fig. 27.1 Reaction profile for dis- "SPrkination sphere of My, 8 ¥ aconey. sociative (D) mechanism ted in the coordination sphere. ThisOE "ae dial Selected Teple n inorganic Ch, . : (¥) to form the products vacancy i by the entering groUP MX, y. x "The producto MX. Y and X have lower energy than the reactants Mandy The reaction profile has one hill'and one plutew. “A eS ° (A) Mechanism (sar 5 Rocedl for Assoviative . tion Prone tor ev oing ligand substitution reaction: Mx, +YO MX, ¥+X associative mechanism (Sx mechanis vg in be shown by the following steps Let us consider the fol If this reaction proceeds thro the conversion of MX, into MX," 2 Association(+¥) MX y —% ux uy Association), MX, MX,1¥ + MX, +¥ AY +X iti te.-* cs (CN.=n) aggre ‘Transition sta Bx & (CN. seep aad Gr In associative mechanism, the energy of the reactant (MX,) and entering group (¥) keeps on increasing till the activation energy for the transition state (intérmedi- ate), MX, Y is reached. Transition state has higher C.N. (= n + 1) than the original complex, MX, (C.N, =n), Now the bond be- tween M and X in transition state is broken ’ and M—Y bond is formed in MX,_, Y. So the intermediate passes through another smaller hill to stable products, MX, , Y and X (See Fig. 27.2) SOS ey tically Labile and Kinetically +++-Reaction coordinate —+ Inert Complexes Fig. 27.2 - Reaction profile for Depending on whether the rate of’ associative (A) mechanism. substitution reaction in complexes is slow or fast, the complexes have been classified as kinetically labile and kinetically inert complexes by Taube (1952). ____ Kinetically labile complexes are those in which one or more ligands present in coordination sphere of the complex gpecies can be replaced by other ligands quickly or rapidly. Thus the complexes in which the ligand substitution = fast are calledjTabile complexes. The rate of substitution of labile complex is difficult to measure and henee special techniques are used to study the kinetics of such complexes. Kinetically inert complexes are those in which the ligands present in coor” dination sphere of the complex species can be replaced slowly. Thus the co™ plexes in which the ligand substitution ig slow are called inert complexes- rate of substitution of inert complexes can bo measured canilyby convention®! techniques.899 I ee = A —— 1 Substitution Reaction in Octahedral Complex Ligant ince the term labile and inert re cuaemplanntaeins kinetically Thermodynafnically Stab! complexes 5 id ions, labile an od gs tions, ively. for te of substitution rea spectivel labile ger ‘Gnetcally inert complexes le and Thermodynamically Unstable Sig tion constant — Hex has high value of its\forma ion constant, aa odynamieally rma has low value eit constant itty & oem clearly that a thermodyKamieally. stal ‘amically unstable- ieehoula labile (fast reacting complex), Similarly a thermodyn odynamic stability, lero {cinetically inert (lov reacting complex), The ‘hermedy tablecempie: andkinetic lability are different, from each otis Beg a yanmically Keel ot) ana may be labile or inert. For example Pe (H,05,1"" (Bond uray = icatahiigr bat (Cr(H,0).)* Bond energy = 129 Kea mot Shave the Same thermodynami dseodalevhat Fe (H,0),]”" is kinetically labile (exchanges its ligands with other ae ee “4 [Cr G1,0),]* is kinetically inert (exchanges ligands slowly). [Cr (WH, el rmods namically unstable because of high value of its dissoci ICoNH,) P+ 6H,Ot BNi (CN) 1% jg thermodynatnically stable bes tion constant, Ka... (= 10”) but is ki cause of low value of it dissodia: netically labile (ast reacti exchanges CN ions very rapidly with added isoto ing complex, Pically labelled eyi UNCON) = yj2+ * ACN, Ra 19-28 BNHENY, PF 4 C4 en)- aquest Tita UNICN Heyyy: +on- eC dral Co, ‘€S On the B; iy : mplexes into Labile and Inert ‘asis of VBT : of ing to VBT, inner orbital octahedral ‘ition series sie formed by (gq)? (4s) (4p) hybrs Gay 48) 4p)» hybrids ‘ation are the orbitals of ee PYY Orcontagn the Clectrons of the mote! i tron pairs d, ted by six ligands. Aves i mE nelekes if8d orbit ita) set ‘ontain no (de), aot itd orbitete otc in 3048 ibinere mood = (CoH, 0), B+ +6NHj, Ki, = 105 >) since it d cyinide ions ene) Classification of Octahe, plex, ert, }——— eral Comptes, ‘ Hon (Crystal mon,9 the Ra.eo Ligand Substitution Reaction in Octahedral Complex . Since the terms labile snd inert refer tothe rate of eubstitution reactions, labile and pert complexes are called kinetically labile and kinetically inert complexes ely: qhermodynathically Stable and Thermodynamically Unstable complexes ‘A thermodynamically stable complex has high value of itsformation constant) while a thermodynamically uristable complex has low value of its Yormation constant, Tt should be understood clearly that a thermodyfiamically stablé complex may be kinetically labile (fast reacting complex). Similarly a thermodynamically unstable" fomplex may be kinetically inert (slow reacting comple). The thermodynamic stability, and kinetic lability are different from each other. ‘Thermodyanmically, stable complex may be labile or inert. For example [Fe (H,0),* (Bond energy = 116 Keal mol?) and [Cr(,0),|° (Bond energy = 122 Keal mol” )have the same thermodynamic stability but [Fe (H,0),]°” is kinetically labile (exchanges its ligands with other ligands rapidly) but [Cr(H,0),]*" is kinetically inert (exchanges ligands slowly). [Cr (NH,)gI*" is thermody- namically unstable because of high value of its dissociation constant, Ky, (= 10”) but is kinetically inert (slow reacting complex), since it remains undeomposed in acid solution. [Co(NH,),}"* +6H,O* =[Co(,0),F* +6NH}, Kaics = 10° {Ni (CN),]* is thermodynamically. stable because of low value of it dissocia~ tion constant, Kg, (= 10°”) but is kinetically labilé (fast reacting complex,) since it exchanges CN" ions very rapidly with added isotopically labelled cyinide ions (“CN) [Ni(CN),}? = Ni +. 4CN, Kgige 10°? er INKCND, P+ C4 ONY — Ya as 9 INUCN) (CNP + CNT we iq Classification of Octahedral Complexes into Labile and Inert of Complexes on the Basis of VBT a follow- MA5L(H,0) MAsL+H)0° a (C.N. = 6) (C.N.=7) Gi) Dissociation (~L) MA, (,0) +b Fast (C.N. = 6) Rute of reaction = & [Complex] [H,O} =h [Complex} =kIMAL) ¢ : z echanisms pretiict. that Itis clear from-the above discussion that both the me ‘ae ofhydrolysis reaction (i) is dependent only on the concentration of the complex, 4.1, Thus the measurement of the rate of hydrolysis reaction is not able to decide “isher the hydrolysis reaction (d) procgeds through Sy" mechanism or through mechanism. Consequently we will have to look to some other factors to decide ‘ype of mechanism, These factors are given below. raj Chatge on the complex. Ithas been observed during the hydrolysis of sev- ifatahedral complexes of Co(II) and other metal ions that the rate of hydrolysis ‘Complex decreases with the increase in the charge on the complex. . ty, temple. The rate of hydrolysis ofcis [Cot en), Cl,J" (D is some hundred timés typepit® that of cis- [Co(en), Cl (H,0)}*" (1): Thus the hydrolysis of (1 is fast and - “ID is slow as shown below Sees, sis (Co™(en), Cl,]*+H,0, "M+. cis [Co(en), CHO) +c (D (Charge=+1) . a sis [(Co** (en), C1 (H,0)1"* +H,0 —*+ cis[Co (en),(H,0),]"" + Cl” GD (Charge = + 2) we.908 Selected Topics in tnorgani Explanation. ‘The above observation eat be explained by Sy! nee, "ey hydrolysis reaction, since the inerease in the positive charge on the compjqy"Wa the dissociation of the leaving group (CI ion) from the metal ion (Co**) more, Taka, and hence the rate of hydrolysis becomes slow. , itiegt If the hydrolysis is supposed to proceed through Sy" mechanism, th, hydrolysis would remain unchanged with the increase or decrease in the on the complex. 2. Basicity of leaving group, L” If we study the rate of hydrolysi, plexes, [Co(NH;),L}”* which contain different L ligands (leaving groups), wi . Ls fexes decreases with the increase of the baa ‘of the rate of hydrolysis of these compl L- ligands. For example the rate ofhydrolysis of the complexes, [Co(NH), uy L” = CF,CO0", CCI,CO0", CH Cl, COO", CH; Cl COO 5 CH, CH, COo7 from CF, COO” to CH, CH, COO" since the basicity of these ligands increases in same direction Basicity of L* ligands Tate a charge 5 Of om, increases as; CF,COO” < CCl, COO” < CH Cl, COO CCI,COO™ > CHCI,COO- > CH,CICOO™ > CH,CH,COO™ trength of Co" L” bond is directly proportional ‘crease in'the basicity of L” ligands Co —1> e rate of hydrolysis decreases, Now Since the tion involves dissociation of Co™*—1° Rate of hydrolysis decreases as: ( ie Explanation. Since the s the basicity of L” ligand; with the in bond becomes stronger and hence thi rate determining step in the hydrolysis react bond, the hydrolysis reaction proceeds through Sy, mechanism. 3. Inductive effect of the inert group. It has been seen that the rate con- stants of acid hydrolysis reaction: {Colen), (A~py) CI] + HyO — [Co (en), (A-py) (H,0))* + Cr, increase with the CH, substitution in pyridine, In this reaction A-py stands fo various derivatives of pyridine which are obtained by removing one of the H-atezt of pyridine by CH, group. A-py is an inert ligand, since it remains coordinated the metal in the produet, [Co (en), (A-py) (Hj0)]"". The increase in rateconstants* due to the inductive effect caused by the increasing CH, substitution which results in distorting electron density towards Co-atom and thus helps the dissociation CI ion (leaving group). This again confirms the fact that the acid hydrolysis rea" tion given above occurs through disceociative Sy’ mechanism. ‘The values of rate constants (in sec) for the acid hydrolysis reaction: ICo(en), (A~py) Cl)?" + H,0 > [Co (en), (A-py) (H,O))* +. CF in which A-py is pyridine, 3-methy idit idine @) 107, 1.3 x 107 and 1.4 x 10° respectively ng ind atmathy pyran’ 4, Steric effects. In the complexes of : + i pidental® figand AA is NHy-CH,~ CH, - NH, NH. He eae Ott TaN # (CH,) ~ CHICHS) at NH, - CH, ~ C(CH,), and meso Hy N-CH (CH) a (CH,) ~ NH,, then the bulk of the ligand, (AA) inerease, i.e. the ligand (AA) becom” re 11* eee eee ar adPr i te tae tjgand Substitution Reactlon in Octshedral Complex 907 nore bulky, Due to the increase in the builk of the li i di : igand the steric overcrowding inindrance) ofthe ligand round the eontral metal ion (Co) also increases. Dug to the inetd 2 the overcrowding of the ligand round the central metal in (Co””)y another | agen cannot be taken up by the complex, ic. there is io possibility of Sw mechanism. On the contrary the removal ofa ligand will reduce the overcrowding ©! the ligand round the central metal ion. This gives the evidence of Sy’ mechanism. The increase in the bulk of the ligand (AA) also increases the value of rate constant for the acid hydrolysis reaction of the complexes as is evident from the following acid hydrolysis reactions. Kihiser Es +c i @ trans {Co (AA); Ch} File [Co tAA), C1 (H,0))?" 4,01" AA = NH, — CH, ~ CH, - NH,, & = 32% 10% 57 Gi) trans [Co (AA), Cl)" oe ane [Co (AA), Cl (H,O)]?* + OF AA = NH, ~ CH, - CH (CH,) - NH,, k= 6.2 x 10s (iii) trans [Co (AA, Clal* 39g [ColAA), CHO)?" CT AA = dl NH, CH (CH) - CH (CH,) — NH, # = 15.0 « 10%" (iv) trans {Co (AA), Cla]* ig? (Co (AA), CLO)" +1 AA = NH, - CH, —C (CH,)y-NH,, #= 22.0 x 10% 8. (v) trans [Co (AA), Ol] Sig [Co (AA), Cl HO} + C1 AA = meso H, N-CH(CH,) ~ CH(CH,) — NH, & = 42.0 x 10-5"? Let us compare the rates of aquation of (Co™ (NH, — CH, ~ CHs— CH, NA) Cly" @) and [Co®* (NH, — CH, - CH, - NH,), Cll” (ID). In complex (D, NH, ~ CH, ~CH, ~ CH, - NH, is propylenediamine and in complex (II), NH, ~ CH, - CH, — NH, is ethylenediamine. Both the complexes are chelated octahedral complexes. Complex (I) contains 6-membered chelate rings while complex (11) has 5-membered chelated rings. Now since 6@-membered chelate ring present in (I) praduces greater steric strain tound the central Co** ion than 5-membered chelate ring present in (II), the aguation of (I) will be fast than that of (II) through dissociative Sj mechanism See Fig. 27.3) ‘ The value of & fo x the aquation of complex (I) is much higher than that of Complex (II), Experimentally this prediction has been found true. 5. Solvation effects. According to solvation theory in aqneous medium, the "eacting complexes, the intermediates formed and the products obtained are all inthe hydrated state. The hydrated state of a species is represented by putting a | scripts, yd in the species. . | (g, Let us compare the rate of aquation of the complexes [Co(NH,), Cll** (1) and ms (en) (NH), Cll?’ (I). Complex (D is smaller in size than complex (LL), since Molex (1) ho. only monodentate ligands while complex (II) has chelated as wellGorected Toplos In Ineryanis 008 H,O Hy He! He H; 2+ te Sie Nt " gia ie > he oe au = 1000 Soon st yO BY é cl ' St a @ Chotated complex containing ‘@-membered chelate xings oO} \2 wo Oe ete) PN Bae hh By oo c. 1 \, Zz PS Ai esate Van oc. He “ Hp: cl He ap Chelated complex containing ‘5-mombered chelate rings Fig. 273 Com) arings of rates of aguation of (OO! Co(NH- © Ss NH), lJ” (D and (Co (NH,-CH,-CH,-NHi)s Ci,]* (ID complexes. ssumed to proceed As monodentate ligands. If the aqua! through dissociative Sx’ mechanism, then the aquatio "represented ast —w Ico (NHy)sliga Intermediate (smaller in size) amp [Co (NH,)5 Cla Non-chelated complex (smaller in size) () tion of the complexes is as n‘of these complexes can be CT pga [Co (NH,),I}54 —FAS [CotNHy)s GH,011%6 Intermediate (IID [Co (en) (NH) Cilia fe [Co (en) (NHg)sl a + Chg Chelated complex Intermediate. (bigger in size) (ID) (bigger in size) (IV) [Co (on) (NH)! nya = {Co (en) (NHy)3 (H, Intermediate (IV) Now since intermediate ( ate (III) is obtaine’ biswer te in size, the intermediate (IV) is stablised by hydration t 20M bya termed IV) is obtained from bigger com} lex (IT) and int dd from smaller complex (1), (IV) is bigger D gizo than (IID). Being it and ‘oa lesser exten!vem _—e yond upetiution Rewetion in Outanadral Compniy ee peace requires more energy for its formation than the intermediate ILD), As @ result, complex (ID) would be Aquated at a slower rate than complex (I). Since the steric overcrowding around the central metal ion in complexes [cotNHy), Clal” and (Co (en), Cl,}* is almost the same, the difference in the rate afaquation of these complexes can be interpreted on the basis of solvation effect. he rate of aquation of these complexes are as: [Co (NH), Cl)" = 180 x 10° s™, {C0 (en); Cl,J” = 3.2 x 10% 5 J. Octahedral Complexes in Which. the Inert Ligand is a pi Donor. Let is study: the aquation reaction of cis [Co (en), (OH) Cl]* and cis (Co (en), (NH) Cl} _ The aquation reaction ofthese complexes.ean be represented asshown in Fig. 27.4. Incis [Co(en),] (OH) Cl]*, OH ligand is a pi donor inert ligand. en | en - 2+ Hl @-or , |____ow |. S | | Gi) 8, ALN& a Soe | NI | Am 1200 x 107 4 > : | —OFs| . a on : | Cis {Co(en),{OR)1}+ [Coven),(OH)H,0)1"* % at a @-cr La @4 ‘ oe, 8} | ver = 0.05x 10% 9) t Se] /—on, en a Cin (Colen)(NH3)C1}2* [Co(en), (NE) (H,0)}9* Fig.27.4 Aquation of cis [Co(én), (OH) Cil* and cis (Co (¢n), (NH) Cl" _itmay be seen from the values of rate, constant (&) that the rate of aquation ee (Co(en), (OH) Cll* is much higher than that of cis {Co(en), (NH) Cll". The “rence in the values of k of the two complexes cari be explained on the basis of whit of OH™ and NH, ligands to form pi bonding. OH™ has filled Pp-orbital NH, molecule has no such orbital. The'lone pair of electrons on N-atom in Ni molecule is used up in coordination. The central metal ion (Co™* ion) of square fal intermediate formed during the aquation of cis {Coten), (OF) Cl]* has ° rlaps wi ? orbital on OH” ion to form a pi bond as shown in Fig. 27.5. me ithe \tis due to the formation of pi-bond that the idal i i : ‘pi at Square pyramidal interm, di i "ietd Asa result, the uation oats Calon, OLN e e easier that thSelected Topics In OFAN’ UNemigyy 910 2+ whose square pyramidal intermediate anno, aquation of cis ICo (em). (NH,) Cll ili bonding. be stabilised by P ne panies ow OF im imply dep bybri bo sipital on 0°" ion 1 en rs e [ cA \ | | Zi | +H,0 46—n, Past t jen| oH [Colen),(OHXH,O)!% ine f OH Cis [Coleone ” [Co(en),(OH]* ‘Square pyramidal interniediate . stablised by pi bonding Fig.27.5 Formation of pi bond in square pyramidal intermediate obtained < during the aquation of [Co (en), (OH) on", Let us consider. the aquation reactions of trans [Co (en), (OH) Cll” and trans {Co(en), (NH) Cl}°*. The aquation reactions of these. complexes proceed through S,' mechanism as shown in Fig. 27,6. + 1 en 1 a | @-cr . | ! (ii) +40 tof Nok on,| +00 b= 160x105 gt 1 i U eH J | trans {Cater ype ePtOHICH trang [Co(en)9 OHM EO) on. a ' " en 13+ wor : Hav o8 |-c] +80 e- | peachy a a | ks0.0%4 x 1951 || * —OH,| + i = LZ | trans (Cote én i en)(NH)01|2+ i trans (Colen)a(NEH,\H,0))* | rans IC trans ICo en), (NH) cant (OH) Ci] and | Fig-276 Aquation reactions ofe poo——— qusnttution Reaction in Octanedtal Compte sai : oi i — 7 _. —— Filled p-orbital on OH ion mn at “183 Empty dsp! hybrid orbital on Co°* ion | 7 | L ie riy. 81:7 Sinwo dep* hybrid orbicat bn Co” jon and p-urbital on OH" do not have same symmetry, they cannot overlap to form pi bond Itmay be seen from the values of rate constant (z) that the rate of aquation of .s(Colen), (OH) Cl] is much faster than that of trans [Co(en), (OH) Cll”. Since sp’ hybrid orbital (empty) on Co™ ion and p orbital (filled) on OH ion do not are incapable, ‘ethe same symmetry as is evident-from Fig. 27.7, these orbitals herlapping. Thus no pi bond is formed. In other words we can say that in the ration of trans [Co(en), (OH) Cl]* square pyramidal intermediate is not stabi- and hence is not formed. In place of square pyramidal intermediate, trigonal amidal intermediate is formed because it can be stabilised by pi bond which is by the overlap between the filled p-orbital on OH ion and empty d-orbital te" ion (See Fig. 27.8) Thepi bonded trigonal bipyramidal intermediate is more stable than square py- ial intermediate. The aquation of trans [Co(en), (OH) Cll* gives a mixture of cis ‘rans isomers of [Co(en), (OHXH,0)]”” as shown in Fig. 27.8: Ifmay be noted that aquation of trans [Co(en)(NH,) Cl* gives only trans [Co (en), (NH) (HO) From the above discussion the following: points may be noted: 4) The aquation reactions discussed above proceed through dissociative Sy Mechanism. Si Like OFF, NH, (hemechanism of aquation aude (NH, CI’, Br ete) is 4 r, Br i bonding inert li donors). Thus Cr, Br etc are also pi bonding inert ligands pi rs). 7 of the complexes containing these pibonding inert fhe same as that of the complexes containing pi inert ligand gives square py- mer containing @ k re ns isomer gives trigonal Aquation of a cis iso! I le the aquation of a tra’ Tidal intermediate whi inyramidal intermédiate. en square pyramidal intermedi mplex of the same geometry. On the o| med, the aquation reaction gives ate is formed, the aquation reaction gives ther hand when trigonal bipyramidal ‘a mixture of cis and trans isomers.Selected Topics in nora i S| trans OH)CII* ‘Trigonal bipyramidal Wofenlat intermediate stablised : by pi bonding | eid dj | rrane {Coten),(OHH,0)* Fig. 27.8 Aguation of trans: Cis [Coten)(OHKH,O)* -(Co(en), (OF) Cll” gives a mixture of cis and trans ism of {Go(en), (OH(H,O)"*. ILL Octahedral Complexes in Which the Inert Ligand is a pi Acco! ‘Aquation of octahedral complexes in which the inert ligand is apt acceptor?) ceeds through associative S3 mechanism. Thus the aquation of [Co(en)(NO»)Cl Gunich the ligand, NO, is an inert pi acceptor and the ligand, CI is the leave! proceeds through associative Sy” mechanism as shown below: (Co (en), (NO,) CII" BLE 4 [Coen), (NO,) (HO + OF ectator ligand. Depend cis to the leaving w ‘The inert pi acceptor ligand, NO’ is called sp. whether the inert pi acceptor ligand (NO, ) is placed trans or i (CI) in the octahedra} complex, the following two cases may be studied. x (a) Aquation of trans [Co(en), (NO,) Cl]* complex. In this comple and CI are placed trans to each other. In this complex one of the filled tag of Co*" ion can overlap with the empty p-orbital of NO, ligand te form SM (See Fig. 27.9). The formation of pi bond strengthens the Co— Cl bond ait the dissociation of Co~ Cl bond to release the leaving group (Cl) becomes: ‘Thus the aquation of ¢rans [Colen), (NO,) Cll” cannot proceed soe T mechanism, Due to the presence of pi-acceptor ligand (NOY sociation Syigand Substitution Reacti , sige eaction in Octahedral Complex ” ee on Co** ion i -Filled ty, orbital Empty p-orbital on NOx: ion , . trans [Co {en),(NO,)CI" trans (Co™(oin)y(NOJELON” j Fig. 27.9 Formation of pi bond by the overlap bet q 2. Nh 1p between filled orbital of Co" ion and empty p orbital of NOx ion during the nauatiin of trans (Co(en), (NO,) Cl". complex, the formation of Co — OH, bond is easier and hence the aquation of the complex proceeds through associative Sy” mechanism as represented by reaction @. (b) Aquation of cis {Co(en), (NO,) Cll’ complex. In this complex NO, and or are placed cis to each other. In this complex, since NOs ion is cis to CY ion, the extent of overlap between one of the filled tay orbitals ‘of Co” ion and empty parbital of NO", ion is less than when NO" jon is placed trans to Cl’ ion. Hence ihe formation of Cu - OH, bond would not be easy in cis complex, This proves that the aquation of cis complex also proceeds ‘through associative Sy” mechanism and not through dissociative Sy’ mechanism ‘The values of rate constants and % cis product obtained by the aquaxion of cis and trans isomers of (Co(en), A Cll" represented as: {Colen), A Cl" + H,0 25°, (Co(en), A(H,ON"?* + Cr are given in Table 27.4. Ais the pi acceptor ligand and CI ionis the leaving group. Table 27.4 Rate constants and % cis product obtained in aqua- tion of [Co(en),.A Cl?! represented as: [CoClA(en,)]"* + H,O Beg, [Co(H,0) A (en),1°°" + OF isomer | Pi acceptor ligand (A) 10°, 5 % cis product cis on 1,30,000 100 eis Ne 2,400 100 : cis cor 2,400 100 | cis NCS" 110 [Zoo trans oH” 14,000 _. 15 trans Na 2,500 20 fons (oY 350 38 1 trans NCS" 0.5 50-70