rganometallic Study eeting#11 Chapter 5. igand Substitution Reactions 5.1 Introdution 011/6/18 K.isaki igand Substitution = A reaction in which a free ligand replaces a coordinated ligand Dissociative echanism S 1reaction <Interchange echanism> Associative echanism S reaction n n-1 n-1 n n-1 rds n-1 coordinatively unsaturated metal - is longer Dessociative interchange TS Associative interchange -' is longer partial bonding transition state 18e - type of complex 16e - or17e - 0thorderin 1st order overall smallpositive S smallpositive V more e-rich metal more e-poor metal sterically hindered metal affected strongly bythestrengthof-bond reduction weakens - bond (acceleration) rate law activation parameters favorable electronic& steric factors others 1storderin nd order overall largenegative S largenegative V morebasic more e-poor metal sterically accessible metal 5.. Thermochemical Considerations n + n-1 + BDE(-) > BDE(-) thermodynamically favorable BDE = bond dissociation energy energy needed for homolytic cleavage(two radical generation) for charged -type ligand energy needed for heterolytic cleavage(unsaturated metal + ewis base) for neutral -type ligand cf) BDE(-C)= 5-46kcal/mol =50-150 o Cheatingleadstocleave BDE(C 3 -C 3 )=88kcal/mol BDE(C 3 -)=104kcal/mol cf) BDE(polyhapto) > BDE(monohapto) cf) BDE(-)tendtobefirst-row<second-row<third-row(butnotalways) BDE(Cr(C) 5 -C) <BDE(o(C) 5 -C) < BDE(W(C) 5 -C) 37 40 46 kcal/mol cf) BDE(- acidic)>bde(- neutral)ifislowvalent cf) BDE(less hindered) > BDE(more hindered)
5.3. echanisms of igand Substitutions of 16e- and 17e- complexes >Associativemechanismsofsquare-planerd 8 complexes #"solvent assistance" = two associative substitution rate=k obs [ 3 ] = (k 1 +k [])[ 3 ] scheme5./figure5.1 solvent assisted path non-solvent assisted path often occurs in parallel #stereochemistry=retentive(butnotalways) //analogyofs c t c c t c c t c c t c - c t c # other factors affecting to rate softness nucleophilicity Cl if pentacoordinate intermediate is long-lived, stereochemistry is lost via Berry pseudorotation. Cl P 3 >>SC - >>I -,Br - > 3 - >Cl - > - ~ 3 Cl leaving ability + BDE o-tol PEt 3 Et 3 P Cl 3 - > >Cl - >Br - >I - > 3 - >SC - > - >C - (butlessdominantthaneffectof) i>pd> o-tol PEt 3 Et 3 P trans effect = trans ligand affect the rate of ligand substitutions = transition state/dynamism/kinetic ( trans infulence = related to bond length = ground state/structure/thermodynamic) - >e - > - >Cl - t PEt 3 Et 3 P Cl spansafactorof x10 4 t PEt 3 Et 3 P cis effect = similar effect by cis ligand, but usually smaller contribution Et 3 P PEt 3 c Cl PEt 3 c Fig 5. e - > - >Cl - spansafactorof x3 largerwhen t is -donating(weakens-bond),or -accepting(stabilizing5-coordinateintermediate).
>Whendessociativemechanismofsquare-planerd 8 complexesisdominant? #weaklybound # strong trans influence ligand # unsaturated metal site is covered by polydentate coordination # axial association of is prohibited # metal geometry is distorted from square planer # coordination number > 4 # very fast association generate super leaving group S S strong trans influence R P t Bu Ir DS-d 6 70-110 o C S covered vacant site R P t Bu Ir S S CD 3 CD 3 esi esi distoted geometry Pe Pe P t Bu strong trans influence P t Bu strong trans influence e e DTf fast D e e D e e dessociative exchange > Associative mechenism of 17e- complexes substitution rate: 17e complexes > 18e complexes associative mech. leads to energetic gains. ) Poe's experiment ref) Re (C) 10 h Re(C) 5 17e P 3 CCl 4 Dessociative mech. Re(C) 4 Cl P 16e 3 C Re(C) 4 (P 3 )Cl+ Re(C) 5 C 18e l 18e Fig. 5.3 P 3 Re(C) 5 (P 3 ) C CCl 4 Re(C) 4 (P 3 ) 19e Associative mech. 17e excesschadnoeffectontheratio dessociative path was denied R affects reaction rate V(C) 6 PR 3 V(C) 5 (PR 3 ) 17e hexane, rt rate=k[v(c) 6 ][PR 3 ] negative S
5.4. echanisms of igand Substitutions of 18e- complexes > Dessociative mechanism k 1 k n - k -1 n n - rate= k 1 k [ n ][] k -1 []+k [] k 1 [ n ] fig 5.4 (usuallyk []>>k -1 []) i(c) 4 C solvent i(c) 3 (solv) i(c) 3 BDE((C) 3 i-c)=5kcal/mol positive S (=+8~+13eu) # Steric bulkiness of ligand(tolman's cone angle) largely affects the rate. R=Et<<p-tol< i Pr<o-tol<<P 3 K D i(p(r) 3 ) 4 i(p(r) 3 ) 3 + P(R) 3, rt #stereochemistry=easilylost//analogytos 1 18e - 18e - - flipof16e - intermediate pseudorotation # cis effect in(pseudo)octahedral complexes =makesdessociationof cis fasterthanthatof trans c c c c t t c c c c c t c c c - 3 >Ac - -,C, RC() - >R>S - >R>Cl - >Br - >I - >carbene>p 3 > -,C larger in case of chelating, -donating, less -donating ligand stablization of unsaturated metal C C C W C Ac C 13 C C C C W C 13 C Ac
> Reagent and catalyst induced dessociation of C # photo-induced # redox, SET-induced Re(C) 5 h PBu 3 Re(C) 4 (PBu 3 ) rt,0min n *(-) analogous to radical chain rxn w/olight:rat75 o Cfor60days scheme 5.8 # ligand oxidation-induced (review: Coord. Chem. Rev. 1984, 53, 7.) (C) -oxide promoted Pauson-Khand rxn(schreiber, S.. et al. T 1990, 31, 589) x R 3 - R 3 (C) x-1 (C) x-1 (R 3 ) + C (faster if C is more electrophilic)
5.4. echanisms of Substitutions Involving Polyhapto igands >DieneandTriene # 18e- complex + strong dative = competitive pathways rate=(k 1 +k [])[(C 4 )(diene)] Fig5,43 dissociative path associative path >Arene # stepwiseringslip( 6-4 - )occurs on the occasion when solvent or ligand income. faster in case of donar solvent, weakly bindin arenes cyclohexanone(1300) > C(600) > TF(30) ~ Cr(C) 3 (C 6 e 6 )(30) >uncatalyzed(1) scheme 5.9 stability # photoirradiation, redox, SET also accelerate the process. ) acceleration by ligand design(semmelhack,. F. et al. JACS 001,13, 8438, JACS 005, 17, 7759.) <concept> = -acidic ligand (comparable to C)
>Cpligand # associative substitution of ligand other than Cp ring stepwiseringslip( 5-3 )occursonthe occasion when solvent or ligand income. scheme 5.48 Fig.5.7 Table 5.11 aromaticity is not preserved during ring slip, in case of rightside Cp families. asotherratioinalization,groundstateenergyof 5 -indenylishigher(becauseofringdissymmetry)than 5 -Cp. 5.6 igand Substitutions in ultimetallic Clusters All associative, dessociative, reagent-induced subsitutions are allowed as mononuclear complexes. > Complex possessing metal-metal bond (C) 4 (C) 4 (C) 4 associative pathway (see17e - complex) -C (C) 4 (C) 3 dessociative pathway (see18e - complex) depends relative strength between BDE(-) and BDE(-C) weaker in case of first-row transition metals ) eq 5.53 1st: associative nd: dessociative 3rd: dessociative relativerate,1st:nd:3rd =1:30:90 presence of bridging C ligand affects largely.