Iridium complexes reductive elimination

One most important observation for the mechanistic discussion is the oxidative addition/insertion/reductive elimination processes of the iridium complex (31) (Scheme 1-10) [62]. The oxidative addition of catecholborane yields an octahedral iridium-boryl complex (32) which allows the anti-Markovnikov insertion of alkyne into the H-Ir bond giving a l-alkenyliridium(III) intermediate (34). The electron-... 

A key feature of the mechanism of Wilkinson s catalyst is that catalysis begins with reaction of the solvated catalyst, RhCl(PPh3)2S (S=solvent), and H2 to form a solvated dihydride Rh(H)2Cl(PPh3)2S [1], In a subsequent step the alkene binds to the catalyst and then is transformed into product via migratory insertion and reductive elimination steps. Schrock and Osborn investigated solvated cationic complexes [M(PR3)2S2]+ (M=Rh, Ir and S= solvent) that are closely related to Wilkinson s catalyst. Similarly to Wilkinson s catalyst, the mechanistic sequence proposed by Schrock and Osborn features initial reaction of the catalyst with H2 followed by reaction of the dihydride with alkene for the case of monophosphine-ligated rhodium and iridium catalysts [12-17]. Such mechanisms commonly are characterized... 

Complexes 6 undergo the second migratory insertion in this scheme to form the acyl complexes 7. Complexes 7 can react either with CO to give the saturated acyl intermediates 8, which have been observed spectroscopically, or with H2 to give the aldehyde product and the unsaturated intermediates 3. The reaction with H2 involves presumably oxidative addition and reductive elimination, but for rhodium no trivalent intermediates have been observed. For iridium the trivalent intermediate acyl dihydrides have been observed [29], The Rh-acyl intermediates 8 have also been observed [26] and due to the influence of the more bulky acyl group, as compared to the hydride atom in 2e and 2a, isomer 8ae is the most abundant species. 

At this point it is worthy of mention that solutions of these alkenyl-hydrido isomers react with hydrogen, at room temperature, to yield styrene and the starting [lrH2(NCMe)3(P Pr3)]BF4 complex. Deuterium treatment of the alkenyl-hydrido isomers shows an easy H/D hydride exchange, which suggests that the reaction with hydrogen is more favorable than C—H reductive elimination. Therefore, the hydrogenahon is dominated by an iridium(lll) species, and most probably iridium(l) species are not involved under catalytic conditions. 

Computational and catalytic studies of the hydrosilylation of terminal alkynes have been very recently reported, with the use of [ Ir( r-Cl)(Cl)(Cp ) 2] catalyst to afford highly stereoselectively P-Z-vinylsilanes with high yields (>90%) [35]. B-isomers can be also found among the products, due to subsequent Z —> E isomerization under the conditions employed. The catalytic cycle is based on an lr(lll)-lr(V) oxidahve addition and direct reductive elimination of the P-Z-vinylsilane. Other iridium complexes have been found to be active in the hydrosilylation of phenylacetylene and 1-alkynes for example, when phenylacetylene is used as a substrate, dehydrogenative silylation products are also formed (see Scheme 14.5 and Table 14.3). 

Similar competitive reductive elimination of C—H and Si—H bonds have been observed for the complex IrH(SiHPh2)(Mes)(CO)(dppe) in benzene, leading to the iridium complexes Ir(Mes)(CO)(dppe) and Ir(SiHPh2)(CO)(dppe) following first-order kinetics for both eliminations200. 

M. J. Wax, J. M. Stryker, J. M. Buchanan, C. A. Kovac, and R. G. Bergman, Reversible C—H Insertion/Reductive Elimination in ( 5-Pentamethylcyclopentadienyl)(trimethyl-phosphine)iridium Complexes. Use in Determining Relative Metal-Carbon Bond Energies and Thermally Activating Methane, J. Am. Chem. Soc. 106, 1121-1122 (1984). 

Homobimetallic iridium(I) complexes containing the binucleating PNNP ligand undergo oxidative addition and reductive elimination reactions with acetyl chloride and methyl iodide. Thus,... 

A different catalytic cycle for alkene hydroamination is initiated by the oxidative addition of the N-H bond to the metal, followed by insertion of the alkene into the metal-nitrogen bond and reductive elimination to form the amine. The oxidative addition of unactivated N-H bonds to platinum(O) complexes is thermodynamically unfavorable, so the catalytic cycle cannot be completed17, but the successful iridium(I)-catalyzed amination of norbornene with aniline has been reported18. 

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