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We report the synthesis and structural characterization of five-coordinate complexes of rhodium and iridium of the type [(η 5 -C 5 Me 5 )M(N^N)] + (3-M + ), where N^N represents the aminopyridinate ligand derived from 2-NH(Ph)-6-(Xyl)C 5 H 3 N (Xyl = 2,6-Me 2 C 6 H 3 ). The two complexes were isolated as salts of the BAr F anion (BAr F = B[3,5-(CF 3 ) 2 C 6 H 3 ] 4 ). The M-N amido bond of complexes 3-M + readily activated CO, C 2 H 4 , and H 2 . Thus, compounds 3-M + reacted with CO under ambient conditions, but whereas for 3-Rh + , CO migratory insertion was fast, yielding a carbamoyl carbonyl species, 4-Rh + , the stronger Ir-N amido bond of complex 3-Ir + caused the reaction to stop at the CO coordination stage. In contrast, 3-Ir + reacted reversibly with C 2 H 4 , forming adduct 5-Ir + , which subsequently rearranged irreversibly to [Ir](H)(═C(Me)N(Ph)-) complex 6-Ir + , which contains an N-stabilized carbene ligand. Computational studies supported a migratory insertion mechanism, giving first a β-stabilized linear alkyl unit, [Ir]CH 2 CH 2 N(Ph)-, followed by a multistep rearrangement that led to the final product 6-Ir + . Both β- and α-H eliminations, as well as their microscopic reverse migratory insertion reactions, were implicated in the alkyl-to-hydride-carbene reorganization. The analogous reaction of 3-Rh + with C 2 H 4 originated a complex mixture of products from which only a branched alkyl [Rh]C(H)(Me)N(Ph)- (5-Rh + ) could be isolated, featuring a β-agostic methyl interaction. Reactions of 3-M + with H 2 promoted a catalytic isomerization of the Ap ligand from classical κ 2 -N,N' binding to κ-N plus η 3 -pseudoallyl coordination mode.

inorganic chemistry

Activation of Small Molecules by the Metal–Amido Bond of Rhodium(III) and Iridium(III) (η5-C5Me5)M-Aminopyridinate Complexes