Preparation, Structure, and Reactivities of Amido-Bridged Dinuclear Rhodium(III) and Rhodium(II) Complexes

Abstract

Reaction of [Cp*RhX(μ2-X)]2 (2a, X = Cl; 2b, X = Br) with (LiNH)2C10H6-1,8 gave the novel amido-bridged dinuclear Rh(III) complex [Cp*Rh{(μ2-NH)2C10H6-1,8}(μ2-X)RhCp*]X (3a, X = Cl; 3b, X = Br), which further converted to the Rh(II) complex Cp*Rh{(μ2-NH)2C10H6-1,8}RhCp* (4) by Na/Hg reduction. Treatment of 4 with benzyl bromides produced 3b and the corresponding bibenzyl derivatives, whereas protonation of 4 with CF3CO2H afforded [Cp*Rh{(μ2-NH)2C10H6-1,8}(μ2-H)RhCp*]O2CCF3 (5). Complex 2a also reacted with 2 equiv of LiNHC6H4R-p to yield [Cp*Rh(μ2-NHC6H4R-p)3RhCp*]Cl (6·Cl: 6a, R = Me; 6b, R = H; 6c, R = Cl).