Preparation, structure, and reactivities of amido-bridged dinuclear rhodium(III) and rhodium(II) complexes

Reaction of [Cp*RhX(mu(2)-X)](2) (2a, X= Cl; 2b, X = Br) with (LiNH)(2)C10H 6-1,8 gave the novel amido-bridged dinuclear Rh(III) complex [Cp*Rh{(mu(2)- NH)(2)C10H6- 1,8}(mu(2)-X)RhCp*]X (3a, X = Cl; 3b, X = Br), which further c onverted to the Rh(II) complex Cp*Rh{(mu(2)-NH)(2)C10H6-1,8}RhCp* (4) by Na /Hg reduction. Treatment of 4 with benzyl bromides produced 3b and the corr esponding bz:benzyl derivatives, whereas protonation of 4 with CF3CO2H affo rded [Cp*Rh{mu(2)-NH)(2)C10H6-1,8}{mu(2)-H)RhCp*]O2CCF3 (5). Complex 2a als o reacted with 2 equiv of LiNHC6H4R-p to yield [Cp*Rh(mu(2)-NHC6H4R-p)(3)Rh Cp*]Cl (6 . Cl: 6a, R = Me; 6b, R = H; 6c, R = Cl).