Reactions of Nitridorhenium(V) and -Osmium(VI) Complexes with Acylating Agents.

Interaction of Re(N)L(2) [L = N(PSPh(2))(2)] 1 with (CF(3)CO)(2)O or RCOCl afforded air-sensitive acylimido-Re(V) complexes trans-Re[NC(O)CF(3)](OCOCF(3))L(2) 2 or trans-Re[NC(O)R]ClL(2) (R = CCl(2)H 3, CClH(2) 4, CH(3) 5), respectively. Treatment of 1 with (CX(3)CO)(2)O followed by recrystallization from CH(2)Cl(2)/hexane in air led to the formation of the corresponding parent imido complexes trans-Re(NH)(OCOCX(3))L(2) (X = F 6, Cl 7). The structure of 7 has been characterized by X-ray crystallography.

Oxidation Reactions of Dithiocarbamate Complexes of Ruthenium(II).

The reaction of Ru(Et(2)dtc)(2)(DMSO)(2) (Et(2)dtc = N,N-diethyldithiocarbamate; DMSO = dimethyl sulfoxide) with t-BuNC gave trans-Ru(Et(2)dtc)(2)(CN-t-Bu)(2), 1. Complex 1 crystallizes in the monoclinic space group P2(1)/n with a = 9.753(2) Å, b = 11.