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. The Re-N, average Re-S, and Re-O distances are 1.664(3), 2.441, and 2.116(3) Å, respectively. Deprotonation of 6 or 7 with Et(3)N gave 1. Recrystallization of 3 from CH(2)Cl(2)/hexane in air resulted in oxo-imido exchange and the isolation of the oxo-Re(V) species trans-Re(O)ClL(2). Treatment of 1 with tosyl anhydride gave trans-Re(NH)(OTs)L(2) (OTs = tosyl) 8. Reaction of [n-Bu(4)N][OsNCl(4)] with KL afforded trans-Os(N)ClL(2) 9, which has been characterized by X-ray crystallography. The Os-N, Os-Cl, and average Os-S bond distances in 9 are 1.64(1), 2.577(4), and 2.429 Å, respectively. Treatment of 10 with (CF(3)CO)(2)O, Ag(CF(3)CO(2)), or CF(3)CO(2)H resulted in chloride substitution and the formation of trans-Os(N)(OCOCF(3))L(2) 10. The Os-N, Os-O, and average Os-S distances in 10 are 1.643(5), 2.271(4), and 2.419 Å, respectively. Treatment of 1 with [Ph(3)C]BF(4) resulted in the isolation of trans-Re(NCPh(3))(F)L(2) 11, presumably via the cationic tritylimido intermediate [Re(NCPh(3))L(2)](+). Reaction of 9 with [Ph(3)C]BF(4) led to chloride abstraction and the formation of five-coordinate [Os(N)L(2)]BF(4) 12. The Os-N and average Os-S distances in 12 are 1.646(5) and 2.364 Å, respectively.