Heterobimetallic µ-nitrido complexes containing ruthenium(II) dithiocarbamate

Abstract

Interaction of [Ru(Co)H(Et2dtc)with triflic acid (HOTf) afforded [Ru(Co)H(Et2dtc)(PPh3)2(OTf) (1), which has been characterized by X-ray crystallography. The Ru-C, Ru-O, average Ru-S and average Ru-P distances in 1 are 1.811(5), 2.216(3), 2.433 and 2.423 Å, respectively. Reaction of 1 with amines L results in the formation of adducts trans-[Ru(CO)(Et2dtc)(PPh3)2L](OTf) (L = N2H4 (2) and NH2OH (3)). The Ru-C, Ru-N, average Ru-S and average Ru-P distance in 3 are 1.85(1), 2.179(8), 2.433 and 2.393, respectively; the Ru-N-O angle being 119.7(5)°. Treatment of 1 with [N(n)Bu4][OsN(C7H6S2)2] ([C7H6S2]2- = 3,4-toluenedithiolate(2-)), and [ReN(Et2dtc)2] (Et2dtc = N,N-diethyldithiocarbamate) gave the corresponding μ-nitrido complexes [Ru(CO)(Et2dtc)(PPh3)2(NOsO3)] (4), [Ru(CO)(Et2dtc)(PPh3)2{NOs(C7H6S2)2}] (5) and [Ru(CO)(Et2dtc)(PPh3)2{NRe(Et2dtc)2}] (6). The structures of complexes 4-6 have been established by X-ray crystallography. The Os-N and Ru-N distances, and Os-N-Ru angle in 4 are 1.719(7) and 2.075(7) Å, and 155.1(4)°, respectively. The Os-N and Ru-N distances and Os-N-Ru angle in 5 are 1.680(6) and 2.068(6) Å, and 166.2(3)°, respectively. The Re-N and Ru-N distances, and Re-N-Ru angle for 6 are 1.670(3) and 2.108(3) Å, and 170.9(2)°, respectively. The bond lengths and angles for these μ-nitrido complexes are indicative of asymmetric bridging mode of nitride, i.e. M≡N→ Ru(II) (M = Os(VIII), Os(VI), Re(V)). (C) 2000 Elsevier Science S.A.