Heterobimetallic mu-nitrido complexes containing ruthenium(II) dithiocarbamate

Interaction of [Ru(Co)H(Et(2)dtc) with triflic acid (HOTf) afforded [Ru(Co)H(Et(2)dtc)(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 an 1.811(5), 2.216(3), 2.433 and 2.423 Angstrom, respectively. Reaction of 1 with amines L results in the formation of adducts trans-[Ru(CO)(Et(2)dtc)(PPh3)(2)L](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)degrees. Treatment of 1 with [(NBu4)-Bu-n][OsN(C7H6S2)(2)] ([C7H6S2](2-) =3,4-toluenedithiolate(2-)), and [ReN(Et(2)dtc)(2)] (Et(2)dtc = N,N-diethyldithiocarbamate) gave the corresponding mu-nitrido complexes [Ru(CO)(Et(2)dtc)(PPh3)(2)(NOsO3)] (4), [Ru(CO)(Et(2)dtc)(PPh3)(2){NOs(C7H6S2)(2)}] (5) and [Ru(CO)(Et(2)dtc)(PPh3)(2){NRe(Et(2)dtc)(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) Angstrom, and 155.1(4)degrees, respectively. The Os-N and Ru-N distances and Os-N-Ru angle in 5 are 1.680(6) and 2.068(6) Angstrom, and 166.2(3)degrees, respectively. The Re-N and Ru-N distances, and Re-N-Ru angle for 6 are 1.670(3) and 2.108(3) Angstrom, and 170.9(2)degrees, respectively. The bond lengths and angles for these mu-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. All rights reserved.