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 = 11.583(2) Å, c = 12.974(2) Å, and beta = 91.8(2) degrees for Z = 2. The crystal structure of 1 shows the trans disposition of the two isocyanides; the mean Ru-S and Ru-C distances are 2.409 and 1.977(2) Å, respectively. Treatment of [Ru(diene)Cl(2)](n)() with Na(Et(2)dtc) afforded Ru(Et(2)dtc)(2)(diene) (diene = bicyclo[2.2.1]hepta-2,5-diene (NBD), 2, 1,5-cyclooctadiene (COD), 3). Complex 2 crystallizes in the triclinic space group P&onemacr; with a = 7.316(1) Å, b = 10.346(1) Å, c = 15.123(2) Å, alpha = 103.69(2) degrees, beta = 93.54(2) degrees, and gamma = 100.61(2) degrees for Z = 2. The mean Ru-S and Ru-C distances in 2 are 2.416 and 2.137 Å, respectively. The reaction of cis-Ru(Et(2)dtc)(2)(CO)(2) with iodine gave the 2:1 molecular iodine complex cis-Ru(Et(2)dtc)(2)(CO)(2).(1)/(2)I(2) 4, which crystallizes in the monoclinic space group P2(1)/c with a = 7.347(2), b = 22.227(2) Å, c = 12.891(2) Å, and beta =95.98 (2) degrees for Z = 4. The mean Ru-S and Ru-C and the I-I distances in complex 4 are 2.427, 1.903, and 2.745(1) Å, respectively. Treatment of Ru(Et(2)dtc)(2)(DMSO)(2) with I(2) gave the linear Ru(II)-Ru(III)-Ru(III) trimer [Ru(3)(Et(2)dtc)(6)(DMSO)(2)](I(3))(2), 5, which crystallizes in the triclinic space group P&onemacr; with a = 14.125(3) Å, b = 20.829(6) Å, c = 13.658(3) Å, alpha = 97.57(2) degrees, beta = 110.01(2) degrees, and gamma = 71.25(2) degrees for Z = 2. The structure of complex 6 can be viewed as consisting of a {Ru(2)(III)(Et(2)dtc)(4)}(2+) core and a {Ru(II)(Et(2)dtc)(2)(DMSO)(2)} moiety, which are linked together via the two dithiocarbamate sulfurs of the latter. While the two Ru(III) centers are connected by a Ru-Ru single bond (Ru-Ru = 2.826(2) Å), there is no direct interaction between the Ru(III) and Ru(II) centers. Oxidation of Ru(Et(2)dtc)(2)L(2) (L = PPh(3), t-BuNC) by I(2) gave the respective [Ru(Et(2)dtc)(2)L(2)](+) cations. The reaction of cis-Ru(Et(2)dtc)(2)(PPh(3))(2) with excess tosyl azide gave the diamagnetic Ru(IV) tetrazene complex Ru(Et(2)dtc)(2)(Ts(2)N(4)), 7. Complex 7 crystallizes in the triclinic space group P&onemacr; with a = 10.380(1) Å, b = 11.322(1) Å, c = 15.310(1) Å, alpha = 106.84(2) degrees, beta = 106.87(2) degrees, and gamma = 92.63(2) degrees for Z = 2. The Ru-S and Ru-N(alpha) distances in 7 are 2.385 and 1.98 Å, respectively. The formal potentials of the Ru dithiocarbamate complexes were determined by cyclic voltammetry.
Leung
Wa-Hung
WH
Departments of Chemistry, Hong Kong University of Science and Technology, Clear Water Bay, Kowloon, Hong Kong, and University of Hong Kong, Pokfulam Road, Hong Kong.
Chim
Joyce L. C.
JL
Hou
Hongwei
H
Hun
Tom S. M.
TS
Williams
Ian D.
ID
Wong
Wing-Tak
WT