METAL METAL BONDS INVOLVING VANADIUM ATOMS - A FACILE SYNTHESIS OF A NOVEL DIVANADIUM TETRAKIS(DITHIOACETATE) THAT CONTAINS 2 MU-ETA-2-S2 BRIDGES FROM BIS(BENZENE)VANADIUM(0) AND DITHIOACETIC ACID

The reaction between bis(benzene)vanadium(0), (η6-C6H6)2V, and dithioacetic acid, CH3CSSH, furnishes a novel dimer, (CH3CS2)2V(μ-η2-S2)2V(S2CCH3)2, in 56–62% yields. The brown product has been characterized by elemental analyses, NMR, IR, and mass spectrometry, magnetic susceptibility measurements, and X-ray crystallography. The immediate coordination sphere of the two vanadium cores is best regarded as consisting of two distorted trigonal prisms that share the four sulfur atoms that form one rectangular face and have each of the other four rectangular faces capped by one sulfur atom. Because the new compound is diamagnetic and the V-V distance equals 2.800 (2) Å, a single metal-metal bond is postulated for this vanadium-vanadium d1–d1 pair. Therefore, each vanadium center has an unusual and rare nine-coordinate geometry, having the form of a tricapped trigonal prism. The compound crystallizes in space group P21/c with a = 10.425 (2) Å, b = 11.123 (2) Å, c = 9.133 (4) A, β = 97.12 (2)°, V = 1051 (1) Å3, Z = 2, R = 0.0476, and Rw = 0.0598. Other important structural features: the S-S distance of the μ-η)2-S2 bridge is 1.997 (3) Å, and the V-S distances range from 2.366 (3) to 2.502 (2) Å. © 1990, American Chemical Society. All rights reserved.