Reaction of the thiurams [R2NC(=S)S](2) (R = Me, Et, Bz) with the trimethylamine complexes of alane (AlH3) and gallane (GaH3) results in the high yield production of the tris-dithiocarbamate complexes [M(S2CNR2)(3)] (M = Al, Ga) formed via the reductive cleavage of the S-S bond. Transmetallation reactions of [(Et2O)(k). AlH3](n) with [M'(S2CNEt2)(n)] (M' = As, Sb, n = 3, M' = Se, n = 2) also result in the synthesis of [Al(S2CNEt2)(3)] in high yield. A number of these complexes have been structurally characterised: [Al(S2CNEt2)(3)] (1), isomorphous with its chromium(III) analogue, belonging to the monoclinic P2(1)/n, Z=4, form of the [M(S2CNEt2)(3)] family; Al-S are 2.377(6)-2.390(6) Angstrom, similar to values previously established for [Al(S2CNMe2)(3)]. CH2Cl2, which is isostructural with its Ga analogue, 3, (triclinic P1, Z = 2), for which Ga-S are 2.418(2)-2.449(2) Angstrom; solvent... tris-dithio-carbamate interactions in these species appear to be of negligible significance. Al-S are anomalously long cf. Ga-S in counterpart complexes ca. 2.37, 2.44 Angstrom, Al, Ga-OH2 in their alums being 1.877(3), 1.944(3) Angstrom. These observations are reinforced by studies of [M(S(2)CNBz(2))(3)], M = Al, Ga, 2, 5, monoclinic P2(1), Z = 4, isomorphous with previously reported M = Fe, Co, Ir complexes, and of orthorhombic Fdd2 [Ga(S2CNEt2)(3)]. 2CHCl(3), 4, in which the molecule lies on a crystallographic 2-axis, the hydrogen atoms of the chloroform molecules being wedged between the sulfur atoms of the pairs of ligands. (C) 2000 Elsevier Science S.A. All rights reserved.
Andrews, P. C., Lawrence, S. M., Raston, C. L., Skelton, B., Tolhurst, V-A., & White, A. (2000). Dithiocarbamate complexes of trivalent aluminium and gallium via metal hydrides. Inorganica Chimica Acta, 300-302(N/A), 56-64. https://doi.org/10.1016/S0020-1693(99)00480-6