Dithiocarbamate complexes of trivalent aluminium and gallium via metal hydrides

Philip C. Andrews, Stacey M. Lawrence, Colin L. Raston, Brian W. Skelton, Vicki Anne Tolhurst, Allan H. White

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Abstract

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 P21/n, Z = 4, form of the [M(S2CNEt2)3] family; Al-S are 2.377(6)-2.390(6) Å, similar to values previously established for [Al(S2CNMe2)3]·CH2Cl2, which is isostructural with its Ga analogue, 3, (triclinic P1̄, Z = 2), for which Ga-S are 2.418(2)-2.449(2) Å solvent···tris-dithiocarbamate 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 A, Al, Ga-OH2 in their alums being 1.877(3), 1.944(3) Å. These observations are reinforced by studies of [M(S2CNBz2)3], M = Al, Ga, 2, 5, monoclinic P21, Z = 4, isomorphous with previously reported M = Fe, Co, Ir complexes, and of orthorhombic Fdd2 [Ga(S2CNEt2)3]·2CHCl3, 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.

Original languageEnglish
Pages (from-to)56-64
Number of pages9
JournalInorganica Chimica Acta
Volume300-302
DOIs
Publication statusPublished - 30 Apr 2000
Externally publishedYes

Keywords

  • Aluminium complexes
  • Crystal structures
  • Dithiocarbamate complexes
  • Gallium complexes

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    Andrews, P. C., Lawrence, S. M., Raston, C. L., Skelton, B. W., Tolhurst, V. A., & White, A. H. (2000). Dithiocarbamate complexes of trivalent aluminium and gallium via metal hydrides. Inorganica Chimica Acta, 300-302, 56-64. https://doi.org/10.1016/S0020-1693(99)00480-6