Please use this identifier to cite or link to this item: https://doi.org/10.1021/ic048882g
Title: Formation of mono(dithiolene)-thiocarboxamido complexes in reactions of thio(dithiocarbamato)-Mo/W complexes and dimethyl acetylenedicarboxylate
Authors: Lim, P.J.
Slizys, D.A.
Tiekink, E.R.T. 
Young, C.G.
Issue Date: 10-Jan-2005
Citation: Lim, P.J., Slizys, D.A., Tiekink, E.R.T., Young, C.G. (2005-01-10). Formation of mono(dithiolene)-thiocarboxamido complexes in reactions of thio(dithiocarbamato)-Mo/W complexes and dimethyl acetylenedicarboxylate. Inorganic Chemistry 44 (1) : 114-121. ScholarBank@NUS Repository. https://doi.org/10.1021/ic048882g
Abstract: Reactions of Tp*MS(S2CNEt2) with dimethyl acetylenedicarboxylate in dichloromethane produce olive green/black Tp*M{S2C2(CO2Me)2}(SCNEt 2-κ2S,C) (M = Mo (1), W (2); Tp* = hydrotris(3,5-dimethylpyrazol-1-yl)borate). The seven-coordinate complexes exhibit pseudo-octahedral (1) and distorted pentagonal bipyramidal (2) coordination spheres comprised of tridentate fac-Tp*, bidentate dithiolene, and thiocarboxamido-κ2S,C ligands. In the solid state, molecules of 1 exhibit pseudo-Cs symmetry, with the thiocarboxamide NEt2 group in a cleft in the Tp* ligand. Molecules of 2 have C1 symmetry in the solid state; here, the thiocarboxamide unit is orientated along one of the W-S(dithiolene) bonds with its NEt2 group projecting away from the Tp* ligand. Both complexes possess effective Cs symmetry in solution. Reaction of Tp*Mol(CO)3 with AgS2CNEt2 affords olive green Tp*Mo(S2CNEt2)(CO)2 (3), which reacts with propylene sulfide in a new synthesis for Tp*MoS(S 2CNEt2), the starting material for 1. Complex 3 exhibits a distorted pentagonal bipyramidal structure, the axial sites being defined by a Tp* nitrogen atom and a carbonyl ligand, the pentagonal plane by the remaining nitrogen and carbonyl donors and the two sulfur atoms of the bidentate dithiocarbamate ligand.
Source Title: Inorganic Chemistry
URI: http://scholarbank.nus.edu.sg/handle/10635/93849
ISSN: 00201669
DOI: 10.1021/ic048882g
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