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https://hdl.handle.net/2440/17780
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Type: | Journal article |
Title: | Formation of Mono(dithiolene)-Thiocarboxamido Complexes in Reactions of Thio(dithiocarbamato)-Mo/W Complexes and Dimethyl Acetylenedicarboxylate |
Author: | Lim, P. J. Slizys, D. A. Tiekink, Edward Richard Tom Young, Charles G. |
Citation: | Inorganic Chemistry. 44 (1), 114 -121, 2005. 10.1021/ic048882g S0020-1669(04)08882-2 |
Publisher: | American Chemical Society |
Issue Date: | 2005 |
ISSN: | 0020-1669 |
School/Discipline: | School of Chemistry and Physics School of Chemistry and Physics |
Statement of Responsibility: | Patrick J. Lim, Damian A. Slizys, Edward R. T. Tiekink, and Charles G. Young |
Abstract: | Reactions of Tp*MS(S2CNEt2) with dimethyl acetylenedicarboxylate in dichloromethane produce olive green/black Tp*M{S2C2(CO2Me)2}(SCNEt2-2S,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-2S,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*MoI(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(S2CNEt2), 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. |
DOI: | 10.1021/ic048882g |
Appears in Collections: | Chemistry publications |
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