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https://hdl.handle.net/2440/4798
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Type: | Journal article |
Title: | Transformations leading to the generation of dithiolene ligands initiated by reactions of sulfur-rich WS(S₂)(S₂CNR₂)₂ complexes with dimethyl acetylenedicarboxylate and phenylacetylene |
Other Titles: | Transformations leading to the generation of dithiolene ligands initiated by reactions of sulfur-rich WS(S(2))(S(2)CNR(2))(2) complexes with dimethyl acetylenedicarboxylate and phenylacetylene |
Author: | Lim, P. Cook, V. Doonan, C. Young, C. Tiekink, E. |
Citation: | Organometallics, 2000; 19(26):5643-5653 |
Publisher: | Amer Chemical Soc |
Issue Date: | 2000 |
ISSN: | 0276-7333 1520-6041 |
Statement of Responsibility: | Patrick J. Lim, Vernon C. Cook, Christian J. Doonan, Charles G. Young and Edward R. T. Tiekink |
Abstract: | Purple W(S2C2R‘2){SC(R‘)C(R‘)SC(NR2)S}(S2CNR2) (1, donor atoms italicized) are formed in the reactions of WS(S2)(S2CNR2)2 (R = Me, Et) with dimethyl acetylenedicarboxylate (DMAC, R‘ = CO2Me) in dichloromethane at room temperature or phenylacetylene (R‘ = Ph/H) in refluxing 1,2-dichloroethane. These complexes undergo CS−C(NR2) bond cleavage upon photolysis to produce green thiocarboxamido species, W(S2C2R‘2)2(S2CNR2)(SCNR2) (2), which in turn convert to orange, anionic, bis(dithiolene) complexes, [W(S2C2R‘2)2(S2CNR2)]- (3, isolated as various tetraalkylammonium salts). The complexes have been characterized by microanalysis, IR, UV−visible, and 1H and 13C NMR spectroscopy. An X-ray crystal structure of 1a·0.5H2O (R = Me, R‘ = CO2Me) revealed two independent, pseudo-enantiomeric, eight-coordinate complexes containing novel κ4-SC(R‘)C(R‘)SC(NR2)S- and bidentate dithiolene and dithiocarbamate ligands. Complexes 2 are fluxional at room temperature and exhibit IR and 13C NMR signals characteristic of thiocarboxamido (ν 1590 cm-1, δ 226−228), dithiocarbamate (ν 1540 cm-1, δ 190−201), and dithiolene ligands. An X-ray crystal structure of NEt4[3a] (R = Me, R‘ = CO2Me) revealed an S6-donor, trigonal-prismatic anion possessing bidentate dithiocarbamate and dithiolene ligands. In the sequence of transformations, WS(S2)(S2CNR2)2→1→2→3, the construction of two dithiolene ligands from two alkyne units and three chemically distinct sulfur-donor ligands (thio, disulfido, dithiocarbamate) has been tracked for the first time. |
Description: | Copyright © 2000 American Chemical Society |
DOI: | 10.1021/om0006561 |
Published version: | http://dx.doi.org/10.1021/om0006561 |
Appears in Collections: | Aurora harvest 6 Chemistry publications Environment Institute publications |
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