Eagle, A. A., Gable, R. W., Thomas, S., Sproules, S. and Young, C. G. (2004) Sulfur atom transfer of tungsten(VI) and tungsten(IV) chalcogenide complexes. Polyhedron, 23(2-3), pp. 385-394. (doi: 10.1016/j.poly.2003.11.026)
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Abstract
The sulfur, oxygen and chlorine atom transfer reactions of thio-W(VI) and -W(IV) complexes containing monodentate and ambidentate dithiophosphinate co-ligands are examined. Systems featuring monodentate ligands are complicated by the instability of the W(IV) species; significantly and in contrast to observations in thio-Mo chemistry, thio-W(VI) complexes such as Tp*WS2Cl fail to react with cyanide. Dithiophosphinate systems are more tractable and amenable to full description. The oxo-thio and bis(thio) complexes, Tp*WOS(S2PPh2-S) and Tp*WS2(S2PPh2-S) [Tp*=hydrotris(3,5-dimethylpyrazol-1-yl)borate] undergo sulfur atom transfer to tertiary phosphines to produce Tp*WO(S2PPh2-S,S′) and Tp*WS(S2PPh2-S,S′), respectively, and phosphine sulfides. The X-ray crystal structures of Tp*WS2(S2PPh2) • 0.5CH2Cl2 and Tp*WS(S2PPh2) have been determined. Both complexes possess six-coordinate, distorted-octahedral tungsten centers ligated by tridentate fac-Tp*, terminal thio (W=S=2.139–2.143 Å) and mono- or bidentate dithiophosphinate ligands, respectively. The W(IV) complexes, Tp*WE(S2PPh2) (E=O, S), react with sulfur atom donors to produce thio-W(VI) complexes, Tp*WES(S2PPh2) but with oxygen atom donors to yield mixtures of Tp*WOE(S2PPh2) and Tp*WES{SP(O)Ph2-S}. The latter result from oxygen atom transfer to phosphorus with concomitant sulfur atom transfer from phosphorus to tungsten. Catalytic sulfur atom transfer by thio-W complexes is demonstrated for the first time.
Item Type: | Articles |
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Status: | Published |
Refereed: | Yes |
Glasgow Author(s) Enlighten ID: | Sproules, Dr Stephen |
Authors: | Eagle, A. A., Gable, R. W., Thomas, S., Sproules, S., and Young, C. G. |
College/School: | College of Science and Engineering > School of Chemistry |
Journal Name: | Polyhedron |
Publisher: | Elsevier |
ISSN: | 0277-5387 |
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