Sulfur atom transfer of tungsten(VI) and tungsten(IV) chalcogenide complexes

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
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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