Sulfur atom transfer reactions of tungsten(VI) and tungsten(IV) chalcogenide complexes
作者： Aston A. Eagle , Robert W. Gable , Simon Thomas , Stephen A. Sproules , Charles G. Young
DOI: 10.1016/J.POLY.2003.11.026
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摘要: Abstract The sulfur, oxygen and chlorine atom transfer reactions of thio-W(VI) -W(IV) complexes containing monodentate ambidentate dithiophosphinate co-ligands are examined. Systems featuring ligands complicated by the instability W(IV) species; significantly in contrast to observations thio-Mo chemistry, such as Tp*WS2Cl fail react with cyanide. Dithiophosphinate systems more tractable amenable full description. oxo-thio bis(thio) complexes, Tp*WOS(S2PPh2-S) Tp*WS2(S2PPh2-S) [Tp*=hydrotris(3,5-dimethylpyrazol-1-yl)borate] undergo sulfur tertiary phosphines produce Tp*WO(S2PPh2-S,S′) Tp*WS(S2PPh2-S,S′), respectively, phosphine sulfides. X-ray crystal structures Tp*WS2(S2PPh2) · 0.5CH2Cl2 Tp*WS(S2PPh2) have been determined. Both possess six-coordinate, distorted-octahedral tungsten centers ligated tridentate fac-Tp*, terminal thio (W=S=2.139–2.143 A) mono- or bidentate ligands, respectively. Tp*WE(S2PPh2) (E=O, S), donors Tp*WES(S2PPh2) but yield mixtures Tp*WOE(S2PPh2) Tp*WES{SP(O)Ph2-S}. latter result from phosphorus concomitant tungsten. Catalytic thio-W is demonstrated for first time.
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