Synthesis and characterisation of cationic bis(cyclopentadienyl)tungsten(IV) complexes

Abstract

Cationic hydride complexes of bis(cyclopentadienyl)tungsten(IV) have been prepared and studied. The complex [W(η-C₅H₅)₂H(thf)][SO₃CF₃] reacts with CS₂ in d⁶-acetone to form the chelated O-alkyl dithiocarbonate tungsten hydride insertion product [W(η-C₅H₅)₂(η²-S₂COCH(CD₃)₂-S,S′)][SO₃CF₃] as demonstrated by single crystal X-ray diffraction and NMR spectroscopy. The styrene complex [W(η-C₅H₅)₂H(η²-CH₂CHC₆H₅)][PF₆] has been prepared as a mixture of exo and endo isomers. This isomeric mixture reacts thermally with NCMe to give [W(η-C₅H₅)₂(CH₂CH₂C₆H₅)(NCMe)][PF₆] and photochemically with NCMe to give [W(η-C₅H₅)₂H(NCMe)][PF₆]. The molecular structures of the exo isomer and of the benzonitrile complex [W(η-C₅H₅)₂H(NCPh)][SO₃CF₃] are reported.