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

Cationic hydride complexes of bis(cyclopentadienyl)tungsten(IV) have been p repared and studied. The complex [W(eta-C5H5)(2)H(thf)][SO3CF3] reacts with CS2 in d(6)-acetone to form the chelated O-alkyl dithiocarbonate tungsten hydride insertion product [W(eta-C5H5)(2)(eta(2)-S2COCH(CD3)(2)-S,S')][SO3C F3] as demonstrated by single crystal X-ray diffraction and NMR spectroscop y. The styrene complex [W(eta-C5H5)(2)H(eta(2)-CH2CHC6H5)][PF6] has been pr epared as a mixture of exo and endo isomers. This isomeric mixture reacts t hermally with NCMe to give [W(eta-C5H5)(2)(CH2CH2C6H5)(NCMe)][PF6] and phot ochemically with NCMe to give [W(eta-C5H5)(2)H(NCMe)][PF6]. The molecular s tructures of the exo isomer and of the benzonitrile complex [W(eta-C5H5)(2) H(NCPh)][SO3CF3] are reported.