Bis(η-cyclopentadienyl)vanadium(III) derivatives as models in insertion reactions

Abstract

Reaction of carbon monoxide with benzyl- or methyl-bis(η-cyclopentadienyl)vanadium(III), [V(cp)₂X], gives acyl derivatives, [V(cp)₂(CO)(COX)], while under the same conditions [V(cp)₂Ph] yields, via phenyl migration to a cyclopentadienyl ligand, dicarbonyl(η-5-phenylcyclopenta-1,3-diene)(η-cyclopentadienyl)vanadium(I), which forms carbonyl(η-cyclopentadienyl)(η-phenylcyclopentadienyl)vanadium(II). Carbon monoxide promotes the insertion of SnCl₂ into the V–Cl bond of [V (cp)₂Cl], and carbonylbis(η-cyclopentadienyl)(trichlorostannio)-vanadium(III) is obtained. Insertions of CS₂ into the V–SR bond of [V(cp)₂(SR)] give bis(η-cyclopentadienyl)-(trithiocarbonato)vanadium(III) complexes, which can be oxidised to the corresponding vanadium(IV) derivaties.