ON THE NATURE AND REACTIVITY OF Cp2TiCH3

Article abstract of DOI:10.1016/S0022-328X(00)83701-8

Reaction of Cp2TiCl with 1 eq. of CH3Li in ether at -78 deg C yields the green, thermally unstable, trivalent Ti compound Cp2TiCH3 * EPR studies on ether solutions of this compound reveal it to be present in solution as the adduct Cp2TiCH3 * OEt2 * By reaction with DCl Cp2TiCl2 and CH3D are formed.Reaction with 2,6 xylylisocyanide leads to insertion of the isocyanide into the Ti-CH3 bond, while reaction with CS2 yields the disproportionation products Cp2-Ti(CH3)2 and Cp2TiCS2.Thermal decomposition studies on deuteriated analogues confirm the Ti-CH3 structure.The ratedetermining step in the decomposition process is the abstraction of a Cp proton by the methyl group.Under nitrogen the decomposition reaction yields NH3 and N2H4 in amounts of up to 0.28 moles N/Ti.Some catalytic applications of Cp2TiCH3 for hydrogenation and isomerisation of olefins and acetylenes are briefly mentioned.