The reactivity of trimethylsilyliminophosphines towards titanium and zirconium halides

Zirconium tetrachloride reacted with C2H4(Ph2P=NSiMe3)(2)-1,2 1 under C-H a ctivation to give the NCN chelate complex ZrCl3{kappa (3)-N,C,N'-C2H3(Ph2P= NSiMe3)(2)}, while the reaction with C5H3N(Ph2P=NSiMe3)(2)-2,6 gave an N-do nor adduct. Cp*TiCl3 reacts with trimethylsilyliminophosphines under dehalo silylation in all cases. In contrast to 1, the potentially C-N chelating be nzylphosphinimine (4-(BuC6H4CH2)-C-t)Ph2P=NSiMe3 undergoes dehalosilylation with TiCl4 in preference to C-H activation, while prolonged reflux with Zr Cl4 affords the salt [4-(BuC6H4CH2P)-C-t(Ph)(2)NHSiMe3](2)[Zr2Cl10]. The mo lecular structures of the latter, ZrCl3{C2H3(Ph2PNSiMe3)(2)}, C5H3N(Ph2P=NT iCl2Cp*)(2)-2,6, and TiCl2Cp*{N=PPh2CH2C6H4But-4} have been determined by X -ray diffraction.