The reactivity of trimethylsilyliminophosphines towards titanium and zirconium halides

摘要

Zirconium tetrachloride reacted with C_2H_4(Ph_2P=NSiMe_3)_2-1,2 1 under C-H activation to give the NCN chelate complex ZrCl_3{k~3-N,C,N'-C_2H_3(Ph_2P=NSiMe_3)_2}, while the reaction with C_5H_3N(Ph_2P=NSiMe_3)_2-2,6 gave an N-donor adduct. Cp~*TiCl_3 reacts with trimethylsilyliminophosphines under dehalosilylationin all cases. In contrast to 1, the potentially C-N chelating benzylphosphinimie (4-Bu~tC_6H_4CH_2)Ph_2P=NSiMe_3 undergoes dehalosilylation with TiCl_4 in preference to C-H activation, while prolonged relux with ZrCl_4 affords the salt [4-Bu~tC_6H_4CH_2P(Ph)_2NHSiMe_3]_2[Zr_2Cl_(10)]. The moleuclar structures of the latter, ZrCl_3{C_2H_3(PNSiMe_3)_2}, C_5H_3N(Ph_2P=NTiCl_2Cp~*)_2-2,6, and TiCl_2Cp~*{N-PPh_2CH_2C_6H_4Bu~t-4} have been determined by X-ray diffraction.