Synthesis, Structure, and Reactivity of the Phosphinimide Complexes (t-Bu3PN)nMX4-n (M = Ti, Zr)

2000 
The phosphinimide complexes (t-Bu3PN)TiCl3 (1) and (t-Bu3PN)2TiCl2 (4) are readily prepared in high yields from the stoichiometric reaction of t-Bu3PNSiMe3 and TiCl4, while (t-Bu3PN)3TiCl (11) is readily obtained from the reaction of t-Bu3PNLi and TiCl4. The analogous 1:1 or 2:1 reactions of ZrCl4 and t-Bu3PNLi afford mixtures of products, although in the 3:1 stoichiometric ratio (t-Bu3PN)3ZrCl (12) is isolable. These complexes are readily alkylated with a variety of reagents to give (t-Bu3PN)TiMe3 (2), (t-Bu3PN)Ti(CH2Ph)3 (3), (t-Bu3PN)2TiMe2 (5), (t-Bu3PN)2Ti(η3-C3H5)2 (6), (t-Bu3PN)2Ti(CH2Ph)2 (7), (t-Bu3PN)2TiPh2 (8), (t-Bu3PN)2Ti(η5-Cp)Cl (9), (t-Bu3PN)2Ti(η5-Cp)Me (10), (t-Bu3PN)3TiMe (13), (t-Bu3PN)3TiPh (14), (t-Bu3PN)3ZrMe (15), (t-Bu3PN)3Zr(CH2Ph) (16), and (t-Bu3PN)3Zr(η5-Cp) (17). Subsequent reactions of some of these alkyl derivatives with [PhNMe2H][B(C6F5)4], [Ph3C][B(C6F5)4], or B(C6F5)3 are investigated. A number of zwitterionic and cationic species complexes have been characterized. These...
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