Group IV phosphinimide amide complexes

Abstract

Complexes of formula TiCp(NPR3)(NMe2)2 (R = t-Bu 1, Ph 2) were prepared via salt metathesis of TiCp(NPR3)Cl2 with a slight excess of LiNMe2. The species Ti(NP-t-Bu3)(NMe2)3 (3) was obtained as a by-product. The related derivative ZrCp(NP-t-Bu3)(NMe2)2 (4) was also prepared. Reaction of TiCp(NP-t-Bu3)Cl2 with LiNHC6H3(2,6-i-Pr2) afforded TiCp(NP-t-Bu3)(NHC6H3(2,6-i-Pr2))Cl (5) and Ti(NP-t-Bu3)(NHC6H3(2,6-i-Pr2))3 (6). In a similar manner, the Zr analogs ZrCp(NP-t-Bu3)(NHC6H3(2,6-i-Pr2))Me (7) and ZrCp(NP-t-Bu3)(NHC6H3(2,6-i-Pr2))2 (8) were also prepared. X-ray structural data for compounds 5, 6, and 8 are reported. Reactivity of these phosphinimide–amide derivatives was explored. While these species do not yield imide derivatives upon thermolysis, reaction of 5 with excess AlMe3 afforded TiCp(NP-t-Bu3)Me2 while reaction with 1 equiv. of AlMe3 gave TiCp(NP-t-Bu3)MeCl (9) and Al2(m-NHC6H3(2,6-i-Pr2))2Me4 (10). Key words: titanium, zirconium, phosphinimide, amide, ligand metathesis.