Titanium and zirconium complexes with novel phenoxy-phosphinimine ligands

A series of novel phenoxy-phosphinimine ligands (L): L = 2-(Ph2Pdouble bond; length as m-dashNR), 4, 6-(CMe3)2-C6H2OH [2, R = SiMe3; 3, R = Ph] have been prepared in the yield of 65–71%. And bis(phenoxy-phosphinimide) group 4 complexes of the type L2MCl2 [4, M = Ti, R = SiMe3; 5, M = Zr, R = SiMe3; 6, M = Ti, R = Ph; 7, M = Zr, R = Ph] have been synthesized by the reaction of the ligands with TiCl4 and ZrCl4. The structure of complex 7 has been determined by X-ray crystallography. The complexes 4–7 showed inactive to ethylene polymerization in the presence of modified methylaluminoxane (MMAO) and i-Bu3Al/Ph3CB(C6 F5)4. These results should be caused by overdoing the steric congestion around central metal.