Ti and Zr bidentate bis-phosphinimide complexes

The diphosphines m-C6H4(CH2Pt-Bu2)21 and m-C6H4(CH2PCy2)22 were prepared and oxidized with Me3SiN3 to m-C6H4(CH2(t-Bu2)PNSiMe3)23 and m-C6H4(CH2(Cy2)PNSiMe3)24, and subsequently converted to m-C6H4(CH2(t-Bu)2PNH)25 and m-C6H4(CH2(Cy)2PNH)26. Reaction of 5 and 6 with Ti(NMe2)4 afforded the yellow compounds m-C6H4(CH2(t-Bu)2PN)2Ti(NMe2)27 and m-C6H4(CH2(Cy)2PN)2Ti(NMe2)28, and the low abundance by-product m-C6H4(CH2(t-Bu)2PN)2TiBr(NMe2) 9. In a similar manner, the species m-C6H4(CH2(t-Bu)2PN)2Zr(NEt2)210 was prepared from Zr(NEt2)4. Compounds 8, 9 and 10 were converted to C6H4(CH2(t-Bu)2PN)2TiBr211, m-C6H4(CH2(Cy)2PN)2TiCl213 and C6H4(CH2(t-Bu)2PN)2ZrCl214via reaction with Me3SiX (X = Br, Cl). Alternatively, m-C6H4(CH2(t-Bu)2PN)2TiCl212 and 13 were prepared in low yield from reaction of 3 or 4 with TiCl4. Alkylation of 11 with MeMgBr and PhCH2MgBr proceeded to give m-C6H4(CH2(t-Bu)2PN)2TiMe215 and m-C6H4(CH2(t-Bu)2PN)2Ti(CH2Ph)216, respectively. The species (m-C6H4(CH2(t-Bu)2PN)2)2Zr 17 was prepared from Zr(CH2Ph)4. These synthetic routes are described and the implications for applications in olefin polymerization catalysis are considered. X-Ray structural data for compounds 1, 3, 4, 5, 8, 9 and 16 are reported.