922144-01-2Relevant academic research and scientific papers
Synthesis and structures of o-phenylene-bridged Cp/phosphinoamide titanium complexes
Wu, Chun Ji,Lee, Sang Hoon,Yun, Hoseop,Lee, Bun Yeoul
, p. 5626 - 5634 (2008/10/09)
Addition of R′ 2 PCl to anilines substituted with di- or trimethylcyclopentadienyl unit at ortho-position affords ortho-phenylene-bridged Me 2 Cp or Me 3 Cp/phosophinoamide ligands, 2-(RMe 2 C 5 H 2 )C 6 H 4 N HPR′ 2 (R = Me or H; R′ = Ph, iPr, or Cyclohexyl).Successive addition of Ti(NMe 2 ) 4 and Me 2SiCl 2 to the ligands affords the desired dichlorotitanium complexes, [2-(η 5 -RMe 2 C 5 H)C 6 H 4 NPR′ 2 - κ 2 N,P]TiCl 2 (R = H, R′ = Ph, 9; R = Me, R′ = Ph, 10; R = H, R′ = iPr, 11; R = Me, R′ = iPr, 12; R = H, R′ = Cy, 13; R = Me, R′ = Cy, 14). By using Zr(NMe 2 ) 4 instead of Ti(NMe 2 ) 4 , a zirconium complex, [2-(η 5 -Me 3 C 5 H)C 6 H 4 NP(iPr) 2 -κ 2 N,P]ZrCl 2 (15) is prepared. Molecular structures of 10, 14 and [2-(η 5 -Me 2 C 5 H 2 ) C 6 H 4 NPPh 2 -κN]Ti(NMe 2 ) 2 (16) were determined. The metr ic parameters determined on the X-ray crystallographic studies and the chemical shifts of the 31 P NMR signal indicate that the phosphorous atom coordinates to the titanium in the dichloro-complexes 9-15. The titanium and zirconium complexes show negligible activity in ethyleneand ethylene/1-hexene (co)polymerization when activated with MAO or iBu 3 Al/[Ph 3 C][B(C 6 F 5 ) 4 ].
