Oxidative Verknüpfung von Phosphinomethanidliganden an Titanocen- und Bismutzentren: selektive CC-, PC- und PP-Bindungsbildung
作者:Hans H. Karsch、Brigitte Deubelly、Gregor Grauvogl、Gerhard Müller
DOI:10.1016/0022-328x(93)86060-u
日期:1993.10
of the PC coupling product Me3SiCH2PMe2C(PMe2)(SiMe3) are found, whereas 95% of the PP coupling product [(Me3Si)(H)CPMe2]2 are obtained. Exclusive PP coupling is also observed from BiCl3 and (TMEDA)Li[C(PMe2)(SiMe3)2] and Li[C(PMe2)2(SiMe3)], respectively. The results clearly indicate that a metal-centered process, sensitive to steric and coordination effects, is active. Selective CC, PC and
描述了Cp 2 TiCl 2与两个当量的锂-次膦酸高锰酸锂的反应。与LiCH 2 PMe 2的反应产生CC偶联产物Cp 2 Ti [Me 2 PCH 2 CH 2 PMe 2 ],而与(TMEDA)Li [CH(PMe 2)(SiMe 3)]} 2,所述PC偶联产物我3 SICH 2 PME 2 C(PME 2)(森达3),一P-叶立德,形成。与Li [CH(PMe 2)2],由此新颖茂钛杂环的Cp 2的Ti(H)[(ME 2 P)2 CPMe 2 CH 2 PME 2)]},与agostic钛⋯ħ⋯Ç相互作用,可以被表征为一个中间的。与此相反,与Li [CH(PME 2)(森达3)](无TMEDA)PP耦合,得到[(ME 3 Si)的(H)CPMe 2 ] 2,专门观察。类似的结果与Li [C(PME获得2)(森达3)2 ],从而导致[(ME 3 Si)的2 CPMe