Synthesis and structure of [1,2-bis(1-indenyl)benzene]titanium and zirconium dichlorides
作者:Ronald L Halterman、Alexander Tretyakov、Masood A Khan
DOI:10.1016/s0022-328x(98)00753-0
日期:1998.10
2-bis(1-indenyl)benzenes in 29–45% yield. New phenyl-bridged ansa-bis(indenyl)titanium and -zirconium dichlorides were obtained from these ligands in good yield either by addition of TiCl3 or ZrCl4 to their lithium salts (61–92% yield) or by addition of Zr(NMe2)4 to the neutral ligands (59–67%). In each case the zirconium tetraamide metalation gave very high dl-selectivity. The n-BuLi/ZrCl4 metalation
钯催化的1,2-二碘代苯与由茚,4-甲基茚,4,7-二甲基茚和得到的茚基锌络合物的偶合反应得到1,2-双(1-茚基)苯,产率为29-45%。新苯基桥接的柄-双(茚基)钛和二氯化-锆从这些配位体以良好的收率或者通过另外的TiCl获得3或的ZrCl 4到其的锂盐(61-92%产率),或通过添加Zr(NME 2)4至中性配体(59–67%)。在每种情况下,四酰胺锆金属化都具有很高的dl-选择性。苯基桥联的未取代茚的n -BuLi / ZrCl 4金属化比为3:2DL -到内消旋-同时将取代基在导致10 4,7-和5,6-位置:1层的选择性有利于的DL异构体。所述Ñ正丁基锂/的TiCl 3金属化,得到1:1的选择性:1和4。通过X射线分析获得[1,2-双(1-茚基)苯]二氯锆(dl - 6a)的固态结构。