Bradley Christopher A, Lobkovsky Emil, Chirik Paul J
Department of Chemistry and Chemical Biology, Baker Laboratory, Cornell University, Ithaca, NY 14853, USA.
J Am Chem Soc. 2003 Jul 9;125(27):8110-1. doi: 10.1021/ja035594v.
Reductive elimination of alkane from a silylated bis-indenyl zirconium isobutyl hydride affords a zirconium sandwich complex with an unusual eta6 indenyl ligand. Crystallographic characterization of its adduct with tetrahydrofuran has been achieved and reveals significant localization in the six-membered ring. Complexation of more potent ligands such as carbon monoxide and diphenylacetylene are effective in promoting haptotropic rearrangement of the eta6 indenyl ligand and provides familiar bent zirconocene derivatives. The zirconium sandwich compound also undergoes oxidative addition of carbon-hydrogen bonds of pyridyl ligands, resulting in a crystallographically characterized dimethylamino pyridyl hydride complex of zirconium.
从硅烷基化的双茚基氢化异丁基锆中还原消除烷烃,得到一种具有不寻常的η6茚基配体的锆夹心配合物。已经实现了其与四氢呋喃加合物的晶体学表征,并揭示了在六元环中的显著定位。与更强效的配体如一氧化碳和二苯乙炔的络合有效地促进了η6茚基配体的迁移重排,并提供了常见的弯曲锆茂衍生物。锆夹心化合物还会发生吡啶基配体碳氢键的氧化加成,生成一种晶体学表征的锆二甲基氨基吡啶基氢化物配合物。