Five-Membered Zirconacycloallenoids: Synthesis and Characterization of Members of a Unique Class of Internally Metal-Stabilized Bent Allenoid Compounds

被引：70

作者：

Ugolotti, Juri ^{[1
]}

Kehr, Gerald ^{[1
]}

Froehlich, Roland ^{[1
]}

Grimme, Stefan ^{[1
]}

Erker, Gerhard ^{[1
]}

机构：

[1] Univ Munster, Inst Organ Chem, D-48149 Munster, Germany

来源：

JOURNAL OF THE AMERICAN CHEMICAL SOCIETY | 2009年 / 131卷 / 05期

关键词：

OLEFIN COMPLEXES; CYCLIC ALLENE; X-RAY; STRUCTURAL-CHARACTERIZATION; ZIRCONOCENE COMPLEXES; NICKEL(0) COMPLEXES; MOLECULAR-STRUCTURE; DYNAMIC PROPERTIES; CRYSTAL-STRUCTURES; CHEMICAL BEHAVIOR;

D O I：

10.1021/ja8084302

中图分类号：

O6 [化学];

学科分类号：

0703 ;

摘要：

Treatment of the bis-acetylicle zirconocene complexes (RCP)(2)Zr(C C-SiMe3)(2) (8a, R = CH3; 8b, R = tert-butyl) with HB(C6F5)(2) results in the formation of the five-membered organometallic zirconacycloallenoid products (9a, 9b). Both were characterized by X-ray diffraction, and the special bonding features of 9a were studied by DFT calculation. The overall reaction was followed by NMR experiments at variable temperature. Starting from 8a the reaction proceeds by alkynyl abstraction to give a zwitterionic [(MeCP)(2)ZrC C-SiMe3](+)[eta-(Ar2B)-B-F(H)C C-SiMe3](-) intermediate (12a), single crystals of which were obtained at -30 degrees C for characterization by X-ray diffraction, followed by a 1,1-hydroboration/sigma-ligand coupling sequence to give the new five-membered zirconacycloallenoid product 9a.

引用

页码：1996 / 2007

页数：12

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