Nucleophilic Scandium Carbene Complexes

被引：87

作者：

Fustier, Marie ^{[1
]}

Le Goff, Xavier F. ^{[1
]}

Le Floch, Pascal ^{[1
]}

Mezailles, Nicolas ^{[1
]}

机构：

[1] Ecole Polytech, Dept Chim, Lab Heteroelements & Coordinat, CNRS,DCPH,UMR 7653, F-91128 Palaiseau, France

来源：

JOURNAL OF THE AMERICAN CHEMICAL SOCIETY | 2010年 / 132卷 / 38期

关键词：

ALKYLIDENE; REAGENTS; ACID;

D O I：

10.1021/ja103220s

中图分类号：

O6 [化学];

学科分类号：

0703 ;

摘要：

Using a geminal dianion as precursor, a nucleophilic scandium carbene complex (2) has been synthesized by salt metathesis on ScCl3(THF)(3) in 52% isolated yield. The X-ray structure as well as an NBO analysis points to a double interaction between the carbon and the scandium atoms. Quantification of the electron density donation from the carbon to the metal center, from both sigma and pi symmetry orbitals, predicts a "nucleophilic carbene" behavior. Addition of benzophenone on complex 2 results in the formation of the expected alkene derivative and the trapping of a rare, mu(3)-oxo-Sc species via a "scandia-Wittig" reaction.

引用

收藏

页码：13108 / 13110

页数：3

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