Phosphine loss from bis(phosphine)rhodium(I) η2-(C,O)-diphenylketene complexes leading to η4-(C4) coordination and fluxionality of the ketene

被引：12

作者：

Grotjahn, DB

Bikzhanova, GA

Hubbard, JL

机构：

[1] San Diego State Univ, Dept Chem, San Diego, CA 92182 USA

[2] Utah State Univ, Dept Chem & Biochem, Logan, UT 84322 USA

来源：

ORGANOMETALLICS | 1999年 / 18卷 / 26期

关键词：

D O I：

10.1021/om990593q

中图分类号：

O61 [无机化学];

学科分类号：

070301 ; 081704 ;

摘要：

Significant structural changes accompany phosphine loss from bis(phosphine) complexes trans-ClRh[eta(2)-(C,O)-Ph2C=C=O](PR3)(2) [4, where PR3 = PMe(t-Bu)(2), P(i-Pr)(3), or PCy3], giving ClRh[eta(4)-(C-4)-Ph2C=C=O](PR3) (5). As shows by the X-ray crystal structure of 5a [PR3 = PMe(t-Bu)(2)] and variable-temperature NMR studies, the metal moves from the ketene C,O bond to the C,C bond and also coordinates weakly to two carbons of a ketene phenyl substituent, resulting in fluxional behavior unique among complexes of aryl- or vinyl-substituted ketenes.

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页码：5614 / 5619

页数：6

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