HYDROSILYLATION OF PHENYLACETYLENE CATALYZED BY [IR(COD)(ETA(2)-(I)PR(2)PCH(2)CH(2)OME)][BF4]

被引：36

作者：

ESTERUELAS, MA

OLIVAN, M

ORO, LA

TOLOSA, JI

机构：

[1] Departamento de Química Inorgánica, Instituto de Ciencia de Materiales de Aragón, Universidad de Zaragoza

来源：

JOURNAL OF ORGANOMETALLIC CHEMISTRY | 1995年 / 487卷 / 1-2期

关键词：

IRIDIUM; HYDROSILATION; ACETYLENES; CATALYSIS; MECHANISM;

D O I：

10.1016/0022-328X(94)05110-W

中图分类号：

O61 [无机化学];

学科分类号：

070301 ; 081704 ;

摘要：

In the presence of the complexes [Ir(diolefin)(eta(2)-(i)Pr(2)PCH(2)CH(2)NMe(2))][BF4] (diolefin = 1,5-cyclooctadiene (COD) (1) or tetrafluorobenzobarrelene (TFB) (2)) and [Ir(diolefin)(eta(2)-(Pr2PCH2CH)-Pr-i(2)OMe)][BF4] (diolefin = COD (3) or TFB (4)), phenylacetylene undergoes reaction with triethylsilane. In all experiments carried out PhCH=CH2, PhC=CSiEt(3), cis-PhCH=CH(SiEt(3)), trans-PhCH=CH(SiEt(3)) and Ph(SiEt(3))C=CH2 were obtained. An investigation in detail for the catalyst 3 suggests that, under catalytic conditions, the complexes [IrH(C(2)Ph)(COD)(eta(2)-(i)Pr(2)PCH(2)CH(2)OMe)]BF4 (5) and [IrH(SiEt(3))(COD)(eta(2)-(i)Pr(2)PCH(2)CH(2)OMe)]BF4 (6) are formed. Complex 5 is the key intermediate for the formation of PhC=CSiEt(3), while 6 is the species leading to cis-PhCH=CH(SiEt(3)). The isomer trans-PhCH=CH(SiEt(3)) is formed by isomerization of cis-PhCH=CH(SiEt(3)). The mechanisms of formation of these compounds are discussed.

引用

页码：143 / 149

页数：7

共 29 条

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