HYDROSILYLATION OF PHENYLACETYLENE VIA AN OS(SIET3)(ETA-2-H2) INTERMEDIATE CATALYZED BY OSHCL(CO)(P(ISO-PR)3)2

被引：92

作者：

ESTERUELAS, MA ^{[1
]}

ORO, LA ^{[1
]}

VALERO, C ^{[1
]}

机构：

[1] UNIV ZARAGOZA,CSIC,INST CIENCIA MAT ARAGON,DEPT QUIM INORGAN,E-50009 ZARAGOZA,SPAIN

来源：

ORGANOMETALLICS | 1991年 / 10卷 / 02期

关键词：

D O I：

10.1021/om00048a024

中图分类号：

O61 [无机化学];

学科分类号：

070301 ; 081704 ;

摘要：

OsHCl(CO)(P(i)Pr3)2 is found to be a very active and highly selective catalyst for the addition of triethylsilane to phenylacetylene. trans- and cis-PhHC = CH(SiEt3) are selectively obtained in high yields depending on the reaction conditions. Although the vinyl compound Os((E)-HC = CHPh)Cl(CO)(P(i)Pr3)2 is the main species under hydrosilylation conditions, the catalytic reaction proceeds via the silyl dihydrogen intermediate Os(SiEt3)Cl(eta-2-H2)(CO)(P(i)Pr3)2 according to the following set of reactions: OsHCl(CO)(P(i)Pr3)2 + HSiEt3 --> Os(SiEt3)Cl(eta-2-H2)(CO)(P(i)Pr3)2 and Os(SiEt3)Cl(eta-2-H2)(CO)(P(i)Pr3)2 + PhC2H --> OsHCl(CO)(P(i)Pr3)2 + trans and cis-PhHC = CH(SiEt3) in which the reaction between OsHCl(CO)(P(i)Pr3)2 and triethylsilane is the rate-determining step.

引用

页码：462 / 466

页数：5

共 45 条

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