DEHYDROGENATIVE SILATION, ISOMERIZATION AND THE CONTROL OF SYN-ADDITION VS ANTI-ADDITION IN THE HYDROSILATION OF ALKYNES

被引：165

作者：

JUN, CH ^{[1
]}

CRABTREE, RH ^{[1
]}

机构：

[1] YALE UNIV,DEPT CHEM,225 PROSPECT ST,NEW HAVEN,CT 06511

来源：

JOURNAL OF ORGANOMETALLIC CHEMISTRY | 1993年 / 447卷 / 02期

基金：

美国国家科学基金会;

关键词：

D O I：

10.1016/0022-328X(93)80236-5

中图分类号：

O61 [无机化学];

学科分类号：

070301 ; 081704 ;

摘要：

Alkyne hydrosilation has been examined in detail for the catalysts [IrH(H2O)(bq)L2]SbF6 (L = PPh3, bq = 7,8-benzoquinolinato) and RhCl(PPh3)3. Factors that favor the normal syn- or the unusual anti-silane addition to the alkynes are examined. Two other unusual products are noted: the dehydrogenative silation product RC=CSiR3, formed by beta-elimination in a vinylmetal intermediate and allylsilane products of vinylsilane isomerization. The iridium catalyst is advantageous in that it does not give fast vinylsilane isomerization, as does RhCl(PPh3)3, so allowing formation and isolation of the thermodynamically less stable cis-, rather than the more stable trans-vinylsilane isomer RCH=CH(SiR3').

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页码：177 / 187

页数：11

相关论文

共 30 条

[1]

ALBENIZ AC, 1991, COMMUNICATION

[2] REACTIONS OF COORDINATED LIGANDS .33. MONONUCLEAR ETA-2-VINYL COMPLEXES - SYNTHESIS, STRUCTURE, AND REACTIVITY [J].

ALLEN, SR ;

BEEVOR, RG ;

GREEN, M ;

NORMAN, NC ;

ORPEN, AG ;

WILLIAMS, ID .

JOURNAL OF THE CHEMICAL SOCIETY-DALTON TRANSACTIONS, 1985, (03) :435-450

[3] STEREOCHEMISTRY OF ADDITION OF SILICOCHLOROFORM TO ACETYLENES - A COMPARISON OF CATALYST SYSTEMS [J].

BENKESER, RA ;

BURROUS, ML ;

SWISHER, JV ;

NELSON, LE .

JOURNAL OF THE AMERICAN CHEMICAL SOCIETY, 1961, 83 (21) :4385-&

[4] HYDROSILYLATION OF 1-PENTYNE BY TRIETHYLSILANE CATALYZED BY PHOSPHINE-RHODIUM COMPLEXES [J].

BRADY, KA ;

NILE, TA .

JOURNAL OF ORGANOMETALLIC CHEMISTRY, 1981, 206 (03) :299-304

[5] RHODIUM (I)-MONOAZADIENE AND RHODIUM(I)-DIAZADIENE COMPLEXES, SYNTHESIS, SPECTROSCOPIC CLASSIFICATION, OXIDATIVE ADDITION-REACTIONS AND USE IN THE HOMOGENEOUS CATALYSIS ON HYDROSILYLATION [J].

BROCKMANN, M ;

DIECK, HT ;

KLAUS, J .

JOURNAL OF ORGANOMETALLIC CHEMISTRY, 1986, 301 (02) :209-226

[6] C-H AND H-H BOND ACTIVATION - DISSOCIATIVE VS NONDISSOCIATIVE BINDING TO IRIDIUM [J].

CRABTREE, RH ;

LAVIN, M .

JOURNAL OF THE CHEMICAL SOCIETY-CHEMICAL COMMUNICATIONS, 1985, (12) :794-795

[7] SOME MOLECULAR-HYDROGEN COMPLEXES OF IRIDIUM [J].

CRABTREE, RH ;

LAVIN, M ;

BONNEVIOT, L .

JOURNAL OF THE AMERICAN CHEMICAL SOCIETY, 1986, 108 (14) :4032-4037

[8] ORGANOSILICON CHEMISTRY .22. CHLOROTRIS (TRIPHENYLPHOSPHINE) RHODIUM(I)-CATALYSIS OF REACTION BETWEEN HEX-1-YNE AND TRIETHYLSILANE [J].

DICKERS, HM ;

HASZELDINE, RN ;

MATHER, AP ;

PARISH, RV .

JOURNAL OF ORGANOMETALLIC CHEMISTRY, 1978, 161 (01) :91-95

[9] RHODIUM(II) PERFLUOROBUTYRATE CATALYZED HYDROSILYLATION OF 1-ALKYNES - TRANS ADDITION AND REARRANGEMENT TO ALLYLSILANES [J].

DOYLE, MP ;

HIGH, KG ;

NESLONEY, CL ;

CLAYTON, TW ;

LIN, J .

ORGANOMETALLICS, 1991, 10 (05) :1225-1226

[10] ADDITION/ELIMINATION IN THE RHODIUM(II) PERFLUOROBUTYRATE CATALYZED HYDROSILYLATION OF 1-ALKENES - RHODIUM HYDRIDE PROMOTED ISOMERIZATION AND HYDROGENATION [J].

DOYLE, MP ;

DEVORA, GA ;

NEFEDOV, AO ;

HIGH, KG .

ORGANOMETALLICS, 1992, 11 (02) :549-555