PENTACOORDINATED SILICON ANIONS - SYNTHESIS AND REACTIVITY .1.

被引：47

作者：

BREFORT, JL ^{[1
]}

CORRIU, RJP ^{[1
]}

GUERIN, C ^{[1
]}

HENNER, BJL ^{[1
]}

WONGCHIMAN, WWC ^{[1
]}

机构：

[1] UNIV MONTPELLIER 2,CNRS,UA 1097,HETEROCHIM & AMINO ACIDES LAB,PL EUGENE BATAILLON,F-34095 MONTPELLIER 05,FRANCE

来源：

ORGANOMETALLICS | 1990年 / 9卷 / 07期

关键词：

D O I：

10.1021/om00157a016

中图分类号：

O61 [无机化学];

学科分类号：

070301 ; 081704 ;

摘要：

Pentacoordinated anionic siliconates Ph3Si(OMe)2-K+(18-crown-6), Ph2Si(OMe)3-K+(18-crown-6), Ph3SiF2-K+(18-crown-6), and MePhSiF3- K+(18-crown-6) reacted with nucleophiles (RMgX, RLi, ROLi, LiAlH4) to give the neutral tetravalent substituted silicon derivatives. Reactivity comparisons between Ph3SiX2-K+(18-crown-6) and Ph3SiX (X = F, OMe) showed that the pentavalent anionic species is more reactive than the tetravalent analogue toward nucleophiles. Hydrolysis reactions of Ph3SiF2-K+(18-crown-6) and Ph3Si(OMe)2-K+(18-crown-6) gave respectively Ph3SiF and a mixture of Ph3SiOMe and Ph3SiOH. Results clearly indicate that nucleophilic attack at pentacoordinated silicon species is a general process. Moreover, the data point out the enhanced reactivity of these species that may mainly arise from a general loosening of the bonds around silicon. © 1990, American Chemical Society. All rights reserved.

引用

收藏

页码：2080 / 2085

页数：6

相关论文

共 53 条

[1] A GENERAL-ROUTE TO 5-COORDINATE HYDRIDOSILICATES [J].

BECKER, B ;

CORRIU, R ;

GUERIN, C ;

HENNER, B ;

WANG, Q .

JOURNAL OF ORGANOMETALLIC CHEMISTRY, 1989, 359 (02) :C33-C35

[2] 5-COORDINATE POTASSIUM DIHYDRIDOSILICATES - SYNTHESIS AND SOME ASPECTS OF THEIR REACTIVITY [J].

BECKER, B ;

CORRIU, RJP ;

GUERIN, C ;

HENNER, B ;

WANG, Q .

JOURNAL OF ORGANOMETALLIC CHEMISTRY, 1989, 368 (02) :C25-C28

[3] HYPERVALENT SILICON HYDRIDES - EVIDENCE FOR THEIR INTERMEDIACY IN THE EXCHANGE-REACTIONS OF DI-HYDROGENOSILANE AND TRI-HYDROGENOSILANE CATALYZED BY HYBRIDES (NAH, KH AND LIALH4) [J].

BECKER, B ;

CORRIU, RJP ;

GUERIN, C ;

HENNER, BJL .

JOURNAL OF ORGANOMETALLIC CHEMISTRY, 1989, 369 (02) :147-154

[4] REACTIVITY OF ANIONIC PENTACOORDINATED SILICON COMPLEXES TOWARDS NUCLEOPHILES [J].

BOUDIN, A ;

CERVEAU, G ;

CHUIT, C ;

CORRIU, RJP ;

REYE, C .

ANGEWANDTE CHEMIE-INTERNATIONAL EDITION IN ENGLISH, 1986, 25 (05) :473-474

[5] SELECTIVE REDUCTION OF CARBONYL-COMPOUNDS BY HETEROGENEOUS CATALYSIS ON SALT SURFACES [J].

BOYER, J ;

CORRIU, RJP ;

PERZ, R ;

REYE, C .

TETRAHEDRON, 1981, 37 (11) :2165-2171

[6] ENHANCEMENT OF SI-H BOND REACTIVITY IN PENTACOORDINATED STRUCTURES [J].

BOYER, J ;

BRELIERE, C ;

CORRIU, RJP ;

KPOTON, A ;

POIRIER, M ;

ROYO, G .

JOURNAL OF ORGANOMETALLIC CHEMISTRY, 1986, 311 (03) :C39-C43

[7]

BOYER J, 1981, SYNTHESIS-STUTTGART, P558

[8] HYPERVALENT SILICON HYDRIDES - EVIDENCE OF THEIR INTERMEDIACY IN THE REACTION OF OPTICALLY-ACTIVE 1-NPPHMESIH(D) WITH HYDRIDES [J].

BREFORT, JL ;

CORRIU, R ;

GUERIN, C ;

HENNER, B .

JOURNAL OF ORGANOMETALLIC CHEMISTRY, 1989, 370 (1-3) :9-15

[9] SELECTIVE REDUCTIONS .3. FURTHER STUDIES OF REACTION OF ALCOHOLS WITH LITHIUM ALUMINUM HYDRIDE AS ROUTE TO LITHIUM ALKOXYALUMINOHYDRIDES [J].

BROWN, HC ;

SHOAF, CJ .

JOURNAL OF THE AMERICAN CHEMICAL SOCIETY, 1964, 86 (06) :1079-&

[10] THE REACTION OF LITHIUM ALUMINUM HYDRIDE WITH ALCOHOLS - LITHIUM TRI-TERT-BUTOXY-ALUMINOHYDRIDE AS A NEW SELECTIVE REDUCING AGENT [J].

BROWN, HC ;

MCFARLIN, RF .

JOURNAL OF THE AMERICAN CHEMICAL SOCIETY, 1958, 80 (20) :5372-5376

← 1 2 3 4 5 6 →