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
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
    BECKER, B
    CORRIU, R
    GUERIN, C
    HENNER, B
    WANG, Q
    [J]. JOURNAL OF ORGANOMETALLIC CHEMISTRY, 1989, 359 (02) : C33 - C35
  • [2] 5-COORDINATE POTASSIUM DIHYDRIDOSILICATES - SYNTHESIS AND SOME ASPECTS OF THEIR REACTIVITY
    BECKER, B
    CORRIU, RJP
    GUERIN, C
    HENNER, B
    WANG, Q
    [J]. 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)
    BECKER, B
    CORRIU, RJP
    GUERIN, C
    HENNER, BJL
    [J]. JOURNAL OF ORGANOMETALLIC CHEMISTRY, 1989, 369 (02) : 147 - 154
  • [4] REACTIVITY OF ANIONIC PENTACOORDINATED SILICON COMPLEXES TOWARDS NUCLEOPHILES
    BOUDIN, A
    CERVEAU, G
    CHUIT, C
    CORRIU, RJP
    REYE, C
    [J]. ANGEWANDTE CHEMIE-INTERNATIONAL EDITION IN ENGLISH, 1986, 25 (05): : 473 - 474
  • [5] SELECTIVE REDUCTION OF CARBONYL-COMPOUNDS BY HETEROGENEOUS CATALYSIS ON SALT SURFACES
    BOYER, J
    CORRIU, RJP
    PERZ, R
    REYE, C
    [J]. TETRAHEDRON, 1981, 37 (11) : 2165 - 2171
  • [6] ENHANCEMENT OF SI-H BOND REACTIVITY IN PENTACOORDINATED STRUCTURES
    BOYER, J
    BRELIERE, C
    CORRIU, RJP
    KPOTON, A
    POIRIER, M
    ROYO, G
    [J]. 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
    BREFORT, JL
    CORRIU, R
    GUERIN, C
    HENNER, B
    [J]. 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
    BROWN, HC
    SHOAF, CJ
    [J]. 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
    BROWN, HC
    MCFARLIN, RF
    [J]. JOURNAL OF THE AMERICAN CHEMICAL SOCIETY, 1958, 80 (20) : 5372 - 5376