In search of stable lithium pentaorganylsilicates; special role of five phenyl ligands and of ligands containing the 1,4-(1,3-butadienediyl) unit

被引：37

作者：

de Keijzer, AHJF ^{[1
]}

de Kanter, FJJ ^{[1
]}

Schakel, M ^{[1
]}

Osinga, VP ^{[1
]}

Klumpp, GW ^{[1
]}

机构：

[1] Vrije Univ Amsterdam, Scheikundig Lab, NL-1081 HV Amsterdam, Netherlands

来源：

JOURNAL OF ORGANOMETALLIC CHEMISTRY | 1997年 / 548卷 / 01期

关键词：

tetraorganylsilanes; lithium pentaorganylsilicates; Si-29-NMR; sigma-organolithiums; trigonal-bipyramidal structures; stereomutation;

D O I：

10.1016/S0022-328X(97)00166-6

中图分类号：

O61 [无机化学];

学科分类号：

070301 ; 081704 ;

摘要：

Among several tetraorganylsilanes tested, only 4-6, containing the 1,4-(1,3-butadienediyl) unit, have been found to form, by addition of a sigma-organolithium, lithium pentaorganylsilicates identifiable by characteristic Si-29-NMR chemical shifts. Lithium silicates formed from 4 are of particular stability (and correspondingly low reactivity) and appear to have trigonal-bipyramidal structures that undergo stereomutation with Delta H-double dagger ca. 50 kJ/mol, Delta S-double dagger ca. -20 J/kmol. So far, lithium pentaphenylsilicate (3) is the only other lithium pentaorganylsilicate that could be identified by Si-29-NMR. (C) 1997 Elsevier Science S.A.

引用

页码：29 / 32

页数：4

共 29 条

[1] APELOIG Y, 1989, CHEM ORGANIC SILICON, P207
[2] TRIMETHYLSILYL ETHYL ORTHOPROPIOLATE - PREPARATION AND USE AS A PROPIOLATE ANION EQUIVALENT
BOCHE, G
BIGALKE, J
[J]. TETRAHEDRON LETTERS, 1984, 25 (09) : 955 - 958
[3] REACTIVITY OF PENTACOORDINATE AND HEXACOORDINATE SILICON-COMPOUNDS AND THEIR ROLE AS REACTION INTERMEDIATES
CHUIT, C
CORRIU, RJP
REYE, C
YOUNG, JC
[J]. CHEMICAL REVIEWS, 1993, 93 (04) : 1371 - 1448
[4] Gas phase studies of silacyclobutanes: Recent developments employing triple quadrupole detection
Damrauer, R
Hankin, JA
[J]. JOURNAL OF ORGANOMETALLIC CHEMISTRY, 1996, 521 (1-2) : 93 - 98
[5] DEKEIJZER AHJ, 1996, ANGEW CHEM, V108, P1183
[6] DEKEIJZER AHJ, UNPUB
[7] Lithium 2,2'-biphenyldiyltrimethylsilicate; First observation of pentaorganosilicates
deKeijzer, AHJF
deKanter, FJJ
Schakel, M
Schmitz, RF
Klumpp, GW
[J]. ANGEWANDTE CHEMIE-INTERNATIONAL EDITION IN ENGLISH, 1996, 35 (10): : 1127 - 1128
[8] CLEAVAGE OF SI-C AND GE-C BONDS IN HETERYLSILANES AND HETERYLGERMANES BY ORGANOLITHIUM REAGENTS
GEVORGYAN, V
BORISOVA, L
LUKEVICS, E
[J]. JOURNAL OF ORGANOMETALLIC CHEMISTRY, 1992, 441 (03) : 381 - 387
[9] THE REACTION OF SOME TETRASUBSTITUTED SILANES WITH NORMAL-BUTYLLITHIUM
GILMAN, H
HARTZFELD, H
[J]. JOURNAL OF THE AMERICAN CHEMICAL SOCIETY, 1951, 73 (12) : 5878 - 5879
[10] THE REACTION OF NORMAL-BUTYLLITHIUM WITH SOME ORGANOSILICON COMPOUNDS
GILMAN, H
BENKESER, RA
DUNN, GE
[J]. JOURNAL OF THE AMERICAN CHEMICAL SOCIETY, 1950, 72 (04) : 1689 - 1691

← 1 2 3 →