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:36
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
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
收藏
页码:29 / 32
页数:4
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