On the chemistry of gallium .8. Synthesis and structure of [tris(trimethylsilyl)silyl]-substituted gallanes and gallates

被引:31
作者
Linti, G [1 ]
Frey, R [1 ]
Kostler, W [1 ]
Urban, H [1 ]
机构
[1] UNIV MUNICH,INST ANORGAN CHEM,D-80333 MUNICH,GERMANY
关键词
silylgallanes; gallium compounds; hydroxygallium compounds; gallium alkoxides;
D O I
10.1002/cber.19961290514
中图分类号
O6 [化学];
学科分类号
0703 ;
摘要
Reaction of lithium tris(trimethylsilyl)silanide . 3THF with R(2)GaCl (R = 2,2,6,6-tetramethylpiperidino, Me, Cl) yields tmp(2)GaSi(SiMe(3))(3) (3) and R(2)Ga(THF)Si(SiMe(3))(3) (R = Me, Cl) (7, 9). Both gallium nitrogen bonds in 3 are cleaved by protic reagents. Depending on the acidity of these agents, either oligomeric gallanes [(RO)(2)GaSi(SiMe(3))(3)](n) (R = Et, H, n = 2, 3) (11, 12) or tetramethylpiperidinium gallates [X(3)GaSi(SiMe(3))(3)](-)(X = OPh, Cl) (13, 14) are formed. Hydroxide 11 adds lithium hydroxide to afford the mixed lithium gallium hydroxide 15. Single-crystal X-ray diffraction studies confirm the suggested constitutions. The gallium-silicon bond can adopt values between 236 and 247 pm. Here electronic influences of the substituents on the gallium center are of great importance as well as their steric demand. This is underlined by quantum chemical calculations on the ab initio (SCF) level.
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页码:561 / 569
页数:9
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