On the Chemistry of Gallium, 8. Synthesis and Structure of [Tris(trimethylsilyl)silyl]‐Substituted Gallanes and Gallates
作者:Gerald Linti、Ronald Frey、Wolfgang Köstler、Horst Urban
DOI:10.1002/cber.19961290514
日期:1996.5
lithium tris(trimethylsilyl)silanide · 3 THF with R2GaCl (R = 2,2,6,6-tetramethylpiperidino, Me, Cl) yields tmp2GaSi(SiMe3)3 (3) and R2Ga(THF)Si(SiMe3)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)2GaSi(SiMe3)3]n (R = Et, H, n = 2, 3) (11, 12) or tetramethylpiperidinium gallates [X3GaSi-(SiMe3)3]–
三(三甲基甲硅烷基)硅铝锂·3 THF与R 2 GaCl(R = 2,2,6,6-tetramethylpiperidino,Me,Cl)反应生成tmp 2 GaSi(SiMe 3)3(3)和R 2 Ga(THF) Si(SiMe 3)3(R = Me,Cl)(7,9)。3中的两个镓氮键均被质子试剂裂解。取决于这些试剂的酸度,低聚没食子烷[(RO)2 GaSi(SiMe 3)3 ] n(R = Et,H,n = 2,3)(11,12)或没食子酸四甲基哌啶[X 3形成GaSi-(SiMe 3)3 ] –(X = OPh,Cl)(13,14)。氢氧化物11添加氢氧化锂以提供混合的氢氧化锂镓15。单晶X射线衍射研究证实了建议的组成。镓-硅键可采用236至247 pm之间的值。在这里,取代基对镓中心的电子影响及其空间需求非常重要。从头算(SCF)级别的量子化学计算强调了这一点。