Dimeric (tris(tert-butyl)silyl)phosphanyl (tris(tert-butyl)silyl)phosphanediyl gallane: a molecule with a Ga-P-Ga heteroallyl system.
Dimeric (tris(tert-butyl)silyl)phosphanyl (tris(tert-butyl)silyl)phosphanediyl gallane: a molecule with a Ga-P-Ga heteroallyl system.
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二聚（三（叔丁基）甲硅烷基）膦酰基（三（叔丁基）甲硅烷基）膦二基镓烷：具有Ga-P-Ga杂烯丙基体系的分子。
DOI：
10.1021/ic0303284
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发表时间：
2004
影响因子：
4.6
通讯作者：
M. Westerhausen
中科院分区：
文献类型：
--
作者：
S. Weinrich;H. Piotrowski;Martin Vogt;A. Schulz;M. Westerhausen
三(叔丁基)硅基磷酰化钾与GaCl3以1：1的摩尔比进行异构化反应，生成了具有很大(1)J(P，H)和(2)J(P，P)偶合常数的[Cl(2)GAP(H)Si(T)Bu(3)](2)(1)。在忽略氢原子和Ga-P距离239Pm的条件下，化合物1的分子结构表现为近平面配位的磷原子的Ga(2)P(2)环GaCl3与3当量的三叔丁基硅基磷酰钾反应，以及1与2当量的KP(H)Si(T)Bu(3)反应生成[(T)Bu(3)Sip(H)Ga(Mu-PSI(T)Bu(3))](2)(2)。中心部分包括一个四元的Ga(2)P(2)环，一个平面的P原子和大约226 pm的极短的Ga-P键，另一个处于角度和为298.4度的金字塔环境中。2的结构可以描述为与磷酰基取代基键合的GaPGa杂烯丙基体系。通过对2的不同异构体的密度泛函计算，研究了这一观点及其对三烷基硅基空间需求的依赖关系。
The metathesis reaction of potassium (tris(tert-butyl)silyl)phosphanide with GaCl(3) in a molar ratio of 1:1 leads to the formation of [Cl(2)GaP(H)Si(t)Bu(3)](2) (1) as a mixture of cis and trans isomers with very large (1)J(P,H) and (2)J(P,P) coupling constants. The molecular structure of 1 shows a Ga(2)P(2) cycle with nearly planar coordinated phosphorus atoms under neglection of the hydrogen atoms and Ga-P distances of 239 pm. The reaction of GaCl(3) with 3 equiv of potassium (tris(tert-butyl)silyl)phosphanide as well as the reaction of 1 with 2 equiv of KP(H)Si(t)Bu(3) yields [(t)Bu(3)SiP(H)Ga(mu-PSi(t)Bu(3))](2) (2). The central moiety comprises a four-membered Ga(2)P(2) cycle with one planar P atom and extremely short Ga-P bonds of approximately 226 pm, the other being in a pyramidal environment with an angle sum of 298.4 degrees. The structure of 2 can be described as a GaPGa heteroallyl system which is bonded to a phosphanidyl substituent. This idea and its dependency on the steric demand of the trialkylsilyl groups are investigated by DFT calculations on different isomers of 2.