Synthesis and Characterization of Organoaluminum Silylamido Complexes

Abstract

The reaction between [Me2AlCl] and 1 equiv of HN(SiMe2H)2 in CH2Cl2 afforded colorless crystals of [Cl(Me)Al{-NH(SiMe2H)}]2 (1). The structure of compound 1 has been determined and shows that the bridging NH(SiMe2H) groups adopt a mutually trans arrangement. The related reaction between [Me2AlCl] and 1 equiv of HN(SiMe2Ph)2 in CH2Cl2 solution resulted in the isolation of colorless crystals. An X-ray crystallographic study showed that the crystals consist of a mixture of [Cl(Me)2Al{NH(SiMe2Ph)2}] (2) and [Cl2(Me)Al{NH(SiMe2Ph)2}] (3) in a 1:4 ratio. The formation of compound 3 involves the exchange of one of the methyl groups attached to the aluminum atom with a chlorine atom.

Organoaluminum Silylamido Complexes

“…The geometry of the AlC 2 NCl core of 1 reflects the larger steric bulk of the NH(SiMe 3 ) 2 and ethyl groups in comparison to Cl. The bond lengths and angles observed in 1 do not differ appreciably from those observed in related complexes, such as [Me 2 AlCl{NH(SiMe 2 Ph) 2 }] . There are no notable intermolecular interactions.…”

“…Recently, we reported the synthesis and structural characterization of the aluminum silylamido complexes [MeAlCl{μ-NH(SiMe 2 H)}] 2 , [Me 2 AlCl{NH(SiMe 2 Ph) 2 }], and [MeAlCl 2 {NH(SiMe 2 Ph) 2 }] . The formation of [MeAlCl 2 {NH(SiMe 2 Ph) 2 }] from [Me 2 AlCl] and NH(SiMe 2 Ph) 2 involved the exchange of one of the methyl groups attached to the aluminum atom with a chlorine atom.…”

Theoretical Study on the Two-Photon Absorption Properties of Pyrazole Aluminum Compounds

“…早在 20 世纪 60 年代, 铝氮烷(AlN)n 化合物就被合成, 9 并引起了 人们的研究兴趣, 主要因为 AlN 化合物是硬的耐高 温材料. 10,11 但到目前为止他们的双光子吸收性质仍 没有报道. 绝大多数的双光子吸收材料的发色团具 有共轭结构, 而最近一系列新颖的双光子材料, 其 中心是 "准共轭" 的硼氮烷杂环引起了人们的关注.…”

5 Aluminium, gallium, indium and thallium

“…Complexes [X 2 Ga(m-HNR)] 2 (X ~Cl, Br, R ~SiMe 3 ; X ~Cl, R ~SiMe 3 , But) were produced by these means although, curiously, the corresponding reactions in dichloromethane simply afforded a range of monomeric adducts [X 3 GaHN(R)R'] in chemistry reminiscent of Al studies originating from the same group. 56 The original purpose was to find precursors for GaN production, but the halogens persisted in impurities in the GaN sintering products due to incomplete dehydrohalogenation and dehalogenosilylation. 102 Several more reports of Ga within porphyrinate cavities emerged in 2003: the synthesis of [HGa(tpp)] from [ClGa(tpp)] was reported along with its crystal structure in which the Ga atom stands a little prouder from the tpp ring than in the starting material which is a possible reflection of increased electron richness and therefore size.…”

“…The analogous reaction with the bulkier HN(SiMe 2 Ph) 2 simply affords the adduct Cl 2 MeAlHN(SiMe 2 Ph) 2 . 56 The known 6-membered cyclic trimer [MeAl{Ndipp}] 3 can be fluorinated with increasing proportion of Me 3 SnF to afford non-planar rings [Me (32x) F x Al{Ndipp}] 3 ?nH 2 O where, sequentially, x ~1, n ~2; x ~2, n ~3; x ~3, n ~3. The first of these is unusual because each of the three chemically equivalent Al atoms in the ring has a qualitatively different coordination sphere.…”