Synthesis, characterisation and structures of thio-, seleno- and telluro-ether complexes of gallium(III).
Synthesis, characterisation and structures of thio-, seleno- and telluro-ether complexes of gallium(III).
复制标题
镓(III)的硫醚、硒醚和碲醚配合物的合成、表征和结构。
作者：
Chitra Gurnani;W. Levason;R. Ratnani;G. Reid;M. Webster
GaX_3（X = Cl，Br或I）与SMe_2，SeMe_2和TeMe_2（L）在非配位溶剂中反应，只生成假四面体[GaX_3L]，其结构已由IR，拉曼和多核NMR（~ 1H，~（71）Ga，~（77）Se或~（125）Te）谱以及[GaCl_3（SeMe_2）]的晶体结构表征。当中性施主从S -> Se -> Te变化时，71 Ga NMR共振显示固定卤化物的小的低频偏移。包括MeS（CH 2）2SMe、PhS（CH 2）2SPh、MeSe（CH 2）2SeMe、nBuSe（CH 2）2Se（n）Bu和MeTe（CH 2）3 TeMe（L-L）的双齿配体也产生具有4-配位镓中心的配合物[（GaX 3）2（mu-L-L）]，由[（GaI 3）2]的晶体结构证实（μ-MeS（CH2）2SMe）]、[（GaCl3）2（μ-PhS（CH2）2SPh）]和[（GaCl3）2（μ-nBuSe（CH2）2Se（n）Bu）]。结构数据与镓的较弱刘易斯酸性一致，因为卤化物共配体变得更重。多核NMR研究表明，在氯烃溶液中，配体发生部分解离，其随着卤化物共配体Cl < Br < I而增加。邻二甲苯基二硫醚，o-C6 H4（CH 2SMe）2，尽管被预先组织用于螯合，也形成[（GaCl 3）2（mu-L-L）]。相应的二硒醚配合物在溶液中分解，C-Se键断裂，形成硒盐[o-C6 H4 CH 2Se（Me）CH 2][GaCl 4]，其结构特征在于。二碲醚o-C_6 H_4（CH_2 TeMe）_2与GaCl_3反应时发生快速的C-Te键断裂和重排，并通过ES ~+质谱从其特征同位素模式中鉴定出碲物种[o-C_6 H_4CH_2 Te（Me）CH_2]~+和[MeTe（CH_2（o-C_6 H_4）CH_2 TeMe）_2]~+。
The reactions of GaX3 (X = Cl, Br or I) with SMe2, SeMe2 and TeMe2 (L) in non-coordinating solvents produces only the pseudo-tetrahedral [GaX3L], which have been characterised by IR, Raman and multinuclear NMR (1H, 71Ga, 77Se or 125Te) spectroscopy, and by the crystal structure of [GaCl3(SeMe2)]. The 71Ga NMR resonances show small low frequency shifts for fixed halides as the neutral donors change from S --> Se --> Te. Bidentate ligands including MeS(CH2)2SMe, PhS(CH2)2SPh, MeSe(CH2)2SeMe, nBuSe(CH2)2Se(n)Bu and MeTe(CH2)3TeMe (L-L) also produce complexes with 4-coordinate gallium centres, [(GaX3)2(mu-L-L)], confirmed by the crystal structures of [(GaI3)2(mu-MeS(CH2)2SMe)], [(GaCl3)2(mu-PhS(CH2)2SPh)] and [(GaCl3)2(mu-nBuSe(CH2)2Se(n)Bu)]. The structural data are consistent with the weaker Lewis acidity of the gallium as the halide co-ligands become heavier. Multinuclear NMR studies suggest that in chlorocarbon solutions partial dissociation of the ligands occur, which increases with the halide co-ligand Cl < Br < I. The o-xylyl dithioether, o-C6H4(CH2SMe)2, despite being pre-organised for chelation, also forms [(GaCl3)2(mu-L-L)]. The corresponding diselenoether complex decomposes in solution with C-Se bond cleavage to form the selenonium salt [o-C6H4CH2Se(Me)CH2][GaCl4], which was structurally characterised. The ditelluroether o-C6H4(CH2TeMe)2 undergoes rapid C-Te bond fission and rearrangement upon reaction with GaCl3, and the telluronium species [o-C6H4CH2Te(Me)CH2]+ and [MeTe(CH2(o-C6H4)CH2TeMe)2]+ have been identified by ES+ mass spectrometry from their characteristic isotope patterns.
影响因子：
62.1
作者：
C. Anderson;M. Welch
通讯作者：
C. Anderson;M. Welch