Synthesis and structures of gallium alkoxides
Synthesis and structures of gallium alkoxides
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醇镓的合成与结构
DOI：
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发表时间：
2008
期刊：
影响因子：
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通讯作者：
D. Tocher
中科院分区：
文献类型：
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作者：
S. Basharat;C. Knapp;C. Carmalt;S. Barnett;D. Tocher
以[Ga（NMe 2）3]2（1）和过量的ROH（R = CH 2CH 2NMe 2（2），CH（CH 3）CH 2NMe 2（3），C（CH 3）2CH 2 OMe（4），CH 2CH 2 OMe（5））为原料，在甲苯中室温反应制备了均配型三烷氧基镓[Ga（OR）3]2。化合物2-5分离为无色油状物。在2、3和4的合成过程中，还分别以低收率分离出副产物[Ga（OCH 2CH 2NMe 2）2Cl]（6）、[Ga（OCH（CH 3）CH 2NMe 2）2Cl]（7）和[Ga（OC（CH 3）2CH 2 OMe）Cl 2]（8）。然而，化合物6和7也直接由[Ga（NMe 2）2Cl]和2当量的ROH（6，R = CH 2CH 2NMe 2; 7，R = CH（CH 3）CH 2NMe 2）的反应制备。类似地，从[Ga（NMe 2）Cl 2]和1当量HOC（CH 3）2CH 2 OMe的反应中分离化合物8。单晶X射线晶体学表明，镓双（醇盐）（6和7）是单体在固态与镓中心采用扭曲的三角双锥几何形状。相反，镓单（烷氧基）8是二聚的。
Homoleptic gallium tris(alkoxides) [Ga(OR)3]2 were prepared by the reaction of [Ga(NMe2)3]2 (1) and excess ROH (R = CH2CH2NMe2 (2), CH(CH3)CH2NMe2 (3), C(CH3)2CH2OMe (4), CH2CH2OMe (5)) in toluene at room temperature. Compounds 2–5 were isolated as colourless oils. The side-products, [Ga(OCH2CH2NMe2)2Cl] (6), [Ga(OCH(CH3)CH2NMe2)2Cl] (7) and [Ga(OC(CH3)2CH2OMe)Cl2]2 (8) were also isolated in low yield during the synthesis of 2, 3 and 4, respectively. However, compounds 6 and 7 were also prepared directly from the reaction of [Ga(NMe2)2Cl] and 2 equivalents of ROH (6, R = CH2CH2NMe2; 7, R = CH(CH3)CH2NMe2). Similarly, compound 8 was isolated from the reaction of [Ga(NMe2)Cl2] and 1 equivalent of HOC(CH3)2CH2OMe. Single crystal X-ray crystallography showed that the gallium bis(alkoxides) (6 and 7) are monomeric in the solid state with the gallium centre adopting a distorted trigonal bipyramidal geometry. In contrast, the gallium mono(alkoxide) 8 is dimeric.