Unexpected Formation of Ga4C2H4 Heteroadamantane Cages by the Reaction of Carbon-Bridged Bis(dichlorogallium) Compounds with tert-Butyllithium
Unexpected Formation of Ga4C2H4 Heteroadamantane Cages by the Reaction of Carbon-Bridged Bis(dichlorogallium) Compounds with tert-Butyllithium
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碳桥双（二氯镓）化合物与叔丁基锂反应意外形成 Ga4C2H4 杂金刚烷笼
DOI：
10.1021/om200573g
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发表时间：
2011
期刊：
影响因子：
2.8
通讯作者：
A. Hepp
中科院分区：
文献类型：
--
作者：
W. Uhl;Dirk Kovert;Sarina Zemke;A. Hepp
碳桥联双(二氯镓)化合物(Cl2Ga)2C(SiR2R‘)-CH2-Ph(1a，R=R’=Me；1b，R=Ph，R‘=Me；1c，R=Me，R’=Cme3)与四个叔丁基锂的当量化合物通过β-消除和异丁烯的释放反应，合成了双[叔丁基(氢化)二氯化镓]化合物{[(Me2Ga)2C(H)Ga]2C(SiR2R‘)-CH2-Ph}2(3a~3c)。3a到3c在溶液和固体中都是二聚体，并且包含前所未有的Ga4C2H4杂金刚烷结构，其中四个金属原子由四个氢原子和两个碳原子桥联。相反，正丙基锂在相似的条件下合成了单体四(正丙基)二锂化合物(NPr2Ga)2C(SiMe3)-CH2-Ph(2)，它含有两个配位不饱和的镓原子，可用作络合Lewis酸。
Reactions of the carbon-bridged bis(dichlorogallium) compounds (Cl2Ga)2C(SiR2R′)-CH2-Ph (1a, R = R′ = Me; 1b, R = Ph, R′ = Me; 1c, R = Me, R′ = CMe3) with four equivalents of tert-butyllithium yielded bis[tert-butyl(hydrido)digallium] compounds {[(Me3C)(H)Ga]2C(SiR2R′)-CH2-Ph}2 (3a to 3c), via β-elimination and release of isobutene. 3a to 3c are dimeric in solution and the solid state and contain unprecedented Ga4C2H4 heteroadamantane structures in which four metal atoms are bridged by four hydrogen and two carbon atoms. In contrast, n-propyllithium gave the monomeric tetra(n-propyl)digallium compound (nPr2Ga)2C(SiMe3)-CH2-Ph (2) under similar conditions, which has two coordinatively unsaturated gallium atoms and may be applicable as a chelating Lewis acid.