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首页> 外文期刊>Organometallics >Stabilized Terphenyl-Substituted Digermene Derivatives of Simple Organic Groups and Their Halide Precursors: Preference for Symmetrically Bonded Structures
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Stabilized Terphenyl-Substituted Digermene Derivatives of Simple Organic Groups and Their Halide Precursors: Preference for Symmetrically Bonded Structures

机译：简单有机基团及其卤化物前体的稳定的三苯取代的Digermene衍生物：对称键合结构的优先选择

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The reaction of 1 equiv of MeMgBr, EtMgBr, or LiPh with Ge(Cl)C6H3-2,6-Trip2 (1; Trip = C~2-2,4,6-i-Pr3) in diethyl ether solution afforded the dimmers {Ge(R)C6H3-2,6-Trip2}2 (R = Me (2), Et (3), Ph (4)), which have trans-bent Ge-Ge-bonded structures that are maintained in solution. The compounds 2 and 3 are rare examples of "digermene" species having alkyl substituents. The previously described halide precursor 1 was found to crystallize simultaneously as both a V-shaped monomer and weakly Ge-Ge-bonded dimer {Ge(Cl)CeH3-2,6-Trip2}2 (5), which dissociated readily to monomers in hydrocarbon solution. This species reacted readily with pyridine (py) to form the monomeric 1:1 adduct py.Ge- (Cl)C~3-2,6-Trip2 (7), which has pyramidal coordination at germanium. The dimeric structures found for 2-4 were in sharp contrast with recently published results for their tin and lead analogues, which displayed either unsymmetric dimeric structures as in 2,6- Trip2H3Ce(Me)2SnSnC6H3-2,6-Trip2 or monomeric structures as in Pb(Me)CeH3-2,6-Trip2. The chloro derivatives {Ge(Cl)C~3-2,6-Trip2}n (n = 1, 2; i.e. 1 and 5) also differed from their tin congeners in that the corresponding tin dimmer is associated through chloride bridging, whereas 5, and the related dimmer {Ge(Cl)C6H3-2,6-Mes2l2 (6), are associated through weak element-element bonding. The experimental results are in general agreement with earlier theoretical data on the hypothetical M2H4 (M = Ge, Sn, Pb) model compounds which predicted a stable, symmetric, dimeric, Ge-Ge-bonded structure for germanium but an unsymmetric methylmethylene analogue structure for tin.
机译：1当量的MeMgBr，EtMgBr或LiPh与Ge（Cl）C6H3-2,6-Trip2（1; Trip = C〜2-2,4,6-i-Pr3）在乙醚溶液中的反应得到二聚体{Ge（R）C6H3-2,6-Trip2} 2（R = Me（2），Et（3），Ph（4）），具有保持在溶液中的反式Ge-Ge键结构。化合物2和3是具有烷基取代基的“ digermene”种类的罕见实例。发现先前描述的卤化物前体1同时结晶为V形单体和弱Ge-Ge键合的二聚体{Ge（Cl）CeH3-2,6-Trip2} 2（5），它们易于解离为碳氢化合物溶液。该物种易于与吡啶（py）反应形成单体1：1加合物py.Ge-（Cl）C〜3-2,6-Trip2（7），在锗上具有锥体配位作用。发现2-4的二聚体结构与其最近发表的锡和铅类似物的结果形成鲜明对比，后者显示了2,6- Trip2H3Ce（Me）2SnSnC6H3-2,6-Trip2中的不对称二聚体结构或显示的单体结构。在Pb（Me）CeH3-2,6-Trip2中氯衍生物{Ge（Cl）C〜3-2,6-Trip2} n（n = 1、2;即1和5）也不同于它们的锡同类物，因为相应的锡二聚体通过氯化物桥联而形成，而如图5所示，相关的调光器{Ge（Cl）C6H3-2,6-Mes2l2（6））通过弱元素-元素键连接。实验结果与假设的M2H4（M = Ge，Sn，Pb）模型化合物的早期理论数据基本相符，该化合物预测了锗的稳定，对称，二聚体，Ge-Ge键结构，但对于M2H4具有不对称的甲基亚甲基类似物结构。锡。

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