一种含有二价锗和具有不寻常Ge4核心的类似重环丁二烯二价阴离子的环戊二烯基类似物。

A cyclopentadienide analogue containing divalent germanium and a heavy cyclobutadiene-like dianion with an unusual Ge4 core.

作者信息

Wang Wenyuan, Yao Shenglai, van Wüllen Christoph, Driess Matthias

机构信息

Institute of Chemistry, Metalorganics and Inorganic Materials, Technische Universität Berlin, D-10623 Berlin, Germany.

出版信息

J Am Chem Soc. 2008 Jul 30;130(30):9640-1. doi: 10.1021/ja802502b. Epub 2008 Jul 2.

DOI:10.1021/ja802502b

PMID:18593161

Abstract

The first isolable cyclogermylidenide salt 2 has been synthesized and isolated by facile dehalogenation of the N-heterocyclic chlorogermylene 1 with elemental potassium in ether and isolated in the form of yellow crystals in 33% yield. Single-crystal X-ray diffraction analysis revealed that 2 crystallizes as a dimeric half-sandwich complex of aromatic C3NGe rings interconnected via intermolecular Ge(II)-->K dative bonds. Its yield can be improved up to 42% by gentle reduction of 1 (or its related GeCl3 complex 8) using potassium graphite. Additionally, the remarkable K2Ge4 cluster compound 9 has been isolated as a side product which consists of an unusual dianionic Ge4 core with parallelogram configuration and pronounced aromaticity as indicated by highly negative NICS values.

摘要

首个可分离的环锗亚胺盐2已通过在乙醚中用单质钾对N-杂环氯锗烯1进行简便的脱卤反应合成并分离出来，以黄色晶体形式分离得到，产率为33%。单晶X射线衍射分析表明，2以芳香族C3NGe环的二聚半夹心配合物形式结晶，通过分子间Ge(II)→K配位键相互连接。使用石墨钾对1（或其相关的GeCl3配合物8）进行温和还原，其产率可提高至42%。此外，还分离得到了引人注目的K2Ge4簇合物9作为副产物，它由一个具有平行四边形构型且具有明显芳香性的不寻常双阴离子Ge4核心组成，这由高度负的NICS值表明。