Classical halides of the heavier Group 14 homologues germanium, tin, and lead are common precursors for the synthesis of exciting compounds, such as polyhedral clusters. To get access to larger metalloid cluster compounds of Group 14, the disproportionation reaction of metastable monohalide solutions, accessible through a preparative co‐condensation reaction, proved to be quite successful. As the identity of the subvalent halides within the metastable solutions were yet unknown the reaction course from a monohalide precursor to a metalloid cluster was mostly unidentified. This might change now, as a first subhalide cluster [Ge₁₄Br₈(Et₃P)₄] could be characterized, being the first trapped intermediate of the disproportionation reaction of Group 14 subhalides. All these aspects are included within this Minireview, together with a short historical overview, dealing with the development of the preparative co‐condensation technique out of the matrix isolation technique, being the essential first step of the synthesis of metastable monohalide solutions of the heavier Group 14 elements Ge and Sn.

中文翻译：

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较重族的卤化物14锗，锡和铅的同系物-经历异常化合物和氧化态的旅程

较重的第14组同系物锗，锡和铅的经典卤化物是合成令人兴奋的化合物（如多面体簇）的常见前体。为了获得第14组更大的准金属簇化合物，通过制备共缩合反应可实现亚稳态一卤化物溶液的歧化反应，该方法非常成功。由于亚稳态溶液中亚价卤化物的身份尚不清楚，因此从一卤化物前体到准金属簇的反应过程大多不确定。作为第一个亚卤化物簇[Ge ₁₄ Br ₈（Et ₃ P）₄可以表征为第14族亚卤化物歧化反应的第一个被捕获的中间体。所有这些方面都包括在本Minireview中，以及简短的历史概述，涉及基质分离技术之外的制备性预缩合技术的发展，这是合成较重族的亚稳态一卤化物溶液的必不可少的第一步14种元素Ge和Sn。