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展现出意外反应活性的磷杂双环己烯锗烯

Phospha-bicyclohexene-germylenes exhibiting unexpected reactivity.

作者信息

Würdemann Marie Sophie, Kühn Steffen, Bötel Tobias, Schmidtmann Marc, Müller Thomas

机构信息

Institute of Chemistry, Carl von Ossietzky Universität Oldenburg Carl von Ossietzky-Str. 9-11 D-26129 Oldenburg Federal Republic of Germany

出版信息

Chem Sci. 2024 Jul 30;15(35):14161-70. doi: 10.1039/d4sc04034a.

DOI:10.1039/d4sc04034a
PMID:39129781
原文链接:https://pmc.ncbi.nlm.nih.gov/articles/PMC11310892/
Abstract

Introducing phospha-bicyclohexene (BCH)-germylenes (BCHGe's) as a novel, multifunctional compound class: the title compounds 15-18 are obtained from simple salt metathesis reactions of dipotassium germacyclopentadienediides K[1] with phosphorusdichlorides. The BCHGe's 15-18 are stabilized by homoconjugation of the germanium(ii) centre with the remote C[double bond, length as m-dash]C double bond. Despite substantial thermodynamic stabilization, phospha-BCHGe's are reactive and undergo a reductive elimination of elemental germanium to give the corresponding phospholes. The elimination is a nucleophilic, bimolecular process and is prevented by large substituents. The reaction of phospha-BCHGe's with small electrophiles gives the corresponding phosphonium salts. Oxidation with chalcogens takes place at both the germanium and the phosphorus atom, and after elimination of germanium chalcogenides the corresponding phosphole chalcogenides were isolated. The introduced germylenes exhibit strong nucleophilic but also non-neglectable electrophilic properties.

摘要

介绍磷杂双环己烯（BCH）-亚锗烯（BCHGe）作为一类新型多功能化合物：标题化合物15 - 18是通过二钾锗杂环戊二烯二负离子K[1]与二氯化磷的简单盐复分解反应制得的。BCHGe 15 - 18通过锗（II）中心与远程碳-碳双键的同共轭作用得以稳定。尽管有显著的热力学稳定性，但磷杂BCHGe具有反应活性，会发生元素锗的还原消除反应生成相应的磷杂环戊二烯。该消除反应是一个亲核双分子过程，大取代基可阻止此反应。磷杂BCHGe与小的亲电试剂反应生成相应的鏻盐。与硫族元素的氧化反应在锗和磷原子上均发生，消除锗硫族化物后分离得到相应的磷杂环戊二烯硫族化物。所引入的亚锗烯表现出强亲核性，但也具有不可忽视的亲电性。

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