Issue 35, 2024

Phospha-bicyclohexene-germylenes exhibiting unexpected reactivity

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 K2[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.

Graphical abstract: Phospha-bicyclohexene-germylenes exhibiting unexpected reactivity

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Article information

Article type
Edge Article
Submitted
19 jun 2024
Accepted
26 jul 2024
First published
30 jul 2024
This article is Open Access

All publication charges for this article have been paid for by the Royal Society of Chemistry
Creative Commons BY license

Chem. Sci., 2024,15, 14161-14170

Phospha-bicyclohexene-germylenes exhibiting unexpected reactivity

M. S. Würdemann, S. Kühn, T. Bötel, M. Schmidtmann and T. Müller, Chem. Sci., 2024, 15, 14161 DOI: 10.1039/D4SC04034A

This article is licensed under a Creative Commons Attribution 3.0 Unported Licence. You can use material from this article in other publications without requesting further permissions from the RSC, provided that the correct acknowledgement is given.

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