Issue 20, 2022

Geometrically constrained square pyramidal phosphoranide

Abstract

Geometrical constriction of main group elements leading to a change in the reactivity of these main group centers has recently become an important tool in main group chemistry. A lot of focus on using this modern method is dedicated to group 15 elements and especially to phosphorus. In this work, we present the synthesis, isolation and preliminary reactivity study of the geometrically constrained, square pyramidal (SP) phosphoranide anion (1). Unlike, trigonal bipyramidal (TBP) phosphoranides that were shown to react as nucleophiles while their redox chemistry was not reported, 1 reacts both as a nucleophile and reductant. The chemical oxidation of 1 leads to a P–P dimer (1-1) that is formed via the dimerization of unstable SP phosphoranyl radical (), an unprecedented decay pathway for phosphoranyl radicals. Reaction of 1 with benzophenone leads via a single electron transfer (SET) to 1-OK and corresponding tetraphenyl epoxide (4).

Graphical abstract: Geometrically constrained square pyramidal phosphoranide

Supplementary files

Article information

Article type
Edge Article
Submitted
20 Febr. 2022
Accepted
27 Apr. 2022
First published
27 Apr. 2022
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., 2022,13, 5957-5963

Geometrically constrained square pyramidal phosphoranide

S. Volodarsky, I. Malahov, D. Bawari, M. Diab, N. Malik, B. Tumanskii and R. Dobrovetsky, Chem. Sci., 2022, 13, 5957 DOI: 10.1039/D2SC01060G

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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