Sequential Radical and Cationic Reactivity at Separated Sites Within One Molecule in Solution

Overview

Journal Chem Sci

Publisher Royal Society of Chemistry

Specialty Chemistry

Date 2024 Apr 5

PMID 38577367

Authors

Shihua Liu

Yinwu Li

Jieli Lin

Zhuofeng Ke

Hansjorg Grutzmacher

Cheng-Yong Su

Zhongshu Li

Affiliations

Soon will be listed here.

Abstract

Distonic radical cations (DRCs) with spatially separated charge and radical sites are expected to show both radical and cationic reactivity at different sites within one molecule. However, such "dual" reactivity has rarely been observed in the condensed phase. Herein we report the isolation of crystalline 1λ,3λ-1-phosphonia-3-phosphinyl-cyclohex-4-enes 2a,b˙, which can be considered delocalized DRCs and were completely characterized by crystallographic, spectroscopic, and computational methods. These DRCs contain a radical and cationic site with seven and six valence electrons, respectively, which are both stabilized conjugation, yet remain spatially separated. They exhibit reactivity that differs from that of conventional radical cations (CRCs); specifically they show sequential radical and cationic reactivity at separated sites within one molecule in solution.

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