Issue 9, 2024

Low-spin to low-spin valence tautomeric transition in cobalt bis-dioxolenes

Abstract

Cobalt dioxolenes are a well-known class of switchable coordination compounds showing intramolecular electron transfer, which is always accompanied by a spin state change at the cobalt center. Here, we present the first example of thermally switchable cobalt bis-dioxolenes where intramolecular electron transfer seems to take place, but the spin state change is suppressed. This leads to the detection of thermal transition between a common ls-CoIII(SQ˙)(Cat2−) and an extremely rare ls-CoII(SQ˙)2 electronic state (hs – high-spin, ls – low-spin, SQ˙ – benzosemiquinonate(1−) radical and Cat2− – catecholate(2−)). Parallel to the present work, a similar work but on cobalt mono-dioxolenes has just appeared (Chem. Eur. J., 2023, 29, e202300091), suggesting thermal transition between ls-CoIII(Cat2−) and ls-CoII(SQ˙) electronic states.

Graphical abstract: Low-spin to low-spin valence tautomeric transition in cobalt bis-dioxolenes

Supplementary files

Article information

Article type
Paper
Submitted
23 Nov 2023
Accepted
16 Jan 2024
First published
24 Jan 2024
This article is Open Access
Creative Commons BY license

Dalton Trans., 2024,53, 4098-4107

Low-spin to low-spin valence tautomeric transition in cobalt bis-dioxolenes

M. Mörtel, S. J. Goodner, J. Oschwald, A. Scheurer, T. Drewello and M. M. Khusniyarov, Dalton Trans., 2024, 53, 4098 DOI: 10.1039/D3DT03935H

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