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One electron reduction transforms high-valent low-spin cobalt alkylidene into high-spin cobalt(ii) carbene radical

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Abstract

One electron reduction of formally CoIV(OR)2(CPh2) forms the [CoII(OR)2(CPh2)] anion. Whereas low-spin Co(OR)2([double bond, length as m-dash]CPh2) demonstrated significant alkylidene character, the high-spin [Co(OR)2(CPh2)] anion features a rare Co(II)–carbene radical. Treatment of [Co(OR)2(CPh2)][CoCp*2] with xylyl isocyanide triggers formation of two new C–C bonds, and is likely mediated by nucleophilic attack of deprotonated CoCp*2+ on a transient ketenimine.

Graphical abstract: One electron reduction transforms high-valent low-spin cobalt alkylidene into high-spin cobalt(ii) carbene radical

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Supplementary files

Article information


Submitted
26 Apr 2020
Accepted
17 Jun 2020
First published
17 Jun 2020

Chem. Commun., 2020, Advance Article
Article type
Communication

One electron reduction transforms high-valent low-spin cobalt alkylidene into high-spin cobalt(II) carbene radical

A. Grass, J. A. Bellow, G. Morrison, H. zur Loye, R. L. Lord and S. Groysman, Chem. Commun., 2020, Advance Article , DOI: 10.1039/D0CC03028G

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