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Issue 30, 2019
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Mechanochemical and slow-chemistry radical transformations: a case of diorganozinc compounds and TEMPO

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Abstract

From the green chemistry perspective, molecular solid-state transformations conducted under mild conditions are of great interest and desirability. However, research in this area lacked popularity in the previous century, and thus progressed slowly. In particular, the application of radical reactions in solid-state chemistry has been hampered by several long-standing challenges that are intrinsically associated with the apparent unpredictable nature of radical chemistry. We present a comparative study of model mechanochemical, slow-chemistry and solution radical reactions between TEMPO and homoleptic organozinc compounds (i.e., di-tert-butylzinc and diphenylzinc). In the case of the tBu2Zn/TEMPO reaction system only a dimeric diamagnetic complex [tBuZn(μ-TEMPO*)]2 is obtained in yields slightly varying with the method chosen. In contrast, when TEMPO is mixed with diphenylzinc in a 2 : 1 molar ratio a novel paramagnetic Lewis acid–base adduct [[Ph2Zn(η1-TEMPO)]·TEMPO] is isolated in high yields regardless of the applied methodology. This adduct is also formed in the slow-chemistry process when TEMPO is gently mixed with Ph2Zn in a 1 : 1 molar ratio and left for two weeks at ambient temperature. Within the next week the reaction mixture gives in high yield a diamagnetic dinuclear compound [PhZn(μ-TEMPO*)][PhZn(μ211-TEMPO*)] and biphenyl. The analogous reaction conducted in toluene results in a much lower conversion rate. The reported results open up a new horizon in molecular solid-state radical transformations.

Graphical abstract: Mechanochemical and slow-chemistry radical transformations: a case of diorganozinc compounds and TEMPO

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Supplementary files

Article information


Submitted
21 Mar 2019
Accepted
16 Jun 2019
First published
17 Jun 2019

This article is Open Access
All publication charges for this article have been paid for by the Royal Society of Chemistry

Chem. Sci., 2019,10, 7149-7155
Article type
Edge Article

Mechanochemical and slow-chemistry radical transformations: a case of diorganozinc compounds and TEMPO

K. Budny-Godlewski, I. Justyniak, M. K. Leszczyński and J. Lewiński, Chem. Sci., 2019, 10, 7149
DOI: 10.1039/C9SC01396B

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