Publication: Analysis of non-innocence of phosphaquinodimethane ligands when charge and aromaticity come into play
Authors
Junker, Philip ; Rey Planells, Alicia ; Espinosa Ferao, Arturo ; Streubel, Rainer
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Publisher
Wiley
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DOI
https://doi.org/10.1002/chem.202100420
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info:eu-repo/semantics/article
Description
© 2021 The Authors. This manuscript version is made available under the CC-BY-NC-ND 4.0 license http://creativecommons.org/licenses/by-nc-nd/4.0/
This document is the Published Manuscript version of a Published Work that appeared in final form in Chemistry - A European Journal. To access the final edited and published work see https://doi.org/10.1002/chem.202100420
Abstract
Several phosphaquinodimethanes and their M(CO)5 complexes (M=Cr, Mo, W) and model derivatives have been theoretically investigated regarding the quest of non-innocence. Computed structural and electronic properties of the P-Me/NH2 substituted phosphaquinodimethanes and tungsten complexes revealed an interesting non-innocent ligand behaviour for the radical anion complexes with distonic ion character and a strong rearomatization of the middle phenyl ring. The latter was further probed taking also geometric aromaticity (HOMA) and quinoid distortion parameters (HOMQc) into account, as well as NICS(1). Furthermore, the effect of the P-substitution was investigated for real (or plausible) complexes and their free ligands focusing on the resulting aromaticity at the middle phenyl ring and vertical one-electron redox processes. The best picture of ligand engagement in redox changes was provided by representing NICS(1) values versus HOMA and the new geometric distortion parameter HOMQc8.
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Citation
Chemistry - A European Journal, 2021, Vol. 27, Issue 36, pp. 9350-9359
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