Analysis of Non-innocence of Phosphaquinodimethane Ligands when Charge and Aromaticity Come into Play |
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| Authors: | Dr Philip Junker Alicia Rey Planells Prof?Dr Arturo Espinosa Ferao Prof?Dr Rainer Streubel |
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| Institution: | 1. Institut für Anorganische Chemie, Rheinische Friedrich-Wilhelms-Universität Bonn, Gerhardt-Domagk-Straße 1, 53121 Bonn, Germany;2. Departamento de Química Orgánica, Facultad de Química, Universidad de Murcia, Campus de Espinardo, 30100 Murcia, Spain |
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| 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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| Keywords: | Aromaticity DFT calculations geometric distortion NICS phosphaquinodimetane |
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