One-electron reduction product of biphosphinine derivative and of its Ni(0) complex: crystal structure, EPR/ENDOR and DFT investigations on (tmbp).- and [Ni(tmbp)2].-

Choua, Sylvie; Sidorenkova Cruz Gonzalez, Elena; Berclaz, Théo; Geoffroy, Michel; Rosa, Patrick; Mézailles, Nicolas; Ricard, Louis; Mathey, François; Le Floch, Pascal

doi:10.1021/ja002125+

Scientific article

English

One-electron reduction product of biphosphinine derivative and of its Ni(0) complex: crystal structure, EPR/ENDOR and DFT investigations on (tmbp).- and [Ni(tmbp)2].-

Contributors

Choua, Sylvie; Sidorenkova Cruz Gonzalez, Elena; Berclaz, Théo; Geoffroy, Michel; Rosa, Patrick; Mézailles, Nicolas; Ricard, Louis; Mathey, François; Le Floch, Pascal

Published in

Journal of the American Chemical Society, vol. 122, no. 49, p. 12227-12234

Publication date

2000

Abstract

The radical anion (tmbp)•-, where tmbp = 4,4‘,5,5‘-tetramethyl-2,2‘-biphosphinine, was generated by reduction of tmbp on a potassium mirror. EPR/ENDOR spectra and DFT calculations show that, in contrast to the neutral species, this anion is planar and that the unpaired electron is mainly delocalized on the PCCP fragment with a large participation of the phosphorus pπ orbitals. This planar structure was confirmed by the first crystal structure of an anionic biphosphinine: [tmbp][Li(2.2.1)]. Reduction of [Ni(tmbp)2] led to the 19-electron complex whose g and 31P hyperfine tensors were obtained from EPR in liquid and frozen solutions. These results, together with DFT calculations on [Ni(bp)2] and [Ni(bp)2]•-, indicate that, by accepting an extra electron, the neutral nickel complex distorts toward a more planar geometry and that the dihedral angle between the two phosphinine rings of each ligand slightly increases. In the reduced Ni complex, the unpaired electron is mainly delocalized on the ligands, in a molecular orbital which retains the characteristics of the SOMO found for the reduced isolated ligand. A charge decomposition analysis (CDA) shows that, in [Ni(bp)2], metal−ligand back-donation strongly contributes to the metal−ligand bonding.

UNIGE affiliation entities

Faculté des sciences / Section de chimie et biochimie / Département de chimie physique

UNIGE research groups

Citation (ISO format)

CHOUA, Sylvie et al. One-electron reduction product of biphosphinine derivative and of its Ni(0) complex: crystal structure, EPR/ENDOR and DFT investigations on (tmbp).- and [Ni(tmbp)2].-. In: Journal of the American Chemical Society, 2000, vol. 122, n° 49, p. 12227–12234. doi: 10.1021/ja002125+

Article (Published version)

Identifiers

PID : unige:3604
DOI : 10.1021/ja002125+

Journal ISSN

0002-7863

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Creation

02/10/2009 15:18:47

First validation

02/10/2009 15:18:47

Update

04/04/2025 12:57:27

Status update

07/11/2023 07:38:35

Last indexation

10/06/2025 21:30:43

One-electron reduction product of biphosphinine derivative and of its Ni(0) complex: crystal structure, EPR/ENDOR and DFT investigations on (tmbp).- and [Ni(tmbp)2].-

Contributors

Published in

Publication date

Abstract

UNIGE affiliation entities

UNIGE research groups

Citation (ISO format)

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First validation

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Status update

Last indexation