A1 Journal article (refereed)
Haptotropism in a Nickel Complex with a Neutral, π‐Bridging cyclo‐P4 Ligand Analogous to Cyclobutadiene (2022)

Gendy, C., Valjus, J., Tuononen, H. M., & Roesler, R. (2022). Haptotropism in a Nickel Complex with a Neutral, π‐Bridging cyclo‐P4 Ligand Analogous to Cyclobutadiene. Angewandte Chemie, 61(18), Article e202115692. https://doi.org/10.1002/anie.202115692

JYU authors or editors

Publication details

All authors or editors: Gendy, Chris; Valjus, Juuso; Tuononen, Heikki M.; Roesler, Roland

Journal or series: Angewandte Chemie

ISSN: 1433-7851

eISSN: 1521-3773

Publication year: 2022

Publication date: 02/02/2022

Volume: 61

Issue number: 18

Article number: e202115692

Publisher: Wiley-VCH Verlag

Publication country: Germany

Publication language: English

DOI: https://doi.org/10.1002/anie.202115692

Publication open access: Openly available

Publication channel open access: Partially open access channel

Publication is parallel published (JYX): https://jyx.jyu.fi/handle/123456789/80640

Abstract

The reaction of ( 1 )Ni(η 2 -cod), 2 , incorporating a chelating bis( N -heterocyclic carbene) 1 , with P 4 in pentane yielded the dinuclear complex [( 2 )Ni] 2 (μ 2 ,η 2 :η 2 -P 4 ), 3 , formally featuring a cyclobutadiene-like, neutral, rectangular, π-bridging P 4 -ring. In toluene, the butterfly-shaped complex [( 1 )Ni] 2 (μ 2 ,η 2 :η 2 -P 2 ), 4 , with a formally neutral P 2 -unit was obtained from 2 and either P 4 or 3 . Computational studies showed that a low energy barrier haptotropic rearrangement involving two isomers of the μ 2 ,η 2 :η 2 -P 4 coordination mode and a low energy μ 2 ,η 4 :η 4 -P 4 coordination mode, as previously predicted for related nickel cyclobutadiene complexes, could explain the coalescence observed in the low temperature NMR spectra of 3 . The insertion of the ( 1 )Ni fragment into a P–P bond of P 7 (SiMe 3 ) 3 , forming complex 5 with a norbornane-like P 7 ligand, was also observed.

Keywords: coordination complexes; phosphorus; nickel

Free keywords: phosphorus; nickel; π-ligands; N-heterocyclic carbene; haptotropism

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Ministry reporting: Yes

VIRTA submission year: 2022

JUFO rating: 3