Haptotropism in a Nickel Complex with a Neutral, π‐Bridging cyclo‐P4 Ligand Analogous to Cyclobutadiene
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
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Angewandte ChemieDate
2022Discipline
Nanoscience CenterEpäorgaaninen kemiaEpäorgaaninen ja analyyttinen kemiaNanoscience CenterInorganic ChemistryInorganic and Analytical ChemistryCopyright
© 2022 the Authors
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.
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Wiley-VCH VerlagISSN Search the Publication Forum
1433-7851Keywords
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https://converis.jyu.fi/converis/portal/detail/Publication/104131798
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Related funder(s)
European Commission; Research Council of FinlandFunding program(s)
ERC Consolidator Grant; Postdoctoral Researcher, AoF
The content of the publication reflects only the author’s view. The funder is not responsible for any use that may be made of the information it contains.
Additional information about funding
Financial support was provided by the Universities of Calgary and Jyväskylä, the Academy of Finland (Grant #340060 to C.G.), as well as the NSERC of Canada in the form of Discovery Grant #2019-07195 to R.R. The project received funding from the European Research Council under the EU’s Horizon 2020 programme (Grant #772510 to H.M.T). Computational resources were provided by the Finnish Grid and Cloud Infrastructure (persistent identifier urn:nbn:fi:research-infras-2016072533). ...License
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