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Direct experimental evaluation of ligand-induced backbonding in nickel metallacyclic complexes

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Abstract

The details of ligand-induced backbonding in nickel diphosphine π complexes are explored using nickel L-edge (3d←2p) X-ray absorption spectroscopy as a means of quantifying the degree of backbonding derived from direct Ni 3d donation into the π ligand. It is observed that backbonding into weakly π acidic ligands such as alkenes and arenes is dominated by contributions from the diphosphine ligand via σ-donation, leading to activated metallacycles with a Ni(0) d10 metal centre. With more strongly π acidic ligands, however, metal contributions to backbonding increase substantially leading to a more electron-deficient metal centre that is best described as having a Ni(I) spectroscopic oxidation state.

Graphical abstract: Direct experimental evaluation of ligand-induced backbonding in nickel metallacyclic complexes

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Publication details

The article was received on 22 Apr 2019, accepted on 05 Jun 2019 and first published on 05 Jun 2019


Article type: Paper
DOI: 10.1039/C9FD00041K
Faraday Discuss., 2019, Advance Article

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    Direct experimental evaluation of ligand-induced backbonding in nickel metallacyclic complexes

    W. He and P. Kennepohl, Faraday Discuss., 2019, Advance Article , DOI: 10.1039/C9FD00041K

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