Journal
FARADAY DISCUSSIONS
Volume 220, Issue -, Pages 133-143Publisher
ROYAL SOC CHEMISTRY
DOI: 10.1039/c9fd00041k
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Funding
- Natural Sciences and Engineering Research Council (NSERC) Canada
- Mitacs Canada
- U.S. Department of Energy, Office of Science, Office of Basic Energy Sciences [DE-AC02-76SF00515]
- DOE Office of Biological and Environmental Research
- National Institutes of Health, National Institute of General Medical Sciences [P41GM103393]
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The details of ligand-induced backbonding in nickel diphosphine pi 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 pi ligand. It is observed that backbonding into weakly pi acidic ligands such as alkenes and arenes is dominated by contributions from the diphosphine ligand via sigma-donation, leading to activated metallacycles with a Ni(0) d(10) metal centre. With more strongly pi 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.
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