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Abstract Formal nickelate(−I) complexes bearing Group 13 metalloligands (M=Al and Ga) were isolated. These 17 e−complexes were synthesized by one‐electron reduction of the corresponding Ni0→MIIIprecursors, and were investigated by single‐crystal X‐ray diffraction, EPR spectroscopy, and quantum chemical calculations. Collectively, the experimental and computational data support: 1) the strengthening of the Ni−M bond upon one‐electron reduction, and 2) the delocalization of the unpaired spin across the Ni and M atoms. An intriguing electronic configuration is revealed where three valence electrons occupy two σ‐type bonding interactions: Ni(3d)2→M and σ‐(Ni−M)1. The latter is an unusual Ni−M σ‐bonding molecular orbital that comprises primarily the Ni 4pzand M npz/ns atomic orbitals.
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Reductive Disproportionation of CO 2 Mediated by Bimetallic Nickelate(-I)/Group 13 Complexes: Reductive Disproportionation of CO 2 Mediated by Bimetallic Nickelate(-I)/Group 13 Complexes
- PAR ID:
- 10085945
- Publisher / Repository:
- Wiley Blackwell (John Wiley & Sons)
- Date Published:
- Journal Name:
- European Journal of Inorganic Chemistry
- Volume:
- 2019
- Issue:
- 15
- ISSN:
- 1434-1948
- Page Range / eLocation ID:
- p. 2140-2145
- Format(s):
- Medium: X
- Sponsoring Org:
- National Science Foundation
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