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- Title
Formal Nickelate(−I) Complexes Supported by Group 13 Ions.
- Authors
Vollmer, Matthew V.; Xie, Jing; Cammarota, Ryan C.; Young, Jr., Victor G.; Gagliardi, Laura; Lu, Connie C.; Bill, Eckhard
- Abstract
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→MIII precursors, 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 z 2 )2→M and σ‐(Ni−M)1. The latter is an unusual Ni−M σ‐bonding molecular orbital that comprises primarily the Ni 4pz and M npz/ns atomic orbitals.
- Subjects
SOLVENTS; WATER purification; ELECTRON paramagnetic resonance; ELECTRODES; ACETONITRILE; CAMBRIDGE Isotope Laboratories Inc.
- Publication
Angewandte Chemie, 2018, Vol 130, Issue 26, p7941
- ISSN
0044-8249
- Publication type
Article
- DOI
10.1002/ange.201803356