Formal Nickelate(-I) Complexes Supported by Group 13 Ions.

Autor: Vollmer MV; Department of Chemistry and Supercomputing Institute, University of Minnesota, 207 Pleasant St. SE, Minneapolis, MN, 55455, USA., Xie J; Department of Chemistry and Supercomputing Institute, University of Minnesota, 207 Pleasant St. SE, Minneapolis, MN, 55455, USA., Cammarota RC; Department of Chemistry and Supercomputing Institute, University of Minnesota, 207 Pleasant St. SE, Minneapolis, MN, 55455, USA., Young VG Jr; Department of Chemistry and Supercomputing Institute, University of Minnesota, 207 Pleasant St. SE, Minneapolis, MN, 55455, USA., Bill E; Max-Planck-Institut für chemische Energiekonversion, Stiftstraße 34-36, 45470, Mülheim an der Ruhr, Germany., Gagliardi L; Department of Chemistry and Supercomputing Institute, University of Minnesota, 207 Pleasant St. SE, Minneapolis, MN, 55455, USA., Lu CC; Department of Chemistry and Supercomputing Institute, University of Minnesota, 207 Pleasant St. SE, Minneapolis, MN, 55455, USA.
Jazyk: angličtina
Zdroj: Angewandte Chemie (International ed. in English) [Angew Chem Int Ed Engl] 2018 Jun 25; Vol. 57 (26), pp. 7815-7819. Date of Electronic Publication: 2018 May 28.
DOI: 10.1002/anie.201803356
Abstrakt: 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 Ni 0 →M III 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(3dz2 ) 2 →M and σ-(Ni-M) 1 . The latter is an unusual Ni-M σ-bonding molecular orbital that comprises primarily the Ni 4p z and M np z /ns atomic orbitals.
(© 2018 Wiley-VCH Verlag GmbH & Co. KGaA, Weinheim.)
Databáze: MEDLINE
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