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Formal Nickelate(−I) Complexes Supported by Group 13 Ions.
- Source :
- Angewandte Chemie International Edition; 6/25/2018, Vol. 57 Issue 26, p7815-7819, 5p
- Publication Year :
- 2018
-
Abstract
- Abstract: Formal nickelate(−I) complexes bearing Group 13 metalloligands (M=Al and Ga) were isolated. These 17 e<superscript>−</superscript> complexes were synthesized by one‐electron reduction of the corresponding Ni<superscript>0</superscript>→M<superscript>III</superscript> 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 )<superscript>2</superscript>→M and σ‐(Ni−M)<superscript>1</superscript>. The latter is an unusual Ni−M σ‐bonding molecular orbital that comprises primarily the Ni 4p<subscript>z</subscript> and M np<subscript>z</subscript>/ns atomic orbitals. [ABSTRACT FROM AUTHOR]
Details
- Language :
- English
- ISSN :
- 14337851
- Volume :
- 57
- Issue :
- 26
- Database :
- Complementary Index
- Journal :
- Angewandte Chemie International Edition
- Publication Type :
- Academic Journal
- Accession number :
- 130266507
- Full Text :
- https://doi.org/10.1002/anie.201803356