Formal Nickelate(−I) Complexes Supported by Group 13 Ions

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 cal...

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Bibliographic Details
Published in:Angewandte Chemie 2018-06, Vol.130 (26), p.7941-7945
Main Authors: Vollmer, Matthew V., Xie, Jing, Cammarota, Ryan C., Young, Victor G., Bill, Eckhard, Gagliardi, Laura, Lu, Connie C.
Format: Article
Language:English
Subjects:
Aluminum
Chemical bonds
Chemistry
Computer applications
EPR-Spektroskopie
Gallium
Gruppe-13-Elemente
Metallate
Molecular chains
Molecular orbitals
Nickel
Organic chemistry
Quantum chemistry
Radikale
Reduction
Spectroscopy
X-ray diffraction
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Summary: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(3dz2 )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. Wo sind die Valenzelektronen? Formale Ni(−I)‐Komplexe mit Gruppe‐13‐Metall‐Liganden wurden isoliert. Charakteristisch für diese Komplexe ist eine bindende Drei‐Elektronen‐Wechselwirkung.
ISSN:0044-8249
1521-3757
DOI:10.1002/ange.201803356