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Formal Nickelate(−I) Complexes Supported by Group 13 Ions
Author(s) -
Vollmer Matthew V.,
Xie Jing,
Cammarota Ryan C.,
Young Victor G.,
Bill Eckhard,
Gagliardi Laura,
Lu Connie C.
Publication year - 2018
Publication title -
angewandte chemie
Language(s) - English
Resource type - Journals
eISSN - 1521-3757
pISSN - 0044-8249
DOI - 10.1002/ange.201803356
Subject(s) - delocalized electron , crystallography , unpaired electron , electron paramagnetic resonance , atomic orbital , valence (chemistry) , ion , chemistry , electron configuration , valence electron , group (periodic table) , molecular orbital , chemical bond , electron , molecule , physics , nuclear magnetic resonance , organic chemistry , quantum mechanics
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 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.