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 →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.