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

Abstract

Formal nickelate(ÀI) complexes bearing Group 13 metalloligands (M = Al and Ga) were isolated. These 17 e À complexes were synthesized by one-electron reduction of the corresponding Ni 0 !M III precursors,a nd were investigated by single-crystal X-ray diffraction, EPR spectroscopy, and quantum chemical calculations.C ollectively,t he experimental and computational data support:1)the strengthening of the Ni À M bond upon one-electron reduction, and 2) the delocalization of the unpaired spin across the Ni and Ma toms.A ni ntriguing electronic configuration is revealed where three valence electrons occupyt wo s-type bonding interactions:N i-(3d z 2 ) 2 !Ma nd s-(NiÀM) 1 .T he latter is an unusual NiÀM sbonding molecular orbital that comprises primarily the Ni 4p z and Mnp z /ns atomic orbitals.

Elucidating the Mechanism of Simultaneous Activation of CH4 and CO2 Mediated by Single Group 10 Metal Anions in Gas Phase

“…This work represents the first example of mutual functionalization of CH 4 and CO 2 mediated by single atomic anions [31] . Efforts were put on developing Pd/Ni‐based catalysts to activate CH 4 and/or CO 2 , and there were attempts to obtain negative charged metallic catalysts [32–35] . Inspired by these findings, we performed high‐level computational studies on Ni − and Pd − , both are group 10 metal anions as Pt − , to explore their capability to simultaneously functionalize CH 4 and CO 2 , and to compare their performance with Pt − .…”