Abstract
The dinickel(II) dihydride complex (1K) of a pyrazolate‐based compartmental ligand with β‐diketiminato (nacnac) chelate arms (L−), providing two pincer‐type {N3} binding pockets, has been reported to readily eliminate H2 and to serve as a masked dinickel(I) species. Discrete dinickel(I) complexes (2Na, 2K) of L− are now synthesized via a direct reduction route. They feature two adjacent T‐shaped metalloradicals that are antiferromagnetically coupled, giving an S=0 ground state. The two singly occupied local dx2-y2 type magnetic orbitals are oriented into the bimetallic cleft, enabling metal–metal cooperative 2 e− substrate reductions as shown by the rapid reaction with H2 or O2. X‐ray crystallography reveals distinctly different positions of the K+ in 1K and 2K, suggesting a stabilizing interaction of K+ with the dihydride unit in 1K. H2 release from 1K is triggered by peripheral γ‐C protonation at the nacnac subunits, which DFT calculations show lowers the barrier for reductive H2 elimination from the bimetallic cleft.
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