Biphenylene Coordination and Ring‐Opening by Alkali‐Metal Nickelates

Abstract

Abstract The pre‐coordination of substrates to heterobimetallic complexes plays a key role in facilitating challenging bond activations and catalytic reactions. Herein, we report a family of low‐valent phenyl‐alkali‐metal nickelates containing a η 4 ‐coordinated biphenylene ligand and demonstrate how the coordination and solvation preferences of the alkali‐metal cation (Li, Na, or K) influence the rate of C─C bond oxidative addition at nickel through combined structural, spectroscopic and computational studies. The rate of C─C bond cleavage can be further manipulated by replacing the two phenyl‐carbanionic ligands with a cyclic 2,2′‐biphenyl scaffold, which affords thermally stable and symmetric spirocyclic nickelates upon ring‐opening.