Synthesis and electronic structure elucidation of bioinspired heterobimetallic nickel complexes†

Despite relevance to metalloenzyme active-sites, the selective synthesis of heterobimetallic compounds featuring unbiased, biologically relevant coordination environments remains a challenge. Herein, we disclose a stepwise synthetic strategy, leveraging kinetic stabilization by an alkali metal cation, as a means of accessing spectroscopically pure M(ii)/Ni(ii) (M = Co & Cu) bimetallics. Electron paramagnetic resonance spectroscopy, variable temperature magnetometry, and DFT calculations support perturbation of the electronic structure as a function of the heterometal within these closely related complexes.