Thiolate-Bridged Dicobalt Complexes Bearing Hydrazine, Hydrazido, and Diazenido Ligands: Synthesis, Structural Characterization, and Interconversion.

Synthetic di- or multimetallic complexes bearing NxHy nitrogenous ligands in a sulfur-rich coordination environment have attracted considerable attention due to their importance in evaluating the complex mechanism of biological nitrogen fixation. Herein, we report a series of thiolate-bridged dicobalt NxHy species obtained by treatment of CoIIICoIII precursor with hydrazine and its substituted derivatives at ambient temperature. Remarkably, when the substituent is the cyclohexyl group, the resulting species can interconvert through different pathways. This Co2S2 skeleton provides a new model system for obtaining valuable information about the early N2Hx-bound intermediate species during the catalytic cycle of nitrogenase.