Examining the Generality of Metal-Ligand Cooperativity Across a Series of First-Row Transition Metals: Capture, Bond Activation, and Stabilization

We outline the generality and requirements for cooperative N2H4 capture, N-N bond scission, and amido stabilization across a series of first-row transition metal complexes bearing a pyridine(dipyrazole) ligand. This ligand contains a pair of flexibly tethered trialkylborane Lewis acids that enable hydrazine capture and M-NH2 stabilization. While the Lewis acids are required to bind N2H4, the identity of the metal dictates whether N-N bond scission can occur. The redox properties of the M(II) bis(amidoborane) series of complexes were investigated and reveal that ligand-based events prevail; oxidation results in the generation of a transiently formed aminyl radical, while reduction occurs at the redox-active pyridine(dipyrazole) ligand.