Work

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

Year: 2020

Type: article

Abstract: 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.

Source: Inorganic Chemistry

DOI: 10.1021/acs.inorgchem.0c01163

Authors: John J. Kiernicki, Matthias Zeller, Nathaniel K. Szymczak

Institutions: University of Michigan, Purdue University West Lafayette

Language: English

Topic: Organometallic Complex Synthesis and Catalysis

Subfield: Organic Chemistry

Field: Chemistry

Domain: Physical Sciences

Open Access status: green

Funders: Camille and Henry Dreyfus Foundation, National Institute of General Medical Sciences

Awards: The Role of Secondary Interactions Relevant to Biological Reductions of Small Molecules, Elucidating the Effects of Secondary Interactions Relevant to Enzymatic Small Molecule Activation