Additive Effects in Metal/Lewis Acid Cooperativity Assessed in a Tetrahedral Copper Hydrazine Complex Featuring an Appended Borane

Emily E Norwine; John J Kiernicki; Matthias Zeller; Nathaniel K Szymczak

doi:10.1021/acs.inorgchem.4c02865

Additive Effects in Metal/Lewis Acid Cooperativity Assessed in a Tetrahedral Copper Hydrazine Complex Featuring an Appended Borane

Inorg Chem. 2024 Sep 17. doi: 10.1021/acs.inorgchem.4c02865. Online ahead of print.

Authors

Emily E Norwine¹, John J Kiernicki², Matthias Zeller³, Nathaniel K Szymczak¹

Affiliations

¹ Department of Chemistry, University of Michigan, Ann Arbor, Michigan 48109, United States.
² Department of Chemistry, Drury University, Springfield, Missouri 65802, United States.
³ H. C. Brown Laboratory, Department of Chemistry, Purdue University, West Lafayette, Indiana 47907, United States.

PMID: 39287153
DOI: 10.1021/acs.inorgchem.4c02865

Abstract

Within metal/ligand cooperative systems employing acidic groups, studies that empirically assess distance relationships are needed to maximize cooperative interactions with substrates. We report the formation of two Cu(I)-N₂H₄ complexes using 1,4,7-triazacyclononane ligand frameworks bearing two tert-butyl groups and either a Lewis acidic trialkylborane or an inert alkyl group. Metal/Lewis acid cooperativity imparts heightened acidification of the hydrazine substrate and plays a key role in the release of substrate to a competitive Lewis acidic group.