Norwine Emily E, Kiernicki John J, Zeller Matthias, Szymczak Nathaniel K
Department of Chemistry, University of Michigan, Ann Arbor, Michigan 48109, United States.
Department of Chemistry, Drury University, Springfield, Missouri 65802, United States.
Inorg Chem. 2024 Oct 7;63(40):18519-18523. doi: 10.1021/acs.inorgchem.4c02865. Epub 2024 Sep 17.
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)-NH complexes using 1,4,7-triazacyclononane ligand frameworks bearing two -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.
在采用酸性基团的金属/配体协同体系中，需要通过实证评估距离关系的研究来最大化与底物的协同相互作用。我们报告了使用带有两个丁基以及一个路易斯酸性三烷基硼烷或一个惰性烷基的1,4,7-三氮杂环壬烷配体框架形成的两种Cu(I)-NH配合物。金属/路易斯酸协同作用使肼底物的酸化增强，并在底物向竞争性路易斯酸性基团的释放中起关键作用。
