Affiliation:
1. Department of Chemistry University of Michigan 930 N. University Ann Arbor MI 48109 USA
2. Present address: Drury University Department of Chemistry and Physics 900 North Benton Ave. Springfield MO 65802 USA
3. H.C. Brown Laboratory Department of Chemistry Purdue University 560 Oval Dr. West Lafayette IN 47907 USA
Abstract
AbstractWe present a ligand platform featuring appended ditopic Lewis acids to facilitate capture/activation of diatomic substrates. We show that incorporation of two 9‐borabicyclo[3.3.1]nonane (9‐BBN) units on a single carbon tethered to a pyridine pyrazole scaffold maintains a set of unquenched nitrogen donors available to coordinate FeII, ZnII, and NiII. Using hydride ion affinity and competition experiments, we establish an additive effect for ditopic secondary sphere boranes, compared to the monotopic analogue. These effects are exploited to achieve high selectivity for binding NO2− in the presence of competitive anions such as F− and NO3−. Finally, we demonstrate hydrazine capture within the second‐sphere of metal complexes, followed by unique activation pathways to generate hydrazido and diazene ligands on Zn and Fe, respectively.
Funder
National Institutes of Health
Camille and Henry Dreyfus Foundation
Division of Chemistry
Subject
General Chemistry,Catalysis
Cited by
4 articles.
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