Keyword search (4,163 papers available)

"Patrick B" Authored Publications:

Title Authors PubMed ID
1 Five Nitrogen Oxidation States from Nitro to Amine: Stabilization and Reactivity of a Metastable Arylhydroxylamine Complex. Zsombor-Pindera J; Effaty F; Escomel L; Patrick B; Kennepohl P; Ottenwaelder X; 33124796
CHEMBIOCHEM

 

Title:Five Nitrogen Oxidation States from Nitro to Amine: Stabilization and Reactivity of a Metastable Arylhydroxylamine Complex.
Authors:Zsombor-Pindera JEffaty FEscomel LPatrick BKennepohl POttenwaelder X
Link:https://www.ncbi.nlm.nih.gov/pubmed/33124796
DOI:10.1021/jacs.0c09300
Publication:Journal of the American Chemical Society
Keywords:
PMID:33124796 Category:J Am Chem Soc Date Added:2020-10-31
Dept Affiliation: CHEMBIOCHEM
1 Department of Chemistry and Biochemistry, Concordia University, Montreal, QC H4B 1R6, Canada.
2 Department of Chemistry, University of British Columbia, Vancouver, BC V6T 1Z1, Canada.

Description:

Redox noninnocent ligands enhance the reactivity of the metal they complex, a strategy used by metalloenzymes and in catalysis. Herein, we report a series of copper complexes with the same ligand framework, but with a pendant nitrogen group that spans five different redox states between nitro and amine. Of particular interest is the synthesis of a unprecedented copper(I)-arylhydroxylamine complex. While hydroxylamines typically disproportionate or decompose in the presence of transition metal ions, the reactivity of this metastable species is arrested by the presence of an intramolecular hydrogen bond. Two-electron oxidation yields a copper(II)-(arylnitrosyl radical) complex that can dissociate to a copper(I) species with uncoordinated arylnitroso. This combination of ligand redox noninnocence and hemilability provides opportunities in catalysis for two-electron chemistry via a one-electron copper(I/II) shuttle, as exemplified with an aerobic alcohol oxidation.

PMID: 33124796 [PubMed - as supplied by publisher]





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