Iron-Catalyzed/Mediated C-N Bond Formation: Competition between Substrate Amination and Ligand Amination
authors Sinha, S; Sikari, R; Sinha, V; Jash, U; Das, S; Brandao, P; Demeshko, S; Meyer, F; de Bruin, B; Paul, ND
nationality International
journal INORGANIC CHEMISTRY
keywords ANTI-MARKOVNIKOV HYDROAMINATION; ANION-RADICAL COMPLEXES; ELECTRON-TRANSFER; ARYL CHLORIDES; CARBENE RADICALS; DIRECT ARYLATION; CROSS-COUPLINGS; RING AMINATION; H AMINATION; REDOX
abstract Iron catalyzed carbon-nitrogen bond formation reactions of a wide variety of nucleophiles and aryl halides using well-defined iron-complexes featuring redox noninnocent 2-(arylazo)-1,10-phenanthroline (L-1) ligands are reported. Besides substrate centered C-N coupling, C-N bond formation reactions were also observed at the ortho- and para-positions of the phenyl ring of the coordinated azo-aromatic scaffolds affording new tetradentate ligands, 2-N-aryl-(2-arylazo)-1,10-phenanthroline (L-2), and tridentate ligands, 4-N-aryl-(2-arylazo)-1,10-phenanthroline (L-3), respectively. Control experiments and mechanistic studies reveal that the complex [(FeLCl2)-Cl-1] (1) undergoes in situ reduction during the catalytic reaction to produce the monoanionic complex [1](-), which then acts as the active catalyst. The metal (iron) and the coordinated ligand were found to work in a cooperative manner during the transfer processes involved in the fundamental steps of the catalytic cycle. Detailed experimental and theoretical (DFT) studies were performed to get insight into the competitive substrate versus ligand centered amination reactions.
publisher AMER CHEMICAL SOC
issn 0020-1669
isbn 1520-510X
year published 2019
volume 58
issue 3
beginning page 1935
ending page 1948
digital object identifier (doi) 10.1021/acs.inorgchem.8b02877
web of science category Chemistry, Inorganic & Nuclear
subject category Chemistry
unique article identifier WOS:000458085900028
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journal analysis (jcr 2019):
journal impact factor 4.825
5 year journal impact factor 4.501
category normalized journal impact factor percentile 92.222
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