Redox Noninnocent Azo-Aromatic Pincers and Their Iron Complexes. Isolation, Characterization, and Catalytic Alcohol Oxidation
authors Sinha, S; Das, S; Sikari, R; Parua, S; Brandao, P; Demeshko, S; Meyer, F; Paul, ND
nationality International
journal INORGANIC CHEMISTRY
keywords TRANSITION-METAL-COMPLEXES; ANION-RADICAL COMPLEXES; ACTIVE TRIS(AMIDO) LIGAND; ELECTRON-TRANSFER SERIES; AEROBIC OXIDATION; NICKEL(II) COMPLEXES; GALACTOSE-OXIDASE; SULFUR CLUSTERS; ALKENES SCOPE; NON-INNOCENCE
abstract The new redox-noninnocent azoaromatic pincers 2-(arylazo)-1,10-phenanthroline (L-1) and 2,9-bis(phenyldiazo)-1,10-phenanthroline (L-2) are reported. The ligand L-1 is a tridentate pincer having NNN donor atoms, whereas L-2 is tetradentate having two azo-N donors and two N-donor atoms from the 1,10-phenanthroline moiety. Reaction of FeCl2 with L-1 or L-2 produced the pentacoordinated mixed-ligand Fe(II) complexes (FeLCl2)-Cl-1 (1) and (FeLCl2)-Cl-2 (2), respectively. Homoleptic octahedral Fe(II) complexes, mer-[Fe(L-1)(2)] (ClO4)(2) [3] (ClO4)(2) and mer-[Fe(L-2)(2)] (ClO4)(2) [4] (ClO4)(2), have been synthesized from the reaction of hydrated Fe(ClO4)(2) and L-1 or L-2. The ligand L-2, although having four donor sites available for coordination, binds the iron center in a tridentate fashion with one uncoordinated pendant azo function. Molecular and electronic structures of the isolated complexes have been scrutinized thoroughly by various spectroscopic techniques, single-crystal X-ray crystallography, and density functional theory. Beyond mere characterization, complexes 1 and 2 were successfully used as catalysts for the aerobic oxidation of primary and secondary benzylic alcohols. A wide variety of substituted benzyl alcohols were found to be converted to the corresponding carbonyl compounds in high yields, catalyzed by complex 1. Several control reactions were carried out to understand the mechanism of this alcohol oxidation reactions.
publisher AMER CHEMICAL SOC
issn 0020-1669
year published 2017
volume 56
issue 22
beginning page 14084
ending page 14100
digital object identifier (doi) 10.1021/acs.inorgchem.7b02238
web of science category Chemistry, Inorganic & Nuclear
subject category Chemistry
unique article identifier WOS:000416297200049
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journal impact factor 4.825
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