Deprotonation Induced Ligand Oxidation in a Ni-II Complex of a Redox Noninnocent N-1-(2-Aminophenyl)benzene-1,2-diamine and Its Use in Catalytic Alcohol Oxidation
authors Sikari, R; Sinha, S; Jash, U; Das, S; Brandao, P; de Bruin, B; Paul, ND
nationality International
journal INORGANIC CHEMISTRY
keywords TRANSITION-METAL-COMPLEXES; ACTIVE TRIS(AMIDO) LIGAND; KUMADA COUPLING REACTIONS; PLANAR NICKEL-COMPLEXES; CORRELATED AB-INITIO; PI-RADICAL LIGANDS; ELECTRONIC-STRUCTURE; PALLADIUM(II) COMPLEX; REACTIVITY; DENSITY
abstract Two nickel(II)-complexes, [Ni-II(H3L)(2)] (ClO4)(2) ( [1]-(ClO4)(2)) and [Ni-II(HL)(2)] (2), containing the redox-active tridentate ligand N-1-(2-aminophenyl)benzene-1,2-diamine (H3L) have been synthesized. Complex [1] (ClO4)(2) is octahedral containing two neutral H3L ligands in a facial coordination mode, whereas complex 2 is a singlet diradical species with approximately planar configuration at the tetracoordinate metal atom with two pendant NH2 side arms from each of the coordinated ligands. Both complexes are found to be chemically interconvertible; complex [1](2+) gets converted to complex 2 when exposed to base and oxygen via simultaneous deprotonation and oxidation of the coordinated ligands. Molecular and electronic structures of the isolated complexes are scrutinized thoroughly by various spectroscopic techniques, single crystal X-ray crystallography, and density functional theory. The observed dissociation of a ligand arm upon oxidation of the ligand was exploited to bring about catalytic alcohol oxidation using coordinatively saturated complex [1] (ClO4)(2) as a catalyst precursor. Both the complexes [1] (ClO4)(2) and 2 were tested for catalytic oxidation of both primary and secondary alcohols.
publisher AMER CHEMICAL SOC
issn 0020-1669
year published 2016
volume 55
issue 12
beginning page 6114
ending page 6123
digital object identifier (doi) 10.1021/acs.inorgchem.6b00646
web of science category Chemistry, Inorganic & Nuclear
subject category Chemistry
unique article identifier WOS:000378369900049
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journal impact factor 4.825
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