Please use this identifier to cite or link to this item: http://hdl.handle.net/10773/18319
Title: 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
Author: Sikari, Rina
Sinha, Suman
Jash, Upasona
Das, Siuli
Brandão, Paula
Bruin, Bas de
Paul, Nanda D.
Issue Date: 2016
Publisher: American Chemical Society
Abstract: Two nickel(II)-complexes, [NiII(H3L)2](ClO4)2 ([1](ClO4)2) and [NiII(HL)2] (2), containing the redox-active tridentate ligand N1-(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)2and 2 were tested for catalytic oxidation of both primary and secondary alcohols.
Peer review: yes
URI: http://hdl.handle.net/10773/18319
DOI: 10.1021/acs.inorgchem.6b00646
ISSN: 0020-1669
Appears in Collections:CICECO - Artigos



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