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
| Autor: | Paula Brandão, Siuli Das, Rina Sikari, Suman Sinha, Nanda D. Paul, Bas de Bruin, Upasona Jash |
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| Přispěvatelé: | Homogeneous and Supramolecular Catalysis (HIMS, FNWI) |
| Jazyk: | angličtina |
| Rok vydání: | 2016 |
| Předmět: |
Stereochemistry
KUMADA COUPLING REACTIONS PLANAR NICKEL-COMPLEXES 010402 general chemistry 01 natural sciences Medicinal chemistry Redox PALLADIUM(II) COMPLEX Inorganic Chemistry chemistry.chemical_compound Deprotonation Diamine CORRELATED AB-INITIO Physical and Theoretical Chemistry Tetracoordinate 010405 organic chemistry Chemistry Diradical Ligand PI-RADICAL LIGANDS TRANSITION-METAL-COMPLEXES REACTIVITY Non-innocent ligand 0104 chemical sciences ELECTRONIC-STRUCTURE DENSITY Alcohol oxidation ACTIVE TRIS(AMIDO) LIGAND |
| Zdroj: | Inorganic Chemistry, 55(12), 6114-6123. American Chemical Society Repositório Científico de Acesso Aberto de Portugal Repositório Científico de Acesso Aberto de Portugal (RCAAP) instacron:RCAAP |
| ISSN: | 0020-1669 |
| Popis: | 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. |
| Databáze: | OpenAIRE |
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