| Autor: |
Bilyj JK; School of Chemistry and Molecular Biosciences, University of Queensland, Brisbane, 4072, Australia. p.bernhardt@uq.edu.au., Riley MJ, Bernhardt PV |
| Jazyk: |
angličtina |
| Zdroj: |
Dalton transactions (Cambridge, England : 2003) [Dalton Trans] 2018 Feb 06; Vol. 47 (6), pp. 2018-2030. |
| DOI: |
10.1039/c7dt04337f |
| Abstrakt: |
The complexation of nickel(ii) with acetylacetonate bis(thiosemicarbazone) N 2 S 2 ligands with varying substituents has revealed that two isomers can exist independently in solution. These isomers differ according to the formation of either a 5,6,5-membered (symmetric) or a 4,7,5-membered (asymmetric) chelate ring arrangement. These two isomers have distinctly different properties. The symmetric complex (sym-[Ni(acacR)]) is unstable in the presence of air and slowly converts to the oxidised analogue sym-[Ni(acacRO)] with a carbonyl group installed at the apical C-atom. The mechanism of this O-atom transfer reaction is still unclear but kinetic and spectroelectrochemical experiments in addition to Density Functional Theory calculations have identified a single electron oxidised Ni II -ligand radical complex as a key intermediate. By contrast the asymmetric complex, asym-[Ni(acacR)] is inert to ligand oxidation. |
| Databáze: |
MEDLINE |
| Externí odkaz: |
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