Issue 6, 2018

Isomerism and reactivity of nickel(ii) acetylacetonate bis(thiosemicarbazone) complexes

Abstract

The complexation of nickel(II) with acetylacetonate bis(thiosemicarbazone) N2S2 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 NiII–ligand radical complex as a key intermediate. By contrast the asymmetric complex, asym-[Ni(acacR)] is inert to ligand oxidation.

Graphical abstract: Isomerism and reactivity of nickel(ii) acetylacetonate bis(thiosemicarbazone) complexes

Supplementary files

Article information

Article type
Paper
Submitted
17 Nov 2017
Accepted
11 Jan 2018
First published
12 Jan 2018

Dalton Trans., 2018,47, 2018-2030

Isomerism and reactivity of nickel(II) acetylacetonate bis(thiosemicarbazone) complexes

J. K. Bilyj, M. J. Riley and P. V. Bernhardt, Dalton Trans., 2018, 47, 2018 DOI: 10.1039/C7DT04337F

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