Issue 41, 2019

Trivalent copper stabilised by acetylacetone dithiocarbazate Schiff base ligands: structural, spectroscopic and electrochemical properties

Abstract

The copper coordination chemistry of N2S2 Schiff base ligands derived from acetylacetone and S-methyl or S-benzyl dithiocarbazate (H3acacsR, R = Me, Bn) reveals a rich variety of products depending on the reaction conditions. The free ligands spontaneously cyclise to their pyrazoline isomers but ring-open upon complexation with CuII. In the absence of oxygen, the ligands form CuIIN2S2 complexes ([CuII(HacacsR)]) that have been characterised electrochemically, spectroscopically and structurally. Intermediates in the complexation reaction are observed with time-resolved UV-Vis spectroscopy. Upon exposure to air, a number of different complexes are formed. Facile oxidation of [CuII(HacacsR)] to the trivalent analogue [CuIII(acacsR)] occurs in air. This compound is the precursor to two further oxidation reactions; one to the ketone [CuII(acacsRO)] where a carbonyl group has been installed at the apical C atom of the acetylacetone moiety and another to afford the novel dinuclear complex [(CuIII(acacsR))2]. The presence of excess base (Et3N) favours formation of the dimer.

Graphical abstract: Trivalent copper stabilised by acetylacetone dithiocarbazate Schiff base ligands: structural, spectroscopic and electrochemical properties

Supplementary files

Article information

Article type
Paper
Submitted
17 mai 2019
Accepted
02 jul 2019
First published
02 jul 2019

Dalton Trans., 2019,48, 15501-15514

Trivalent copper stabilised by acetylacetone dithiocarbazate Schiff base ligands: structural, spectroscopic and electrochemical properties

J. K. Bilyj, N. V. Silajew, G. R. Hanson, J. R. Harmer and P. V. Bernhardt, Dalton Trans., 2019, 48, 15501 DOI: 10.1039/C9DT02071C

To request permission to reproduce material from this article, please go to the Copyright Clearance Center request page.

If you are an author contributing to an RSC publication, you do not need to request permission provided correct acknowledgement is given.

If you are the author of this article, you do not need to request permission to reproduce figures and diagrams provided correct acknowledgement is given. If you want to reproduce the whole article in a third-party publication (excluding your thesis/dissertation for which permission is not required) please go to the Copyright Clearance Center request page.

Read more about how to correctly acknowledge RSC content.

Social activity

Spotlight

Advertisements