The Trivalent Copper Complex of a Conjugated Bis-dithiocarbazate Schiff Base: Stabilization of Cu in Three Different Oxidation States

The new tribasic N2S2 ligand H3ttfasbz has been synthesized by condensation of 4-thenoyl 2,2,2-trifluoroacetone and S-benzyl dithiocarbazate. On complexation with copper(II) acetate, spontaneous oxidation to the CuIII oxidation state is observed, and the complex [Cu(ttfasbz)] has been isolated and c...

Full description

Saved in:
Bibliographic Details
Published in:Inorganic chemistry Vol. 52; no. 3; pp. 1650 - 1657
Main Authors: Akbar Ali, Mohammad, Bernhardt, Paul V, Brax, Mathilde A. H, England, Jason, Farlow, Anthony J, Hanson, Graeme R, Yeng, Lee Len, Mirza, Aminul Huq, Wieghardt, Karl
Format: Journal Article
Language:English
Published: United States American Chemical Society 04-02-2013
Subjects:
Online Access:Get full text
Tags: Add Tag
No Tags, Be the first to tag this record!
Description
Summary:The new tribasic N2S2 ligand H3ttfasbz has been synthesized by condensation of 4-thenoyl 2,2,2-trifluoroacetone and S-benzyl dithiocarbazate. On complexation with copper(II) acetate, spontaneous oxidation to the CuIII oxidation state is observed, and the complex [Cu(ttfasbz)] has been isolated and characterized structurally. Reduction to the EPR active CuII analogue has been achieved chemically and also electrochemically, and in both cases, the process is totally reversible. The CuIII/II redox potential of the complex is remarkably low and similar to that of the ferrocenium/ferrocene couple. Further reduction to the formally monovalent (d 10) dianion [CuI(ttfasbz)]2– may be achieved electrochemically. Computational chemistry demonstrates that the three redox states [Cu(ttfasbz)], [Cu(ttfasbz)]−, and [Cu(ttfasbz)]2– are truly CuIII, CuII, and CuI complexes, respectively, and the potentially noninnocent ligand does not undergo any redox reactions.
Bibliography:ObjectType-Article-1
SourceType-Scholarly Journals-1
ObjectType-Feature-2
content type line 23
ISSN:0020-1669
1520-510X
DOI:10.1021/ic302596h