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

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• 作者：Mohammad Akbar Ali ; Paul V. Bernhardt ; Mathilde A. H. Brax ; Jason England ; Anthony J. Farlow ; Graeme R. Hanson ; Lee Len Yeng ; Aminul Huq Mirza ; Karl Wieghardt
• 刊名：Inorganic Chemistry
• 出版年：2013
• 出版时间：February 4, 2013
• 年：2013
• 卷：52
• 期：3
• 页码：1650-1657
• 全文大小：455K
• 年卷期：v.52,no.3(February 4, 2013)
• ISSN：1520-510X

文摘

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 Cu^III oxidation state is observed, and the complex [Cu(ttfasbz)] has been isolated and characterized structurally. Reduction to the EPR active Cu^II analogue has been achieved chemically and also electrochemically, and in both cases, the process is totally reversible. The Cu^III/II redox potential of the complex is remarkably low and similar to that of the ferrocenium/ferrocene couple. Further reduction to the formally monovalent (d¹⁰) dianion [Cu^I(ttfasbz)]^{2鈥?/sup> may be achieved electrochemically. Computational chemistry demonstrates that the three redox states [Cu(ttfasbz)], [Cu(ttfasbz)]鈭?/sup>, and [Cu(ttfasbz)]2鈥?/sup> are truly CuIII, CuII, and CuI complexes, respectively, and the potentially noninnocent ligand does not undergo any redox reactions.}