Chemistry Programme, Faculty of Science, Universiti Brunei Darussalam, BE 1410, Brunei Darussalam.
Inorg Chem. 2013 Feb 4;52(3):1650-7. doi: 10.1021/ic302596h. Epub 2013 Jan 16.
The new tribasic N(2)S(2) ligand H(3)ttfasbz 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 (d(10)) dianion Cu(I)(ttfasbz) may be achieved electrochemically. Computational chemistry demonstrates that the three redox states [Cu(ttfasbz)], Cu(ttfasbz), and Cu(ttfasbz) are truly Cu(III), Cu(II), and Cu(I) complexes, respectively, and the potentially noninnocent ligand does not undergo any redox reactions.
新型三齿 N(2)S(2)配体 H(3)ttfasbz 通过 4-邻三氟乙酰基-2,2,2-三氟丙酮和 S-苄基二硫代氨基甲酸盐缩合反应合成。与醋酸铜配位时，观察到自发氧化至 Cu(III)氧化态，并且已分离并结构表征了配合物 [Cu(ttfasbz)]。通过化学和电化学还原实现了对 EPR 活性 Cu(II)类似物的还原，在这两种情况下，该过程都是完全可逆的。该配合物的 Cu(III/II)氧化还原电位非常低，与 ferrocenium/ferrocene 对相似。通过电化学还可进一步还原为形式上单价（d(10)）二阴离子 Cu(I)(ttfasbz)。计算化学表明，三种氧化还原态 [Cu(ttfasbz)]、Cu(ttfasbz)和Cu(ttfasbz)分别是真正的 Cu(III)、Cu(II)和 Cu(I)配合物，潜在的非惰性配体不会发生任何氧化还原反应。
