A copper thiolate centre for electron transfer: mononuclear vs. dinuclear complexes

We have structurally and spectroscopically investigated a rare example of a mononuclear aliphatic dithiolate Cu(II) complex characterized by a reversible Cu(II)/Cu(I) redox couple. By DFT, we have shown that this system has a lower reorganization energy than its previously described bis(μ-thiolato) dicopper parent complex, which reversibly cycles between the Cu(1.5)Cu(1.5) and Cu(I)Cu(I) redox states.