The one-electron reduction of (Au(mnt)(2)](2-) (mnt = [S(2)C(2)(CN)(2)](2-), maleonitriledithiolate), 1(2-), stands out in the rich redox chemistry of metal-mnt complexes as a chemically reversible but electrochemically irreversible process. Although the E(1/2) value of the primary redox reaction 1(2-)/1(3-) is only slightly medium dependent (ca. -1.36 V to -1.53 V vs FcH in several nonaqueous solvents and supporting electrolytes), its chemical reversibility is dramatically solvent dependent. A quasi-Nernstian process was observed only in tetrahydrofuran (THF) at low supporting electrolyte concentrations. Fast reversible follow-up reactions, ascribed to formation of solvento-complexes [Au(mnt)(2)center dot Solv](3-), were observed through cyclic voltammetry (CV) studies in dichloromethane and acetonitrile. The specifically solvated trianion reverts to "unsolvated" 1(2-) when reoxidized, accounting for the overall chemical reversibility of the process. Owing to the fact that the ligands in 1(3-) are highly negatively charged, the strong specific solvation is likely to involve H-bonding interactions between the solvent and the sulfur atoms of the trianion. Ion-pairing interactions between 1(3-) and electrolyte cations were also shown to have a discernible effect on the 1(2-)/1(3-) couple in THF. The heterogeneous electron-transfer (ET) rate constant (k(s)) for this couple was sufficiently low (k(s) = similar to 10(-3) cm s(-1)) to suggest a square-planar to quasi-tetrahedral structural rearrangement being intrinsic to the 1(2-)/1(3-) ET process. The E(1/2) separation between the 1(-)/1(2-) and 1(2-)/1(3-) couples (ca. 220 mV) is much smaller than any of those previously reported for metal-mnt complexes. The behavior of the gold-mnt trianion is a rare example of a ligand-based solvento-complex, which contrasts with the well-known metal-based solvento-complexes that are commonly observed between electron-deficient complexes and strong donor solvents.
