Three-coordinate bipyridyl complexes of gold, [(κ²-bipy)Au(η²-C₂H₄)][NTf₂], are readily accessed by direct reaction of 2,2′-bipyridine (bipy), or its derivatives, with the homoleptic gold ethylene complex [Au(C₂H₄)₃][NTf₂]. The cheap and readily available bipyridyl ligands facilitate oxidative addition of aryl iodides to the Au(I) center to give [(κ²-bipy)Au(Ar)I][NTf₂], which undergo first aryl-zinc transmetalation and second C–C reductive elimination to produce biaryl products. The products of each distinct step have been characterized. Computational techniques are used to probe the mechanism of the oxidative addition step, offering insight into both the origin of the reversibility of this process and the observation that electron-rich aryl iodides add faster than electron-poor substrates. Thus, for the first time, all steps that are characteristic of a conventional intermolecular Pd(0)-catalyzed biaryl synthesis are demonstrated from a common monometallic Au complex and in the absence of directing groups.

The complexes [Fe₂(CO)₆{μ-SCH₂N(R)CH₂S}] (R = CH₂CH₂OCH₃, 1a; R = ⁱPr, 1b) and [Fe₂(CO)₆(μ-pdt)] 2 (pdt = S(CH₂)₃S) are structural analogues of the [2Fe]_H subsite of [FeFe]H₂ases. Electrochemical investigation of 1 and 2 in MeCN–[NBu₄][PF₆] under Ar and under CO has demonstrated that the reduction can be resolved into two one-electron transfer steps by using fast scan cyclic voltammetry. At slow scan rates the reduction of 1 tends towards a two-electron process owing to the fast disproportionation of the anion, while the two-electron reduction of 2 is clearly favoured in the presence of CO. Substitution of a CO ligand in 2 by a N-heterocyclic carbene results in the destabilisation of the anion. Thus, in MeCN–, thf- or CH₂Cl₂–[NBu₄][PF₆], the electrochemical reduction of Fe₂(CO)₅L_NHC(μ-pdt)] 3 (L_NHC = 1,3-bis(methyl)-imidazol-2-ylidene, 3a; 1,3-bis(2,4,6-trimethylphenyl)-imidazol-2-ylidene, 3b) occurs in a single-step, two-electron process at moderate scan rates; under appropriate conditions this process can be separated into two one-electron steps. Density Functional Theory calculations successfully rationalize the effects of the S-to-S linkage on the electrochemistry of the complexes.