Bio-inspired, Multifunctional Metal-Thiolate Motif: From Electron Transfer to Sulfur Reactivity and Small-Molecule Activation

CONSPECTUS: Sulfur-rich metalloproteins and metalloenzymes, containing strongly covalent metal-thiolate (cysteinate) or metal-sulfide bonds in their active site, are ubiquitous in nature. The metal-sulfur motif is a highly versatile tool involved in various biological processes: (i) metal storage, transport, and detoxification; (ii) electron transfer; (iii) activation of the sulfur atom to promote different types of S-based reactions including S-alkylation, S-oxygenation, S-nitrosylation, or disulfide or thiyl radicals formation; (iv) activation of small earth-abundant molecules (such as water, dioxygen, superoxide radical anion, carbon oxides, nitrous oxide, and dinitrogen). This Account describes our investigations carried out during the past 10 years on bio-inspired and biomimetic low-nuclearity complexes containing metal-thiolate bonds. The general objective of these structural, spectroscopic, electrochemical, and catalytic studies was to determine structure-properties-function correlations useful to (i) understanding the peculiar features or the mechanism of the mimicked natural systems and/or (ii) reproducing enzymatic reactivities for specific catalytic applications. By employing a unique highly preorganized N2S2-donor ligand with two thiolate functions, in combination with different first-row transition metals (Mn, Fe, Co, Ni, Cu, Zn, or V), we got access to a series of bio-inspired sulfur-rich complexes displaying a widespread spectrum of structures, properties, and functions. We isolated a dicopper(I) complex that, for the first time, mimicked concomitantly the key structural, spectroscopic, and redox features of the biological Cu-A center, a highly efficient electron transfer agent involved in the respiratory enzyme cytochrome c oxidase. In the field of sulfur activation, we explored (i) sulfur methylation promoted by a Zn-dithiolate complex that mimics Zn-dependent thiolate alkylation proteins and shows different selectivity compared to the Ni and Co congeners and (ii) a series of Co, Fe, and Mn complexes as the first copper-free systems able to promote thiolate/disulfide interconversion mediated by (de)coordination of halides. Concerning metal-centered reactivity, we investigated two families of metal-thiolate catalysts for small-molecule activation, especially relevant in the fields of sustainable fuel production and energy conversion: (i) two isostructural Mn and Fe dinuclear complexes that activate and reduce dioxygen selectively, either to hydrogen peroxide or water as a function of the experimental conditions; (ii) a family of dinuclear MFe (M = Ni or Fe) hydrogenase mimics active for catalytic H-2 evolution both in organic solution and on modified electrodes in water. This Account thus illustrates how the versatility of thiolate ligation can support selected functions for transition metal complexes, depending on the nature of the metal, the nuclearity of the complex, the presence and type of co-ligands, the second coordination sphere effects, and the experimental conditions.