Cooperative Catalysis at Metal-Sulfur Bonds

Cooperative catalysis has attracted tremendous attention in recent years, emerging as a key strategy for the development of novel atom-economic and environmentally more benign catalytic processes. In particular, Noyori-type complexes with metal-nitrogen bonds have been extensively studied and evolved as privileged catalysts in hydrogenation chemistry. In contrast, catalysts containing metal-sulfur bonds as the reactive site are out of the ordinary, despite their abundance in living systems, where they are assumed to play a key role in biologically relevant processes. For instance, the heterolysis of dihydrogen catalyzed by [NiFe] hydrogenase is likely to proceed through cooperative H-H bond splitting at a polar nickel-sulfur bond. This Account provides an overview of reported metal-sulfur complexes that allow for cooperative E-H bond (E = H, Si, and B) activation and highlights the potential of this motif in catalytic applications. In recent years, our contributions to this research field have led to the development of a broad spectrum of synthetically useful transformations catalyzed by cationic ruthenium(II) thiolate complexes of type [(DmpS)Ru(PR₃)]⁺BAr^F₄^- (DmpS = 2,6-dimesitylphenyl thiolate, Ar^F = 3,5-bis(trifluoromethyl)phenyl). The tethered coordination mode of the bulky 2,6-dimesitylphenyl thiolate ligand is crucial, stabilizing the coordinatively unsaturated ruthenium atom and also preventing formation of binuclear sulfur-bridged complexes. The ruthenium-sulfur bond of these complexes combines Lewis acidity at the metal center and Lewis basicity at the adjacent sulfur atom. This structural motif allows for reversible heterolytic splitting of E-H bonds (E = H, Si, and B) across the polar ruthenium-sulfur bond, generating a metal hydride and a sulfur-stabilized E⁺ cation. Hence, this activation mode provides a new strategy to catalytically generate silicon and boron electrophiles. After transfer of the electrophile to a Lewis-basic substrate, the resulting neutral ruthenium(II) hydride can either act as a hydride donor (reductant) or as a proton acceptor (Brønsted base); the latter scenario is followed by dihydrogen release. On the basis of this concept, the tethered ruthenium(II) thiolate complexes emerged as widely applicable catalysts for various transformations, which can be categorized into (i) dehydrogenative couplings [Si-C(sp²), Si-O, Si-N, and B-C(sp²)], (ii) chemoselective reductions (hydrogenation and hydrosilylation), and (iii) hydrodefluorination reactions. All reactions are promoted by a single catalyst motif through synergistic metal-sulfur interplay. The most prominent examples of these transformations are the first catalytic protocols for the regioselective C-H silylation and borylation of electron-rich heterocycles following a Friedel-Crafts mechanism.