Reactant or reagent? Oxidation of H2 at electronically distinct nickel-thiolate sites [Ni2(μ-SR)2]+ and [Ni–SR]+
The chemical bond between a Lewis-acidic metal and a Brønsted/Lewis-basic sulphur donor provides M–S structures with functional properties that are relevant for a variety of processes such as the heterolytic cleavage of H2. Direct comparison of reactivity properties between molecular M–S structures can be difficult owing to divergent electronic properties of stabilizing ligand scaffolds. This work reports on a mechanistic study of stoichiometric H2 oxidation at electronically distinct [Ni2(μ-SR)2]+ and [Ni–SR]+ structures that derive from the same 1,4-terphenyldithiophenol ligand. In this context, the effect of metal containing side-products such as [HNi(PMe3)4]+ on overall H2 oxidation reactivity displayed by Ni–S structures has been investigated quantitatively in addition to external parameters such as solvent and H2 pressure.
- This article is part of the themed collection: New Talent: Europe