Reactant or reagent? Oxidation of H2 at electronically distinct nickel-thiolate sites [Ni2(μ-SR)2]+ and [Ni-SR]+Electronic supplementary information (ESI) available: Cyclic voltammetry, NMR, X-band cw-EPR, and UV/Vis spectroscopic data. See DOI: 10.1039/c8dt00275d

• Main Authors: Koch, Felix, Berkefeld, Andreas
• Format: Journal Article
• Language: English
• Published: 07.08.2018
• ISSN: 1477-9226; 1477-9234
• DOI: 10.1039/c8dt00275d

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 H 2 . 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 H 2 oxidation at electronically distinct [Ni 2 (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(PMe 3 ) 4 ] + on overall H 2 oxidation reactivity displayed by Ni-S structures has been investigated quantitatively in addition to external parameters such as solvent and H 2 pressure. 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 H 2 .