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...

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Bibliographic Details
Published inDalton transactions : an international journal of inorganic chemistry Vol. 47; no. 31; pp. 10561 - 10568
Main Authors Koch, Felix, Berkefeld, Andreas
Format Journal Article
LanguageEnglish
Published Cambridge Royal Society of Chemistry 2018
Subjects
Chemical bonds
External pressure
Ligands
Nickel
Organic chemistry
Oxidation
Properties (attributes)
Reagents
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Summary: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.
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ISSN:1477-9226
1477-9234
DOI:10.1039/c8dt00275d