Institut für Anorganische Chemie, Eberhard Karls Universität Tübingen, Auf der Morgenstelle 18, 72076 Tübingen, Germany.
Dalton Trans. 2018 Aug 21;47(31):10561-10568. doi: 10.1039/c8dt00275d. Epub 2018 Feb 26.
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. 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 oxidation at electronically distinct [Ni(μ-SR)] 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)] on overall H oxidation reactivity displayed by Ni-S structures has been investigated quantitatively in addition to external parameters such as solvent and H pressure.
路易斯酸性金属与布朗斯特/路易斯碱性硫供体之间的化学键为 M-S 结构提供了具有各种功能的特性，这些特性与许多过程有关，例如 H 的异裂。由于稳定配体支架的电子性质不同，分子 M-S 结构之间的反应性性质的直接比较可能很困难。这项工作报道了电子上不同的[Ni(μ-SR)]和[Ni-SR]结构的 H 氧化的计量学研究，这些结构源自相同的 1,4-三联苯二硫酚配体。在这种情况下，除了溶剂和 H 压力等外部参数外，还定量研究了含金属副产物（如[HNi(PMe)]）对 Ni-S 结构显示的整体 H 氧化反应性的影响。
