Gellrich Urs
Institut für Organische Chemie, Justus-Liebig-Universität Giessen, Heinrich-Buff-Ring 17, 35392, Giessen, Germany.
Angew Chem Int Ed Engl. 2018 Apr 16;57(17):4779-4782. doi: 10.1002/anie.201713119. Epub 2018 Mar 12.
A pyridone borane complex that liberates dihydrogen under mild conditions is described. The reverse reaction, dihydrogen activation by the formed pyridonate borane complex, is achieved under moderate H pressure (2 bar) at room temperature. DFT and DLPNO-CCSD(T) computations reveal that the active form of the pyridonate borane complex is a boroxypyridine that can be described as a single component frustrated Lewis pair (FLP). Significantly, the boroxypyridine undergoes a chemical transformation to a neutral pyridone donor ligand in the course of the hydrogen activation. This unprecedented mode of action may thus, in analogy to metal-ligand cooperation, be regarded as an example of boron-ligand cooperation.
本文描述了一种在温和条件下能释放出氢气的吡啶硼烷配合物。通过所形成的吡啶硼酸盐配合物实现的逆反应——氢气活化，在室温下中等氢气压力（2 巴）条件下得以实现。密度泛函理论（DFT）和密度拟合二级微扰理论耦合簇方法（DLPNO-CCSD(T)）计算表明，吡啶硼酸盐配合物的活性形式是一种硼氧基吡啶，可将其描述为单一组分的受阻路易斯酸碱对（FLP）。值得注意的是，在氢气活化过程中，硼氧基吡啶会发生化学转化，生成中性的吡啶酮供体配体。因此，这种前所未有的作用模式类似于金属-配体协同作用，可被视为硼-配体协同作用的一个例子。
