Liu Gaoxiang, Fedik Nikita, Martinez-Martinez Chalynette, Ciborowski Sandra M, Zhang Xinxing, Boldyrev Alexander I, Bowen Kit H
Department of Chemistry, Johns Hopkins University, Baltimore, MD, 21218, USA.
Department of Chemistry and Biochemistry, Utah State University, Logan, UT, 84322, USA.
Angew Chem Int Ed Engl. 2019 Sep 23;58(39):13789-13793. doi: 10.1002/anie.201907089. Epub 2019 Aug 19.
We report a Na: →B dative bond in the NaBH cluster, which was designed on the principle of minimum-energy rupture, prepared by laser vaporization, and characterized by a synergy of anion photoelectron spectroscopy and electronic structure calculations. The global minimum of NaBH features a Na-B bond. Its preferred heterolytic dissociation conforms with the IUPAC definition of dative bond. The lone electron pair revealed on Na and the negative Laplacian of electron density at the bond critical point further confirm the dative nature of the Na-B bond. This study represents the first example of a Lewis adduct with an alkalide as the Lewis base.
我们报道了在NaBH团簇中存在一种钠→硼配位键，该团簇基于最小能量断裂原理设计，通过激光蒸发制备，并通过阴离子光电子能谱和电子结构计算相结合的方法进行表征。NaBH的全局最小值具有钠-硼键。其优先的异裂解离符合国际纯粹与应用化学联合会（IUPAC）对配位键的定义。钠上显示的孤电子对以及键临界点处电子密度的负拉普拉斯进一步证实了钠-硼键的配位性质。这项研究代表了以碱化物作为路易斯碱的路易斯加合物的首个实例。
