Kenzler Sebastian, Fetzer Florian, Schrenk Claudio, Pollard Nia, Frojd Andrew R, Clayborne Andre Z, Schnepf Andreas
Institute of Inorganic Chemistry, Universität Tübingen, Auf der Morgenstelle 18, 72076, Tübingen, Germany.
Department of Chemistry, Howard University, 525 College Street, NW, Washington, D.C., 20059, USA.
Angew Chem Int Ed Engl. 2019 Apr 23;58(18):5902-5905. doi: 10.1002/anie.201900644. Epub 2019 Mar 26.
Three multi-shell metalloid gold clusters of the composition Au (R P) Cl (R=Et, Pr, Bu) were synthesized in a straightforward fashion by reducing R PAuCl with NaBH in ethanol. The Au core comprises two shells, with the inner one constituting a tilted icosahedron and the outer one showing a distorted dodecahedral arrangement. The outer shell is completed by eight chloride atoms and twelve R P groups. The inner icosahedron shows bond lengths typical for elemental gold while the distances of the gold atoms in the dodecahedral arrangement are in the region of aurophilic interactions. Quantum-chemical calculations illustrate that the Jahn-Teller effect observed within the cluster core can be attributed to the electronic shell filling. The easily reproducible synthesis, good solubility, and high yields of these clusters render them perfect starting points for further research.
通过在乙醇中用硼氢化钠还原RPAuCl，以直接的方式合成了三种组成分别为Au (R P) Cl（R = 乙基、丙基、丁基）的多壳层类金属金簇合物。金核由两个壳层组成，内层构成一个倾斜的二十面体，外层呈现出扭曲的十二面体排列。外壳由八个氯原子和十二个R P基团构成。内层二十面体显示出元素金典型的键长，而十二面体排列中金原子之间的距离处于亲金相互作用的范围内。量子化学计算表明，在簇合物核心观察到的 Jahn - Teller效应可归因于电子壳层填充。这些簇合物易于重现的合成方法、良好的溶解性和高产率使其成为进一步研究的理想起点。
