Thakur Gohil S, Dinnebier Robert, Hansen Thomas C, Assenmacher Wilfried, Felser Claudia, Jansen Martin
Max-Planck-Institut für Chemische Physik fester Stoffe, Nöthnitzer Str. 40, 01187, Dresden, Germany.
Max-Planck-Institut für Festkörperforschung, Heisenbergstr. 1, 70569, Stuttgart, Germany.
Angew Chem Int Ed Engl. 2020 Nov 2;59(45):19910-19913. doi: 10.1002/anie.202008874. Epub 2020 Sep 15.
The seminal qualitative concepts of chemical bonding, as presented by Walter Kossel and Gilbert Newton Lewis back in 1916, have lasting general validity. These basic rules of chemical valence still serve as a touchstone for validating the plausibility of composition and constitution of a given chemical compound. We report on AgPtO, with a composition that violates the basic rules of chemical valence and an exotic crystal structure. The first coordination sphere of platinum is characteristic of tetravalent platinum. Thus, the electron count corresponds to AgPtO*e, where excess electrons are associated with the silver substructure. Such conditions given, it is commonly assumed that the excess electrons are either itinerant or localized in Ag-Ag bonds. However, the material does not show metallic conductivity, nor does the structure feature Ag-Ag pairs. Instead, the excess electrons organize themselves in 2e-4c bonds within the silver substructure. This subvalent silver oxide reveals a new general facet pertinent to silver chemistry.
沃尔特·科塞尔（Walter Kossel）和吉尔伯特·牛顿·刘易斯（Gilbert Newton Lewis）早在1916年提出的化学键定性概念具有持久的普遍有效性。这些化学价的基本规则仍然是验证给定化合物组成和结构合理性的试金石。我们报道了AgPtO，其组成违反了化学价的基本规则且具有奇特的晶体结构。铂的第一配位层具有四价铂的特征。因此，电子数对应于AgPtO*e，其中多余的电子与银亚结构相关。在这种情况下，通常认为多余的电子要么是离域的，要么定域于Ag-Ag键中。然而，该材料不显示金属导电性，其结构中也没有Ag-Ag对。相反，多余的电子在银亚结构内以2e-4c键的形式自行组织。这种低价银氧化物揭示了银化学中一个新的普遍方面。
