Hydrides of Alkaline Earth–Tetrel (AeTt) Zintl Phases: Covalent Tt–H Bonds from Silicon to Tin

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• 作者：Henry AuerRobin Guehne ; Marko Bertmer ; Sebastian Weber ; Patrick Wenderoth ; Thomas Christian Hansen ; Jürgen Haase ; Holger Kohlmann
• 刊名：Inorganic Chemistry
• 出版年：2017
• 出版时间：February 6, 2017
• 年：2017
• 卷：56
• 期：3
• 页码：1061-1071
• 全文大小：544K
• ISSN：1520-510X

文摘

Zintl phases form hydrides either by incorporating hydride anions (interstitial hydrides) or by covalent bonding of H to the polyanion (polyanionic hydrides), which yields a variety of different compositions and bonding situations. Hydrides (deuterides) of SrGe, BaSi, and BaSn were prepared by hydrogenation (deuteration) of the CrB-type Zintl phases AeTt and characterized by laboratory X-ray, synchrotron, and neutron diffraction, NMR spectroscopy, and quantum-chemical calculations. SrGeD_4/3–x and BaSnD_4/3–x show condensed boatlike six-membered rings of Tt atoms, formed by joining three of the zigzag chains contained in the Zintl phase. These new polyanionic motifs are terminated by covalently bound H atoms with d(Ge–D) = 1.521(9) Å and d(Sn–D) = 1.858(8) Å. Additional hydride anions are located in Ae₄ tetrahedra; thus, the features of both interstitial hydrides and polyanionic hydrides are represented. BaSiD_2–x retains the zigzag Si chain as in the parent Zintl phase, but in the hydride (deuteride), it is terminated by H (D) atoms, thus forming a linear (SiD) chain with d(Si–D) = 1.641(5) Å.