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

作者：Auer Henry; Guehne Robin; Bertmer Marko; Weber Sebastian; Wenderoth Patrick; Hansen Thomas Christian; Haase Juergen; Kohlmann Holger^*

来源：Inorganic Chemistry, 2017, 56(3): 1061-1071.

DOI：10.1021/acs.inorgchem.6b01944

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. SrGeD4/3-x and BaSnD4/3-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) angstrom and d(Sn-D) = 1.858(8) angstrom. Additional hydride anions are located in Ae(4) tetrahedra; thus, the features of both interstitial hydrides and polyanionic hydrides are represented. BaSiD2-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) angstrom.

• 出版日期2017-2-6