Auer Henry, Guehne Robin, Bertmer Marko, Weber Sebastian, Wenderoth Patrick, Hansen Thomas Christian, Haase Jürgen, Kohlmann Holger
Department of Inorganic Solid-State Chemistry, Saarland University , Am Markt, Zeile 3, 66125 Saarbrücken, Germany.
Institut Laue-Langevin , 71 Avenue des Martyrs, CS 20156, 38042 Grenoble Cedex 9, France.
Inorg Chem. 2017 Feb 6;56(3):1061-1071. doi: 10.1021/acs.inorgchem.6b01944. Epub 2017 Jan 18.
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 and BaSnD 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 Ae tetrahedra; thus, the features of both interstitial hydrides and polyanionic hydrides are represented. BaSiD 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.
津特耳相通过纳入氢负离子（间隙氢化物）或通过氢与聚阴离子的共价键合（聚阴离子氢化物）形成氢化物，这产生了各种不同的组成和键合情况。SrGe、BaSi和BaSn的氢化物（氘化物）通过CrB型津特耳相AeTt的氢化（氘化）制备，并通过实验室X射线、同步加速器和中子衍射、核磁共振光谱以及量子化学计算进行表征。SrGeD和BaSnD显示出由津特耳相中包含的三条锯齿链连接而成的Tt原子的凝聚船状六元环。这些新的聚阴离子基序由共价键合的H原子终止，d(Ge-D) = 1.521(9) Å，d(Sn-D) = 1.858(8) Å。额外的氢负离子位于Ae四面体中；因此，间隙氢化物和聚阴离子氢化物的特征都得到了体现。BaSiD保留了与母体津特耳相中相同的锯齿状Si链，但在氢化物（氘化物）中，它由H（D）原子终止，从而形成了d(Si-D) = 1.641(5) Å的线性（SiD）链。
