Department of Chemistry, Iowa State University, Ames, Iowa 50011, USA.
Inorg Chem. 2012 Mar 19;51(6):3548-56. doi: 10.1021/ic202342v. Epub 2012 Feb 24.
Two series of rare-earth-metal (R) compounds, R(7)Au(2)Te(2) (R = Tb, Dy, Ho) and R(6)AuTe(2) (R = Sc, Y, Dy, Ho, Lu), have been synthesized by high-temperature techniques and characterized by X-ray diffraction analyses as monoclinic Er(7)Au(2)Te(2)-type and orthorhombic Sc(6)PdTe(2)-type structures, respectively. Single-crystal diffraction results are reported for Ho(7)Au(2)Te(2), Lu(6)AuTe(2), Sc(6)Au(0.856(2))Te(2), and Sc(6)Au(0.892(3))Te(2). The structure of Ho(7)Au(2)Te(2) consists of columns of Au-centered tricapped trigonal prisms (TCTPs) of Ho condensed into 2D zigzag sheets that are interbridged by Te and additional Ho to form the 3D network. The structure of Lu(6)AuTe(2) is built of pairs of Au-centered Lu TCTP chains condensed with double Lu octahedra in chains into 2D zigzag sheets that are separated by Te atoms. Tight binding-linear muffin-tin orbital-atomic sphere approximation electronic structure calculations on Lu(6)AuTe(2) indicate a metallic property. The principal polar Lu-Au and Lu-Te interactions constitute 75% of the total Hamilton populations, in contrast to the small values for Lu-Lu bonding even though these comprise the majority of the atoms. A comparison of the theoretical results for Lu(6)AuTe(2) with those for isotypic Lu(6)AgTe(2) and Lu(6)CuTe(2) provides clear evidence of the greater relativistic effects in the bonding of Au. The parallels and noteworthy contrasts between Ho(7)Au(2)Te(2) (35 valence electrons) and the isotypic but much electron-richer Nb(7)P(4) (55 valence electrons) are analyzed and discussed.
两种系列的稀土金属(R)化合物,R(7)Au(2)Te(2)(R = Tb,Dy,Ho)和 R(6)AuTe(2)(R = Sc,Y,Dy,Ho,Lu),已经通过高温技术合成,并通过 X 射线衍射分析分别鉴定为单斜的 Er(7)Au(2)Te(2)-型和正交的 Sc(6)PdTe(2)-型结构。报道了 Ho(7)Au(2)Te(2)、Lu(6)AuTe(2)、Sc(6)Au(0.856(2))Te(2)和 Sc(6)Au(0.892(3))Te(2)的单晶衍射结果。Ho(7)Au(2)Te(2)的结构由 Ho 原子中心的三帽三角棱柱(TCTP)的 Au 柱凝结成二维之字形薄片,这些薄片由 Te 和额外的 Ho 桥接,形成 3D 网络。Lu(6)AuTe(2)的结构由 Au 中心的 Lu TCTP 链与链中的双 Lu 八面体凝结而成,形成二维之字形薄片,这些薄片由 Te 原子隔开。对 Lu(6)AuTe(2)的紧束缚-线性 muffin-tin 轨道-原子球近似电子结构计算表明其具有金属性质。主要的极性 Lu-Au 和 Lu-Te 相互作用构成了总 Hamilton 人口的 75%,而 Lu-Lu 键合的数值很小,尽管这些键合占大多数原子。Lu(6)AuTe(2)的理论结果与等结构的 Lu(6)AgTe(2)和 Lu(6)CuTe(2)的理论结果进行比较,清楚地证明了 Au 键合中相对论效应的增强。对 Ho(7)Au(2)Te(2)(35 个价电子)和等结构但电子数更多的 Nb(7)P(4)(55 个价电子)进行了分析和讨论,比较了它们的相似之处和显著差异。