Department of Chemistry, University of California, Davis, One Shields Avenue, Davis, California 95616, United States.
Inorg Chem. 2013 Jun 17;52(12):7061-7. doi: 10.1021/ic400584w. Epub 2013 Jun 4.
Barium gold polyphosphide BaAu2P4 was synthesized from elements and structurally characterized by single crystal X-ray diffraction. BaAu2P4 crystallizes in a new structure type, in the orthorhombic space group Fddd (No. 70) with a = 6.517(1) Å, b = 8.867(2) Å, c = 21.844(5) Å. The crystal structure of BaAu2P4 consists of Au–P layers separated by layers of Ba atoms. Each Au–P layer is composed of infinite ∞(1)(P–) chains of unique topology linked together by almost linearly coordinated Au atoms. According to Zintl–Klemm formalism, this compound is charge balanced assuming closed shell d10 configuration for Au: Ba2+(Au+)2(P–)4. Magnetic and solid state NMR measurements together with quantum-chemical calculations reveal diamagnetic and semiconducting behavior for the investigated polyphosphide, which is as expected for the charged balanced Zintl phase. Electron localization function and crystal orbital Hamilton population analyses reveal strong P–P and Au–P bonding and almost nonbonding Au–Au interactions in BaAu2P4.
钡金多磷化物 BaAu2P4 由元素合成，并通过单晶 X 射线衍射进行结构表征。BaAu2P4 结晶为新的结构类型，属于正交晶系 Fddd（No.70）空间群，a = 6.517(1)Å，b = 8.867(2)Å，c = 21.844(5)Å。BaAu2P4 的晶体结构由 Au-P 层和 Ba 原子层交替组成。每个 Au-P 层由独特拓扑的无限 ∞(1)(P–)链组成，这些链通过几乎线性配位的 Au 原子连接在一起。根据 Zintl-Klemm 形式，假设 Au 具有闭合壳层 d10 构型，该化合物的电荷平衡：Ba2+(Au+)2(P–)4。磁性和固态 NMR 测量以及量子化学计算表明，所研究的多磷化物具有抗磁性和半导体行为，这与带电荷的 Zintl 相一致。电子定域函数和晶体轨道哈密顿人口分析表明，BaAu2P4 中存在强烈的 P-P 和 Au-P 键合，以及几乎非键合的 Au-Au 相互作用。
