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首页> 外文期刊>Inorganic Chemistry: A Research Journal that Includes Bioinorganic, Catalytic, Organometallic, Solid-State, and Synthetic Chemistry and Reaction Dynamics >Syntheses;~(77)Se,~(203)Tl,and ~(205)Tl NMR;and Theoretical Studies of the Tl_2Se_6~(6-),Tl_3Se_6~(5-),and Tl_3Se_7~(5-) Anions and the X-ray Crystal Structures of [2,2,2-crypt-Na]_4[Tl_4Se_8] centre dot en and [2,2,2-crypt-Na]_2[Tl_2Se_4]_(infinity)
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Syntheses;~(77)Se,~(203)Tl,and ~(205)Tl NMR;and Theoretical Studies of the Tl_2Se_6~(6-),Tl_3Se_6~(5-),and Tl_3Se_7~(5-) Anions and the X-ray Crystal Structures of [2,2,2-crypt-Na]_4[Tl_4Se_8] centre dot en and [2,2,2-crypt-Na]_2[Tl_2Se_4]_(infinity)

机译：合成〜（77）Se，〜（203）Tl和〜（205）Tl NMR;以及Tl_2Se_6〜（6-），Tl_3Se_6〜（5-）和Tl_3Se_7〜（5-）阴离子的理论研究[2,2,2-crypt-Na] _4 [Tl_4Se_8]中心点en和[2,2,2-crypt-Na] _2 [Tl_2Se_4] _（无穷大）的X射线晶体结构

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摘要

The 2,2,2-crypt salts of the Tl_4Se_8~(4-) and [Tl_2Se_4~(2-)]_(infinity)~1 anions have been obtained by extracTlon of the ternary alloy NaTl_(0.5)Se in ethylenediamine (en) in the presence of 2,2,2-crypt and 18-crown-6 followed by vapor-phase diffusion of THF into the en extract.The [2,2,2-crypt-Na]_4[Tl_4Se_8] centre dot en crystallizes in the monoclinic space group P2_1,with Z = 2 and a = 14.768(3) A,b = 16.635(3) A,c = 21.254(4) A,beta = 94.17(3) deg at -123 deg C,and the [2,2,2-crypt-Na]_2[Tl_2Se_4]_(infinity)~1 en crystallizes in the monoclinic space group P2_1/c,with Z - 4 and a = 14.246(2) A,b = 14.360(3) A,c = 26.673(8) A,beta = 99.87(3) deg at -123 deg C.The Tl~(III) anions,Tl_2Se_6~(6-) and Tl_3Se_7~(5-) and the mixed oxidaTlon state Tl~I/Tl~(III) anion,Tl_3Se_6~(5-),have been obtained by extracTlon of NaTl_(0.5)Se and NaTlSe in en,in the presence of 2,2,2-crypt and/or in liquid NH_3,and have been characterized in soluTlon by low-temperature ~(77)Se,~(203)Tl,and ~(205)Tl NMR spectroscopy.The ~1J(~(203,205)Tl-~(77)Se) and ~2J(~(203,205)Tl-~(203,205)Tl) couplings of the three anions have been used to arrive at their soluTlon structures by detailed analyses and simulaTlons of all spin mulTlplets that comprise the ~(205,203)Tl NMR subspectra arising from natural abundance ~(205,203)Tl and ~(77)Se isotopomer distribuTlons.The structure of Tl_2Se_6~(6-) is based on a Tl_2Se_2 ring in which each thallium is bonded to two exo-selenium atoms so that these thalliums are four-coordinate and possess a formal oxidaTlon state of +3.The Tl_4Se_8~(4-) anion is formally derived from the Tl_2Se_6~(6-) anion by coordinaTlon of each pair of terminal Se atoms to the Tl~(III) atom of a TlSe~+ caTlon.The structure of the [Tl_2Se_4~(2-)]_(infinity)~1anion is comprised of edge-sharing distorted TlSe_4 tetrahedra that form infinite,one-dimensional [Tl_2Se_4~(2-)]l chains.The structures of Tl_3Se_6~(5-) and Tl_3Se_7~(5-) are derived from Tl_4Se_4-cubes in which one thallium atom has been removed and two and three exo-selenium atoms are bonded to thallium atoms,respecTlvely,so that each is four-coordinate and possesses a formal oxidaTlon state of +3 with the remaining three-coordinate thallium atom in the +1 oxidaTlon state.Quantum mechanical calculaTlons at the MP2 level of theory show that the Tl_2Se_6~(6-),Tl_3Se_6~(5-),Tl_3Se_7~(5-),and Tl_4Se_8~(4-) anions exhibit true minima and display geometries that are in agreement with their experimental structures.Natural bond orbital and electron localizaTlon funcTlon analyses were uTllized in describing the bonding in the present and previously published Tl/Se anions,and showed that the Tl_2Se_6~(6-),Tl_3Se_6~(5-),Tl_3Se_7~(5-),and Tl_4Se_8~(4-) anions are electron-precise rings and cages.
机译：Tl_4Se_8〜（4-）和[Tl_2Se_4〜（2-）] _（无穷大）〜1阴离子的2,2,2-crypt盐是通过在乙二胺中将三元合金NaTl_（0.5）Se萃取得到的（ en）在2,2,2-crypt和18-crown-6存在下，然后将THF气相扩散至en提取物中。[2,2,2-crypt-Na] _4 [Tl_4Se_8]中心点en在单斜空间群P2_1 / n中结晶，Z = 2并且a = 14.768（3）A，b = 16.635（3）A，c = 21.254（4）A，beta = 94.17（3）度-123摄氏度，[2,2,2-crypt-Na] _2 [Tl_2Se_4] _（infinity）〜1在单斜空间群P2_1 / c中结晶，Z-4且a = 14.246（2）A，在-123℃下b = 14.360（3）A，c = 26.673（8）A，β= 99.87（3）度.Tl〜（III）阴离子Tl_2Se_6〜（6-）和Tl_3Se_7〜（5-）在2,2,2-crypt的存在下，通过NaTl_（0.5）Se和NaTlSe的萃取制备了混合态的Tl〜I / Tl〜（III）阴离子Tl_3Se_6〜（5-）。和/或液态NH_3，并且在溶液中的特征是低温〜（77）Se，〜（203）Tl和〜（205）Tl N MR光谱法。三种阴离子的〜1J（〜（203,205）Tl ~~（77）Se）和〜2J（〜（203,205）Tl ~~（203,205）Tl）偶联已用于通过以下方法得出它们的溶液结构由自然丰度〜（205,203）T1和〜（77）Se同位素异构体分布引起的〜（205,203）T1 NMR亚谱的所有自旋多核苷酸的详细分析和模拟.Tl_2Se_6〜（6-）的结构基于Tl_2Se_2每个each与两个外硒原子键合的环，使这些four具有四配位并具有+3的形式氧化态。Tl_4Se_8〜（4-）阴离子是从Tl_2Se_6〜（6-）形式衍生而来的每个末端Se原子对与TlSe〜+ caTlon的Tl〜（III）原子的配位阴离子。[Tl_2Se_4〜（2-）] _（无限）〜1阴离子的结构由扭曲的边共享构成TlSe_4四面体形成无限的一维[Tl_2Se_4〜（2-）] l链。Tl_3Se_6〜（5-）和Tl_3Se_7〜（5-）的结构源自Tl_4Se_4-立方体，其中一个al原子分别被除去，并且两个和三个外硒原子分别与th原子键合，从而每个原子都是四配位的，并具有+3的形式氧化态，其余三配位的th原子处于+1氧化态。在MP2理论水平上的量子力学计算结果表明Tl_2Se_6〜（6-），Tl_3Se_6〜（5-），Tl_3Se_7〜（5-）和Tl_4Se_8〜（4-）阴离子表现出真正的极小值并显示出几何形状运用自然键轨道和电子定位功能分析描述了目前和以前发表的Tl / Se阴离子的键合情况，结果表明Tl_2Se_6〜（6-），Tl_3Se_6〜（5-），Tl_3Se_7 〜（5-）和Tl_4Se_8〜（4-）阴离子是电子精确的环和笼子。

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