Coordination of Halide and Chalcogenolate Anions to Heavier 1,2,5-Chalcogenadiazoles: Experiment and Theory
Coordination of Halide and Chalcogenolate Anions to Heavier 1,2,5-Chalcogenadiazoles: Experiment and Theory
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DOI：
10.1021/om5006403
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发表时间：
2014-08
期刊：
影响因子：
2.8
通讯作者：
N. Semenov;A. V. Lonchakov;N. Pushkarevsky;E. Suturina;V. V. Korolev-V.;E. Lork;V. Vasiliev;S. Konchenko;J. Beckmann;N. Gritsan;A. Zibarev
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文献类型：
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作者：
N. Semenov;A. V. Lonchakov;N. Pushkarevsky;E. Suturina;V. V. Korolev-V.;E. Lork;V. Vasiliev;S. Konchenko;J. Beckmann;N. Gritsan;A. Zibarev
阴离子X-配位的新产物（X = F，I，PhS）与3，4-二氰基-1，2，5-碲二唑（1）的Te原子反应合成了[（Me 2N）3S]+[1-F]−（9），[K（18-冠-6）]+[1-I]-（10）和[K（18-冠-6）]+[1-SPh]-·THF（11）。在10的晶格中，I原子桥接在两个Te原子之间。用DFT、QTAIM和NBO计算，结合UV-vis、IR/拉曼和MS-ESI技术，研究了9 - 11盐和1，2，5-硫属二唑（硫属元素= S、Se、Te）与阴离子X-（X = F、Cl、Br、I、PhS）的加合物阴离子的成键情况.在所有情况下，配位键的性质是负超共轭，涉及电子密度从X-转移到杂环。成键相互作用的能量在与弱化学键的能量（例如，有机叠氮化物中的内部N-N键）至1.86千卡mol-1，与...
New products of coordination of anions X– (X = F, I, PhS) to the Te atom of 3,4-dicyano-1,2,5-telluradiazole (1) were synthesized in high yields and characterized by X-ray diffraction (XRD) as the salts [(Me2N)3S]+[1-F]− (9), [K(18-crown-6)]+[1-I]− (10), and [K(18-crown-6)]+[1-SPh]−·THF (11), respectively. In the crystal lattice of 10, I atoms are bridging between two Te atoms. The bonding situation in anions of the salts 9–11 and some other adducts of 1,2,5-chalcogenadiazoles (chalcogen = S, Se, Te) and anions X– (X = F, Cl, Br, I, PhS) was studied using DFT, QTAIM, and NBO calculations, for 9–11 in combination with UV–vis, IR/Raman, and MS-ESI techniques. In all cases, the nature of the coordinate bond is negative hyperconjugation involving the transfer of electron density from X– to the heterocycles. The energy of the bonding interaction varies in a range from ∼30 kcal mol–1 comparable with energies of weak chemical bonds (e.g., internal N–N bond in organic azides) to ∼86 kcal mol–1 comparable with an ...