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Structure and Reactivity of 1,8-Bis(naphthalenediyl)dipnictanes

机译:1,8-双(萘二噻yl)二维烷的结构和反应性

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摘要

Syntheses and solid-state structures of diarsane Naph(2)As(2) (Naph = 1,8-naphthalenediyl, 1) and (Naph)(5)Sb4Cl2 3 are reported and the sigma-donor capacity of Naph(2)E(2) (E = As 1, Sb 2) was studied in reactions with (coe)Cr(CO)(5) (coe = Z-cyclooctene), yielding [Naph(2)As(2)]-[Cr(CO)(5)](2) (4) and [Naph(2)E(2)][Cr(CO)(5)] (E = As 5, Sb 6). In contrast, reactions of 1 and 3 with Me2SAuCl proceed with oxidation and formation of elemental gold as well as Naph(2)(AsCl)(2) (7) and [NaphSbCl(2)](2) 8. All complexes were characterized by elemental analyses, heteronuclear (H-1, C-13) NMR and FT-IR spectroscopy, as well as single crystal X-ray diffraction. Intermolecular E center dot center dot center dot pi interactions (E = As, Sb), which were observed in 7 and 8, were quantified by use of density functional theory and local coupled cluster electronic structure theory calculations. These allow to assess the nature and relative importance of covalent and noncovalent interactions and illustrate how dispersion interactions change with the electronic structure of the compounds.
机译:报告的液态酸锡(2)(2)(锡甘氨酸钠,1)和(锡)(5)Sb4Cl2 3的合成和固态结构,纳华(2)E的Sigma-供体能力(2)(E = As 1,SB 2)在与(COE)Cr(CO)(5)(CoE = Z-环偶)(Coe = Z-Cyclocentene)的反应中研究,得到[纳华(2)为(2)] - [Cr( CO)(5)](2)(4)和[锡(2)e(2)] [Cr(CO)(5)](E = 5,SB 6)。相反,用ME2SauCl的1和3的反应进行氧化和元素金以及萘(2)(2)(2)(7)和[萘氯(2)](2)8。所有复合物都是表征通过元素分析,异核(H-1,C-13)NMR和FT-IR光谱,以及单晶X射线衍射。通过使用密度泛函理论和局部耦合集群电子结构理论计算来量化在7和8中观察到的分子间E中心点中心点中心点PI相互作用(E = AS,SB)。这些允许评估共价和非价相互作用的性质和相对重要性,并说明了分散相互作用如何随化合物的电子结构而变化。

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