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首页> 外文期刊>Chemistry: A European journal >Intramolecular triarylmethane-triarylmethylium complexes with a naphthalene-1,8-diyl skeleton: Isolation, structure, and reactivities of the C-H-bridged carbocations
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Intramolecular triarylmethane-triarylmethylium complexes with a naphthalene-1,8-diyl skeleton: Isolation, structure, and reactivities of the C-H-bridged carbocations

机译：带有萘-1,8-二基骨架的分子内三芳基甲烷-三芳基甲基鎓配合物：C-H-桥连碳正离子的分离，结构和反应性

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摘要

Isolation and low-temperature X-ray analyses of intramolecular triarylmethane-triarylmethylium complexes with a naphthalene-1,8-diyl-type skeleton have been achieved. These bridged cations prefer a C-H localized structure both in solution and in the solid state. The bridging hydrogen undergoes a facile intramolecular 1,5-hydride shift from one carbon to another in solution. The C-H delocalized geometry is suggested to be the transition-state structure of the degenerate rearrangement. Charge-transfer interaction from the triarylmethane to the triarylmethylium units is evident in the electronic spectra. This interaction stabilizes the present cations. Low reactivity toward Bronsted acids indicates that these species are not the reaction intermediates in the acid-assisted long-bond cleavage of 1, 1,2,2-tetraarylace-naphthene derivatives.
机译：具有萘-1,8-二基型骨架的分子内三芳基甲烷-三芳基甲基鎓配合物的分离和低温X射线分析已实现。这些桥连的阳离子在溶液和固态中均优选C-H局部结构。桥接的氢在溶液中经历从一个碳到另一个碳的容易的分子内1，5-氢化物转变。 C-H离域几何结构被建议是简并重排的过渡态结构。从三芳基甲烷到三芳基甲基鎓单元的电荷转移相互作用在电子光谱中是明显的。这种相互作用稳定了目前的阳离子。对布朗斯台德酸的低反应性表明，这些物质不是1、1,2,2-四芳基环烷衍生物的酸辅助长键裂解中的反应中间体。

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