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首页> 外文期刊>Chemistry: A European journal >Insights into the Tautomerism in meso-Substituted Corroles: A Variable-Temperature ~1H, ~(13)C, ~(15)N, and ~(19)F NMR Spectroscopy Study
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Insights into the Tautomerism in meso-Substituted Corroles: A Variable-Temperature ~1H, ~(13)C, ~(15)N, and ~(19)F NMR Spectroscopy Study

机译：内消旋取代的互变异构体中互变异构的见解：〜1H，〜（13）C，〜（15）N和〜（19）F NMR光谱研究

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摘要

Tris(pentafluorophenyl)corrole and its ~(15)N-enriched isotopomer were studied in [D_8]toluene solution by 1D and 2D variable-temperature NMR techniques to establish the mechanisms of tautomerization of the NH protons inside the interior of the corrole macrocycle. Three such rate processes could be identified of which two modulate the spectral line shapes at temperatures above 205 K and the third is NMR-inaccessible as it is very fast. The latter involves the proton engaged in an unsymmetrical proton sponge unit formed by two pyrrole nitrogen atoms. Temperature and concentration dependences of the two remaining processes were determined. One of them is purely intramolecular and the other is intermolecular at low temperatures, with growing contribution of an intramolecular mechanism at elevated temperatures. The proposed microscopic mechanisms of all these processes are semi-quantitatively confirmed by quantum chemical calculations using density functional theory.
机译：通过一维和二维可变温度核磁共振技术，在[D_8]甲苯溶液中研究了三（五氟苯基）甲氧基及其富集〜（15）N的同位素异构体，以建立该甲氧基大环内部的NH质子互变异构的机理。可以确定三个这样的速率过程，其中两个在205 K以上的温度下调制光谱线的形状，第三个是NMR无法访问的，因为它非常快。后者涉及质子接合在由两个吡咯氮原子形成的不对称质子海绵单元中。确定了其余两个过程的温度和浓度依赖性。其中之一是纯分子内的，而另一个在低温下是分子间的，随着温度升高，分子内机理的作用越来越大。通过使用密度泛函理论的量子化学计算，对所有这些过程提出的微观机理进行了半定量确认。

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