理解质子化盒子配体的结构:来自光谱学和计算研究的见解

IF 1.5 4区 化学 Q3 CHEMISTRY, MULTIDISCIPLINARY
Vladimir Gorbachev, Lara van Tetering, Jonathan Martens, Jos Oomens, Giel Berden, Alexandra Tsybizova, Peter Chen
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引用次数: 0

摘要

质子化和互变异构化显著影响着双(恶唑啉)(BOX)配体的构象景观和非共价相互作用,这对其在催化中的应用至关重要。这些相互作用影响诸如结合亲和力和催化效率等性质。虽然中性BOX配体的重异构化已被报道,但其在质子化形式中的作用仍鲜为人知。本文报道了(S,S−Ph-BOX)H+及其抗变异构衍生物(S,S−Ph-diMeBOX)H+的结构和光谱表征。通过IRMPD光谱和TIMS实验,结合DFT计算,我们发现(S,S−Ph-BOX)H+以互变异构体形式存在,而(S,S−Ph-diMeBOX)H+的构象范围更广,其中确定了N−H⋅⋅⋅N质子共享构象。这些发现提供了对质子化BOX配体中互变异构化和非共价相互作用之间关系的更深入理解,为催化系统的设计提供了见解。
本文章由计算机程序翻译,如有差异,请以英文原文为准。
Understanding the Structure of Protonated Box Ligands: Insights from Spectroscopy and Computational Studies

Protonation and tautomerization significantly impact the conformational landscape and non-covalent interactions in bis(oxazoline) (BOX) ligands, which are crucial for their applications in catalysis. These interactions influence properties such as binding affinity and catalytic efficiency. While tautomerization has been reported for neutral BOX ligands, its role in protonated forms remains less understood. Here we report the structural and spectroscopic characterization of (S,S−Ph-BOX)H+ and its tautomerization-resistant derivative (S,S−Ph-diMeBOX)H+. We show through IRMPD spectroscopy and TIMS experiments, combined with DFT calculations that (S,S−Ph-BOX)H+ is present in its tautomeric form, while a broader conformational landscape is observed for (S,S−Ph-diMeBOX)H+, in which an N−H⋅⋅⋅N proton-shared conformer is identified. These findings provide a deeper understanding of the relationship between tautomerization and non-covalent interactions in protonated BOX ligands, offering insights for the design of catalytic systems.

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来源期刊
Helvetica Chimica Acta
Helvetica Chimica Acta 化学-化学综合
CiteScore
3.00
自引率
0.00%
发文量
60
审稿时长
2.3 months
期刊介绍: Helvetica Chimica Acta, founded by the Swiss Chemical Society in 1917, is a monthly multidisciplinary journal dedicated to the dissemination of knowledge in all disciplines of chemistry (organic, inorganic, physical, technical, theoretical and analytical chemistry) as well as research at the interface with other sciences, where molecular aspects are key to the findings. Helvetica Chimica Acta is committed to the publication of original, high quality papers at the frontier of scientific research. All contributions will be peer reviewed with the highest possible standards and published within 3 months of receipt, with no restriction on the length of the papers and in full color.
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