A validated experimental NMR parameter dataset of organic molecules to assist benchmarking of 3D structure determination methods.

IF 3.6 3区化学 Q2 CHEMISTRY, ANALYTICAL

Analyst Pub Date : 2025-05-29 DOI:10.1039/d5an00240k

Claire Louise Dickson, Sadia Mohammed, Lyrelle S. L. Jones, Duncan J Crick, Wojciech Augustyniak, Michael Beaumont, Jan-Christoph Westermann, Sarah Henshaw, Steven T Johnston, Zoltan Takacs, Charles Blundell, Martin Watson, Craig Philip Butts

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Abstract

Over 1000 accurately defined and validated experimental long-range proton-carbon (nJCH) and proton-proton (nJHH) scalar coupling constants, with assigned 1H/13C chemical shifts and their corresponding 3D structures are reported for fourteen relatively complex organic molecules. The experimental dataset comprises 775 nJCH, 300 nJHH, 332 1H chemical shifts and 336 13C chemical shifts, all validated against DFT-calculated values to identify misassignments. A subset of 565 nJCH, 205 nJHH, 172 1H chemical shifts and 202 13C chemical shifts from rigid portions of these molecules have been identified which could be particularly valuable for benchmarking computational methods for predicting NMR parameters. An exemplar application of this dataset is presented through benchmarking of the DFT mPW1PW91/6-311g(dp) level of theory for computation of chemical shifts and scalar coupling constants and for testing scaling approaches for generating experimentally-relevant chemical shifts from DFT-computed magnetic shielding tensors.

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一个经过验证的有机分子实验核磁共振参数数据集，以协助对标三维结构确定方法。

报道了14种相对复杂的有机分子中1000多个精确定义和验证的实验远程质子-碳（nJCH）和质子-质子（nJHH）标量耦合常数，具有指定的1H/13C化学位移及其相应的三维结构。实验数据集包括775个nJCH， 300个nJHH， 332个1H化学位移和336个13C化学位移，所有化学位移都根据dft计算值进行验证以识别错误分配。已经确定了这些分子刚性部分的565个nJCH， 205个nJHH， 172个1H化学位移和202个13C化学位移的子集，这对于预测核磁共振参数的基准计算方法特别有价值。通过对DFT mPW1PW91/6-311g（dp）水平的理论进行基准测试，提出了该数据集的一个示例应用，用于计算化学位移和标量耦合常数，并用于测试从DFT计算的磁屏蔽张量生成实验相关化学位移的缩放方法。

本文章由计算机程序翻译，如有差异，请以英文原文为准。

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