199Hg NMR Shielding and Chemical Shifts of 2-, 3-, and 4-Coordinate Hg(II)-Thiolate Species.

IF 4.3 2区 化学 Q1 CHEMISTRY, INORGANIC & NUCLEAR
Inorganic Chemistry Pub Date : 2024-12-16 Epub Date: 2024-11-29 DOI:10.1021/acs.inorgchem.4c03518
Louise M Jessen, Stephan P A Sauer, Lars Hemmingsen
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引用次数: 0

Abstract

Spectroscopic characterization of Hg(II)-thiolate complexes is central to the bioinorganic chemistry of Hg(II). Interpretation of 199Hg NMR usually relies on data recorded for reference compounds; however, here, it is demonstrated that 199Hg NMR chemical shifts may be calculated within 40 ppm of experimental values for 2-, 3-, and 4-coordinate Hg(II)-thiolate complexes, using the PBE0 functional, the QZ4P basis set on Hg and S and TZP on all other atoms, and SO-ZORA to account for relativistic effects. The chemical shift is particularly sensitive to the Hg-S bond length (ca. 300 ppm/0.1 Å per Hg-S bond), while it is less sensitive to changes of S-Hg-S angles (up to 40 ppm/10 degrees 1). Rigid rotation of the methyl groups around the Hg-S axis in model complexes, [Hg(SCH3)n]2-n (n = 2, 3, 4), may give rise to changes of up to 100 ppm. Finally, calculations of the 199Hg NMR chemical shift for a model system of the Hg(II) binding site in the MerR protein demonstrate that experimental 199Hg NMR chemical shift data in combination with DFT calculations may be used as a constraint in the optimization of Hg(II) sites in proteins.

2-、3-和4-配位Hg(II)-硫化物的核磁共振屏蔽和化学位移。
Hg(II)-硫酸盐配合物的光谱表征是Hg(II)生物无机化学的核心。199Hg核磁共振解译通常依赖于参考化合物的记录数据;然而,这里证明了199Hg NMR化学位移可以在实验值的40ppm范围内计算2-,3-和4-坐标Hg(II)-硫代酸盐配合物,使用PBE0功能,在Hg和S上设置QZ4P基,在所有其他原子上设置TZP,以及SO-ZORA来解释相对论效应。化学位移对Hg- s键长度特别敏感(每个Hg- s键约300 ppm/0.1 Å),而对S-Hg-S角度的变化不太敏感(高达40 ppm/10度1)。在模型配合物中,甲基围绕Hg- s轴的刚性旋转,[Hg(SCH3)n]2-n (n = 2,3,4),可能会引起高达100 ppm的变化。最后,对MerR蛋白中Hg(II)结合位点模型系统的199Hg NMR化学位移计算表明,结合DFT计算的实验199Hg NMR化学位移数据可以作为蛋白质中Hg(II)位点优化的约束。
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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来源期刊
Inorganic Chemistry
Inorganic Chemistry 化学-无机化学与核化学
CiteScore
7.60
自引率
13.00%
发文量
1960
审稿时长
1.9 months
期刊介绍: Inorganic Chemistry publishes fundamental studies in all phases of inorganic chemistry. Coverage includes experimental and theoretical reports on quantitative studies of structure and thermodynamics, kinetics, mechanisms of inorganic reactions, bioinorganic chemistry, and relevant aspects of organometallic chemistry, solid-state phenomena, and chemical bonding theory. Emphasis is placed on the synthesis, structure, thermodynamics, reactivity, spectroscopy, and bonding properties of significant new and known compounds.
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