Direct structural and mechanistic insights into fast bimolecular chemical reactions in solution through a coupled XAS/UV–Vis multivariate statistical analysis,Dalton Transactions

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Direct structural and mechanistic insights into fast bimolecular chemical reactions in solution through a coupled XAS/UV–Vis multivariate statistical analysis
Dalton Transactions ( IF 3.5 ) Pub Date : 2020-11-25 , DOI: 10.1039/d0dt03083j
Francesco Tavani ₁ , Giorgio Capocasa , Andrea Martini , Francesco Sessa , Stefano Di Stefano , Osvaldo Lanzalunga , Paola D'Angelo

Affiliation

In this work, we obtain detailed mechanistic and structural information on bimolecular chemical reactions occurring in solution on the second to millisecond time scales through the combination of a statistical, multivariate and theoretical analysis of time-resolved coupled X-ray Absorption Spectroscopy (XAS) and UV–Vis data. We apply this innovative method to investigate the sulfoxidation of p-cyanothioanisole and p-methoxythioanisole by the nonheme Fe^IV oxo complex [N4Py·Fe^IV(O)]²⁺ (N4Py = N,N-bis(2-pyridylmethyl)-N-bis(2-pyridyl)methylamine) in acetonitrile at room temperature. By employing statistical and multivariate techniques we determine the number of key chemical species involved along the reaction paths and derive spectral and concentration profiles for the reaction intermediates. From the quantitative analysis of the XAS spectra we obtain accurate structural information for all reaction intermediates and provide the first structural characterization in solution of complex [N4Py·Fe^III(OH)]²⁺. The employed strategy is promising for the spectroscopic characterization of transient species formed in redox reactions.

中文翻译：

通过耦合 XAS/UV-Vis 多变量统计分析，直接了解溶液中快速双分子化学反应的结构和机理

在这项工作中，我们通过结合时间分辨耦合 X 射线吸收光谱 (XAS) 和紫外-可见数据。我们应用此创新方法来研究的磺化氧化p -cyanothioanisole和p -methoxythioanisole由非血红素铁^IV氧络合物[N4Py·铁^IV（O）] ^{2 +}（N4Py = Ñ，ñ -双（2-吡啶基甲基） - ñ-双（2-吡啶基）甲胺）的乙腈溶液，室温下。通过采用统计和多元技术，我们确定了反应路径中涉及的关键化学物质的数量，并推导出反应中间体的光谱和浓度分布。通过对 XAS 光谱的定量分析，我们获得了所有反应中间体的准确结构信息，并首次提供了复合物 [N4Py·Fe ^III (OH)] ²⁺溶液中的结构表征。所采用的策略有望用于氧化还原反应中形成的瞬态物种的光谱表征。

更新日期：2020-12-09

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