Harnying Wacharee, Wen Hui-Chung, Martens Jonathan, Berden Giel, Oomens Jos, Roithová Jana, Berkessel Albrecht, Schäfer Mathias, Meijer Anthony J H M
Department of Chemistry, Institute of Organic Chemistry, University of Cologne, Cologne, Germany.
Radboud University, Institute for Molecules and Materials, FELIX Laboratory, Nijmegen, The Netherlands.
Phys Chem Chem Phys. 2025 Jun 25;27(25):13543-13556. doi: 10.1039/d5cp01532d.
The Curtius and the Wolff rearrangement reactions are investigated in the gas phase by tandem mass spectrometry (MS) and infrared ion spectroscopy (IRIS), probing the nature and intrinsic reactivity of three acyl azides and of one α-diazo keto analyte and that of their N-loss products at temperatures around 300 K. Our study uses tailor-made precursor ions with innocent charge tags, which are activated upon collision-induced dissociation (CID). Our tandem-MS infrared ion spectroscopy (IRIS) study clearly evidences concerted N-loss reactions delivering the ultimate reaction products of the Curtius reaction, , the isocyanates, and the ones of the Wolff reaction, , the ketenes. We show that this is fully consistent with the reaction mechanism predicted by quantum-chemical calculations. All IRIS data interpretation rests on computed linear IR spectra of ion structures identified by computational analysis based on DFT calculations with CCSD(T)-F12b energies.
通过串联质谱（MS）和红外离子光谱（IRIS）在气相中研究了库尔提斯重排反应和沃尔夫重排反应，在约300 K的温度下探究了三种酰基叠氮化物和一种α-重氮酮分析物及其脱氮产物的性质和固有反应活性。我们的研究使用了带有无害电荷标签的特制前体离子，这些离子在碰撞诱导解离（CID）时被激活。我们的串联质谱红外离子光谱（IRIS）研究清楚地证明了协同脱氮反应生成了库尔提斯反应的最终反应产物异氰酸酯，以及沃尔夫反应的最终反应产物烯酮。我们表明，这与量子化学计算预测的反应机理完全一致。所有IRIS数据解释均基于通过基于DFT计算和CCSD(T)-F12b能量的计算分析确定的离子结构的计算线性红外光谱。
