对所声称的稳定非环状1,2 - 二亚砜分离方法的重新审视。

Re-examination of the Claimed Isolation of Stable Noncyclic 1,2-Disulfoxides.

作者信息

Block Eric, Cotelesage Julien J H, Dikarev Evgeny, Garosi Benedetta, George Graham N, Musah Rabi A, Vogt Linda I, Wei Zheng, Zhang Yuxuan

机构信息

Department of Chemistry, University at Albany, State University of New York, Albany, New York 12222, United States.

Molecular and Environmental Sciences Group, Department of Geological Sciences, University of Saskatchewan, Saskatoon, Saskatchewan S7N 5E2, Canada.

出版信息

Org Lett. 2024 Nov 15;26(45):9619-9624. doi: 10.1021/acs.orglett.4c02849. Epub 2024 Sep 4.

DOI:10.1021/acs.orglett.4c02849

PMID:39230394

原文链接:https://pmc.ncbi.nlm.nih.gov/articles/PMC11574841/

Abstract

Re-examination of the claimed isolation and X-ray characterization of di--tolyl and dimesityl 1,2-disulfoxides from thermolysis of the corresponding aryl sulfinimines and thiosulfinates showed that the isolated disulfide dioxides are instead the well-known isomeric thiosulfonates, as confirmed by XAS, DART-MS, X-ray, IR and NMR methods. Concerns with the original X-ray structures are addressed. Our results agree with the DFT prediction of very weak diaryl 1,2-disulfoxide S-S bond dissociation enthalpies. For now, room-temperature-stable noncyclic 1,2-disulfoxides remain unknown.

摘要

对从相应芳基亚磺酰亚胺和硫代亚磺酸盐热解中声称分离出的二 - 甲苯基和二均三甲苯基1,2 - 二亚砜进行重新检查，并通过X射线表征发现，分离出的二硫化物二氧化物实际上是众所周知的异构体硫代磺酸盐，这已通过X射线吸收光谱（XAS）、直接分析实时质谱（DART-MS）、X射线、红外光谱（IR）和核磁共振（NMR）方法得到证实。文中还讨论了对原始X射线结构的相关问题。我们的结果与密度泛函理论（DFT）对非常弱的二芳基1,2 - 二亚砜S - S键解离焓的预测一致。目前，室温稳定的非环状1,2 - 二亚砜仍然未知。