Institute of Organic Chemistry, National Academy of Sciences, Murmanska Str. 5, 02094 Kyiv, Ukraine.
Igor Sikorsky Kyiv Polytechnic Institute, National Technical University of Ukraine, Prosp. Peremohy 37, 03056 Kyiv, Ukraine.
Molecules. 2022 Feb 22;27(5):1458. doi: 10.3390/molecules27051458.
Recently, an unusual elongation of the C-S bond was observed experimentally for some sulfur-containing heterocycles. Using a superior ab initio (SCS-MP2/cc-pVTZ) level of theory, we showed that the phenomenon can be explained by a contribution of a donor-acceptor adduct of a carbene with an unsaturated ligand. One may achieve further elongation of the C-S bond, eventually turning it to a coordinate one, by increasing the stability of each part of the system as, e.g., in the utmost case of spiro adducts with Arduengo carbenes. The effect of carbene stability was quantified by employing the isodesmic reactions of carbene exchange.
最近，一些含硫杂环的实验中观察到 C-S 键的异常伸长。使用优越的从头算（SCS-MP2/cc-pVTZ）理论水平，我们表明这种现象可以通过卡宾与不饱和配体的给体-受体加合物的贡献来解释。通过增加系统各部分的稳定性，可以进一步延长 C-S 键，最终使其成为配位键，例如，在与 Arduengo 卡宾的螺加合物的极限情况下。通过使用卡宾交换的等电子反应来量化卡宾稳定性的影响。
