杂环 OSNSO 中的光诱导硫-氮键旋转和热氮反转
Photoinduced Sulfur-Nitrogen Bond Rotation and Thermal Nitrogen Inversion in Heterocumulene OSNSO.
机构信息
College of Chemistry, Chemical Engineering and Materials Science, Soochow University , 215123 Suzhou, China.
Fachbereich Chemie, Philipps-Universität Marburg , Marburg D-35032, Germany.
出版信息
J Am Chem Soc. 2018 Jan 31;140(4):1231-1234. doi: 10.1021/jacs.7b12622. Epub 2018 Jan 19.
An exotic ternary S, N, O heterocumulene OSNSO in syn-syn (A) and syn-anti (B) conformations has been generated in the gas phase through flash vacuum pyrolysis of CFS(O)NSO at 700 K. Upon visible light irradiation (570 ± 20 or 532 nm), both A and B, isolated in cryogenic matrices (N, Ne, Ar, and Kr, <30 K), convert to a higher-energy anti-anti conformer (C). The reverse conformational transformation occurs either through S═N bond rotation (C to A and B) under visible light irradiation (400 ± 20 nm) at 2.8 K or through thermal nitrogen inversion (C to A) in the temperature range of 20-30 K, for which an exceptionally low activation barrier of 1.18 ± 0.07 kcal mol has been experimentally determined.
通过在 700 K 下对 CFS（O）NSO 进行闪光真空热解，在气相中生成了具有 syn-syn（A）和 syn-anti（B）构象的奇异三元 S、N、O 杂Cumulene OSNSO。在可见光照射（570 ± 20 或 532nm）下，在低温基质（N、Ne、Ar 和 Kr，<30 K）中分离的 A 和 B 均转化为高能 anti-anti 构象体（C）。通过在 2.8 K 下通过可见光照射（400 ± 20nm）进行 S=N 键旋转（C 到 A 和 B），或者通过在 20-30 K 的温度范围内进行热氮反转（C 到 A），可以发生反向构象转变，实验确定其活化能垒非常低，为 1.18 ± 0.07 kcal/mol。
Zotero 插件