Rotational Isomerization of Carbon–Carbon Single Bonds in Ethyl Radical Derivatives in a Room-Temperature Solution

• Published in: The journal of physical chemistry letters 2022-12, Vol.13 (49), p.11551-11557
• Main Authors: Park, Seongchul, Shin, Juhyang, Yoon, Hojeong, Lim, Manho
• Format: Article
• Language: English
• Subjects: Physical Insights into Chemistry, Catalysis, and Interfaces
• ISSN: 1948-7185; 1948-7185
• DOI: 10.1021/acs.jpclett.2c03154

The rotational isomerization of 1,2-disubstituted ethyl radical derivatives, reaction intermediates often found in the reaction of 1,2-disubstituted ethane derivatives, has never been measured because of their short lifetime and ultrafast rotation. However, the rotational time constant is critical for understanding the detailed reaction mechanism involving these radicals, which determine the stereoisomers of compounds produced via the intermediates. Using time-resolved infrared spectroscopy, we found that the CF2BrCF2 radical in a CCl4 solution rotationally isomerizes with a time constant of 47 ± 5 ps at 280 ± 2 K. From this value and the rotational barrier heights of related compounds, CH3CH2 and CH3CH2CHCH3 radicals in CCl4 were estimated to rotationally isomerize within 1 ps at 298 K, considerably faster than ethane and n-butane, which rotationally isomerize with time constants of 1.8 and 81 ps, respectively. The time constant for the rotational isomerization was similar to that calculated using transition state theory with a transmission coefficient of 0.75.