Direct femtosecond observation of the transient intermediate in the α-cleavage reaction of (CH3)2CO to 2CH3+CO: Resolving the issue of concertedness

Publisher Website
Google Scholar
Abstract
When a reaction involving two equivalent bonds has sufficient energy to break both of them, it can proceed by either a concerted or a stepwise mechanism. For Norrish type‐I and other reactions, this issue has been controversial since direct time resolution of the individual C–C cleavage events was not possible. Here, for the elementary α‐cleavage of acetone, we report on the femtosecond resolution of the intermediates using mass spectrometry. The results show the nonconcertedness of the reaction, provide the times for the primary and secondary C–C breakage, and indicate the role of electronic structure (σ*, antibonding impulse) and the vibrational motions involved.

This publication has 28 references indexed in Scilit: