Symposium on Molecular Modeling of Petroleum Processes and Catalysis 1992
Conference paper

Studies on the structure and β-bond scission reactions of primary alkyl radicals, from n-propyl to n-octyl


Alkyl radicals are perhaps the simplest but yet some of the most reactive organic radicals. Previously, the authors reported a number of studies on small alkyl systems like methyl, ethyl, isopropyl and tertiary butyl which aided structural, kinetic, and thermodynamic studies. However, in order for this work to be more pertinent encompassing studies on larger systems should be conducted. Therefore, they have theoretically investigated the structures of primary alkyl radicals with chain lengths up to nine carbon atoms to obtain: (i) optimized geometry for a number of pertinent conformations; (ii) barriers for internal rotations about αC-C, βC-C, and γC-C bonds; (iii) energetics for the βC-H and βC-C bond scission reactions; (iv) energetics for 1-3, 1-4, and 1-6 hydrogen atom migration; and (v) vibrational frequencies and intensities, and force fields. Due to the length of this study only the first four parts are presented herein. The force fields, vibrational frequencies and intensities will be given in another report along with experimental spectra of primary alkyl radicals. In addition, similar reports on large secondary and tertiary radicals are forthcoming.