Inter- and intra-molecular two-centre three-electron bonding in radical cations of alkyl bromides

摘要: Abstract The reaction of hydroxyl radicals with different alkyl bromides in acidic aqueous solution has been studied by nanosecond pulse radiolysis technique at a high solute concentration where dimer radical cations are formed. observed rate constant for the decay is deconvoluted to processes and deprotonation cation found be determining step. inter- intra-molecular two-centre three-electron bond strength determined series from dibromoalkanes semi-empirical level AM1 parametrization. Calculations indicate that strengths hemi-bond decreases as length methylene linkage increases case cations.