Electron addition to organic halides. An electron spin resonance study.

It had always been assumed that electron addition to organic halides resulted in dissociation as in reaction [1]. RX + e- → R. + X- .... [1] In more recent years, intermediate species have been isolated; in particular the R./X- adduct (where R is an alkyl group) and the (R-.X)- o* anion (where R is, for example, the -CF3 group). Chapters 2-5 document the isolation of a range of alkyl radical/ halide ion adducts in a range of matrices. Particularly exemplary results were obtained from the adamantane matrix, Chapter 1 therefore reviews the physical properties of the compound and the chemical methods employed for its purification and for the incorporation of substrates into its lattice. Conversely, Chapters 6 and 7 discuss the theory of formation of o* anions and documents a series of attempts at their isolation. Finally, Chapter 8 probes and compares the thermally and photo-lytically induced [1,2] hydrogen atom shift isomerisation processes of the But. and isoBu. radicals and But./X- and isoBu./X- adducts (X = C1, Br, I) in a range of matrices (reactions [2] and [3]).