29997-99-7Relevant academic research and scientific papers
Monomer and Dimer Cations of Trimethylphosphine: A Radiation Chemical and E.S.R. Study
Symons, Martyn C. R.,McConnachie, Glen D. G.
, p. 851 - 853 (1982)
The 1H hyperfine coupling for Me3P.+ ions generated radiolytically in Freon at 77 K (ca. 11.5 G) is much greater than that for the dimer cations (Me3P)2+ (ca. 3.3 G): this is explained in terms of a decreasing tendency for ?-? delocalisation as the pyramidal character of the Me3P unit increases, coupled with a tendency towards ?-orbital localisation in ?*-radicals.
Three-electron ?-Bonded Radicals: An Electron Paramagnetic Resonance Spectroscopic Study of R3PCl Radicals in Freon
Abu-Raqabah, Atieh,Symons, Martyn C. R.
, p. 3293 - 3298 (2007/10/02)
Our main purpose is to draw attention to the relative stability of three-electron ?-bonded radicals (?12, ?21), the large number of such radicals that have been studied by EPR spectroscopists, and their potential importance as reaction intermediates.The topic is illustrated by experiments which show that when R3P.+ radical cations (Me3P.+ amd Ph3P.+) are generated in CFCl3 at 77 K by exposure to 60Co γ-rays, and the system is annealed to ca. 155 K, features characteristic of R3PCl radicals are detected, with well defined hyperfine coupling to 31P and 35/37Cl nuclei.It is argued that these must have been formed from chloride ions released from (CFCl3).- radical-anions following electron capture.
Preparation and Structure of Certain Phosphorus-centred Radical Cations
Hasegawa, Akinori,McConnachie, Glen D. G.,Symons, Martyn C. R.
, p. 1005 - 1016 (2007/10/02)
Exposure of dilute solutions of various trivalent phosphorus derivatives, PL3, in fluorotrichloromethane to (60)Co γ-rays at 77 K gave the corresponding cations, (1+), characterised by their e.s.r. spectra.The spectra establish that the SOMO for these cations is considerably localised on phosphorus, which contributes extensive atomic 3s and 3p character.The results confirm and extend previous studies using sulphuric acid matrices.The tendency for these cations to react with corresponding neutral molecules to give ?* dimer-cations PL3>(1+) is also confirmed. The structures of these species are discussed and compared with those of related radicals.
