Phosphadioxirane: a peroxide from an ortho-substituted arylphosphine and singlet dioxygen.
We prepared the primary adduct for the reaction of singlet dioxygen (1O2) with an arylphosphine by using the sterically hindered arylphosphine tris(o-methoxyphenyl)phosphine. The resulting phosphadioxirane has a dioxygen molecule triangularly bound to the phosphorus atom. Olefin trapping experiments show that the phosphadioxirane can undergo nonradical oxygen atom-transfer reactions. Under protic conditions, two different intermediates are formed during the reaction of singlet dioxygen with tris(o-methoxyphenyl)phosphine, namely, the corresponding hydroperoxy arylphosphine and a hydroxy phosphorane. Experiments with other arylphosphines possessing different electronic and steric properties demonstrate that the relative stability of the tris(o-methoxyphenyl)phosphadioxirane is due to both steric and electronic effects.
Ho
David G
DG
Department of Chemistry and Biochemistry, California State University, Los Angeles, Los Angeles, CA 90032, USA.
Gao
Ruomei
R
Celaje
Jeff
J
Chung
Ha-Yong
HY
Selke
Matthias
M
D055598:Chemical Phenomena; D002627:Chemistry, Physical; D004852:Epoxy Compounds / Q000737:chemistry*; D006573:Heterocyclic Compounds, 1-Ring / Q000737:chemistry*; D007700:Kinetics; D009682:Magnetic Resonance Spectroscopy; D015394:Molecular Structure; D009943:Organophosphorus Compounds / Q000737:chemistry*; D010084:Oxidation-Reduction; D010100:Oxygen / Q000737:chemistry; D010545:Peroxides / Q000737:chemistry*; D010720:Phosphines / Q000737:chemistry; D010758:Phosphorus; D026082:Singlet Oxygen / Q000737:chemistry; D013696:Temperature
D004852:Epoxy Compounds; D006573:Heterocyclic Compounds, 1-Ring; D009943:Organophosphorus Compounds; D010545:Peroxides; D010720:Phosphines; C478246:tris(2-methoxyphenyl)phosphadioxirane; C478247:tris(2-methoxyphenyl)phosphine; C061799:dioxirane; D026082:Singlet Oxygen; D010758:Phosphorus; D010100:Oxygen