Reaction of arylphosphines with singlet oxygen: intra- vs intermolecular oxidation.
[reaction--see text] The chemistry of singlet oxygen with all three isomers of tris(methoxyphenyl)phosphine has been studied. For the severely hindered ortho isomer, intramolecular rearrangement to form phenyl diphenyl phosphinate is preferred to formation of phosphine oxide at low concentration in aprotic solvents. In protic solvents, no intramolecular reactivity is observed. A detailed kinetic analyses has been undertaken. There is no physical quenching, regardless of solvent. Mechanistic implications of these findings are discussed.
Gao
R
R
Department of Chemistry and Biochemistry, California State University, Los Angeles, Los Angeles, California 90032, USA.
Ho
D G
DG
Dong
T
T
Khuu
D
D
Franco
N
N
Sezer
O
O
Selke
M
M
D000465:Algorithms; D005609:Free Radicals; D007700:Kinetics; D009682:Magnetic Resonance Spectroscopy; D010084:Oxidation-Reduction; D010720:Phosphines / Q000737:chemistry*; D010777:Photochemistry; D026082:Singlet Oxygen / Q000737:chemistry*; D012997:Solvents
D005609:Free Radicals; D010720:Phosphines; D012997:Solvents; D026082:Singlet Oxygen