The kinetics of oxygen atom transfer from four oxo(salen)manganese(V) complexes to various para-substituted phenyl methyl sulfides have been studied spectrophotometrically in 90% acetonitrile-10% water(v/v) at 20oC. Electron-releasing substituents in sulfides and electron-withdrawing substituents in oxo(salen)manganese(V) complexes enhance the rate of oxidation. Correlation analyses establish that there is an inverse relationship between reactivity and selectivity in both the sulfide and the complex series. Mathematical treatment of the results shows the operation of a valid reactivity-selectivity principle in this redox system.
References
1.
JohnsonC.D., Chem. Rev., 1975, 75, 755.
2.
ProssA., Adv. Phys. Org. Chem., 1977, 14, 69.
3.
JohnsonC.D., Tetrahedron, 1980, 36, 3461 and references cited therein.
4.
ExnerO., J. Chem. Soc., Perkin Trans. 2, 1993, 973.
5.
SendegaR.V., VizgertR. V., and MikhalevichM. K., Reakts. Sposobnost Org. Soedin. (Tartu), 1970, 7, 512.
6.
SrinivasanC., KuthalingamP., and ArumugamN., Can. J. Chem., 1978, 56, 3043; J. Chem. Soc., Perkin Trans. 2, 1980, 170.
7.
LeeI., KohH. J., ParkY. S., and LeeH. W., J. Chem. Soc., Perkin Trans.2, 1993, 1575.
8.
BethellD., GrahamA. E., HeerJ. P., MarkopoulouO., PageP. C. B., and ParkB. K., J. Chem. Soc., Perkin Trans. 2, 1993, 2161.
BuncelE., and ChanquiC. J., J. Org. Chem., 1980, 45, 2825; M.E. Arnett and K.E. Molter, Acc. Chem. Res., 1985, 18, 339.
11.
JencksD.A., and JencksW. P., J. Am. Chem. Soc., 1977, 99, 7984; W.P. Jencks, Chem. Rev., 1985, 85, 511.
12.
BuncelE., and WilsonH., J. Chem. Ed., 1987, 64, 476.
13.
CurciR., DinoiA., and RubinoM. F., Pure and Appl. Chem., 1995, 67, 811.
14.
BonchioM., CampestriniS., ConteV., Di FuriaF., and MoroS., Tetrahedron, 1995, 51, 12363.
15.
ChellamaniA., AlhajiN. M. I., and RajagopalS., J. Chem. Soc., Perkin Trans. 2, 1997, 299; A. Chellamani and N.M.I. Alhaji, Indian J. Chem., 1999, 38A, 888.
16.
SevvelR., RajagopalS., SrinivasanC., AlhajiN. M. I., and ChellamaniA., J. Org. Chem., 2000, 65, 334.
