Oxidation of hydrocarbons by aqueous platinum salts: mechanism and selectivity
Water-soluble organic compounds are selectively oxidized by aqueous solutions of chloroplatinum(II) and chloroplatinum(IV) salts. p-Toluenesulfonic acid undergoes stepwise hydroxylation to the corresponding alcohol and aldehyde, with no further oxidation to the carboxylic acid; p-ethylbenzenesulfonic acid is functionalized at both the benzylic and methyl positions. Ethanol is converted to a spectrum of C_2 (chloro)oxygenates, including ethylene glycol and 2-chloroethanol, products resulting from methyl fundionalization. n-Propanol is also significantly attacked at the methyl position. ^(13)C labeling and kinetics studies were used to elucidate mechanistic pathways. The reactivity of a methyl group C-H bond is at least as high as that of a C-H bond CY to oxygen, in contrast to most alkane conversion systems.
Additional Information© 1993 American Chemical Society. Received September 30, 1992. This work was supported by the Caltech Consortium in Chemistry and Chemical Engineering (founding members E. I. du Pont de Nemours and Co., Inc., Eastman Kodak Co., Minnesota Mining and Manufacturing Co., and Shell Development Co.) and by the Office of Naval Research. A.M.H. thanks the SERC (U.K.) for a fellowship. K.E. thanks the BASF Corp. (Ludwigshafen, Germany) for fellowship support. We thank Professors Kool and Sen for communicating results prior to publication.
Supplemental Material - om00027a045_si_001.pdf