Important factors in oxygen atom transfer to metal carbonyls. Rate of carbonyl substitution of chromium hexacarbonyl and iron pentacarbonyl in the presence of para-methoxyphenol chalcogenide oxide (p-CH3OC6H4)2EO (E = selenium, tellurium) and of triphenyl metal oxide (C6H5)3EO (E = arsenic, antimony). Syntheses and x-ray structure of Cr(CO)5E(p-CH3OC6H4)2

Abstract

An attempt is made to obtain information on the various factors that contribute to the overall O atom transfer rates of reactions of metal carbonyls of the type M-CO+E-O→M+CO 2 E. The metal carbonyls used were Cr(CO) 6 and Fe(CO) 5 , and the O atom transfer reagents were (p-CH 3 OC 6 H 4 ) 2 EO (E=Se, Te), (C 6 H 5 ) 3 EO (E=P, As, Sb), and (C 6 H 5 ) 2 SO. There was no reaction with either (C 6 H 5 ) 3 PO or (C 6 H 5 ) 2 SO, under the experimental conditions used. The reagents that did react transfer their O atoms at the relative rates of TeO>SeO>SbO>AsO. These results, along with previously reported data, are discussed in terms of the various important factors believed to contribute to the energetics of these overall reactions