REACTION OF THE RHODIUM AND IRIDIUM COMPLEXES WITH ALDEHYDES TO GIVE , AND RELATED REACTIONS

Article abstract of DOI:10.1016/0022-328X(85)80349-1

The complexes (1a, M = Rh; 1b, M = Ir) react with aldehydes (RCHO) (cyclohexane, 80 deg C) to give , methane, and Me2SO; the reaction is strongly inhibited by dimethyl sulphoxide but is unaffected by addition of di-t-butyl peroxide.Benzaldehyde reacts with the rhodium complex ca. 30 times as fast as with the iridium complex; the relative rates of reaction of tolualdehydes with both 1a and 1b are in the ratio, 1/2/2 for the o-, m- and p-isomers.The complexes are also formed by carbonylation of .Reaction of with ArCHO gave a mixture of and (ca. 4/1); replacement of aryl being favoured over replacement of methyl. gave on reaction with p-MeC6H4CHO.Possible mechanisms are discussed; the evidence favours one involving metal(V) intermediates.