Preparation and oxygen-transfer properties of novel palladium(II) and platinum(II) hydroperoxo and alkylperoxo complexes

A series of mononuclear hydroperoxo and tert-butylperoxo complexes L2M(Rx)(OOR) (L = 1/2, diphosphine or monophosphine; M = Pd or Pt; Rx = activated alkyl; R = H or t-Bu) have been prepared by condensation reactions of L2M(Rx)(OH) with ROOH (R = H or t-Bu). While t-BuOOH reacts in all the cases tested, with H202 the preparation reaction is sensitive to the nature of the alkyl ligand Rx. These compounds behave as typical oxygen-transfer agents, reacting with PPh3, CO, NO, and benzaldehyde. In one case it is possible to oxidize terminal olefins to the corresponding methyl ketones