METAL HYDRIDE OXIDATION CHEMISTRY - ADDITION OF A TRITYL CATION TO THE CYCLOPENTADIENYL RING IN CPRU(PPH3)2H VIA INITIAL ELECTRON-TRANSFER

Treatment of CpRu(PPh3)2H (1) with 1 equivalent of the substituted trityl reagent Tol3C+PF6-(Tol = p-MeC6H4) in 9/1 dichloromethane-d2/acetonitrile-d3 at -80-degrees-C led to attachment of the trityl cation to the Cp ring and generation of the ring-substituted dihydride complex trans-[eta-5-C5H4(Tol3C)]Ru(PPh3)2H2+ (5). At ambient temperature the reaction yielded a mixture of 5, CpRu(PPh3)2H2+ (2), and CpRu(PPh3)2(NCCD3)+ (3-d3). Oxidation of 1 with 1 equivalent of CP2Fe+PF6- yielded a 1:1 mixture of 2 and 3-d3. The mechanism of the generation of the products is discussed in the light of the experimental evidence that suggests that 5 is formed by electrophilic attack by the trityl cation at the Cp ring of 1 via initial electron transfer.