摘要:
Transformations of 2-methyl-2-propanol, 2-methyl-2-butanol, 2-methyl-2-pentanol, 1-methyl-1-cyclohexanol, and 1-ethyl-1-cyclohexanol in the presence of tetraaquapalladium(II) ions in perchloric acid madium were studied. It was found that the reactions give rise to palladium(II) pi-allyl complexes. The reaction rate increases and the yield of the corresponding pi-allyl complex decreases with increasing hydrocarbon chain length. Addition of iron(III) ions to the systems essentially increases the yield of palladium pi-allyl complexes. The olefin formed from the corresponding tertiary alcohol participates in the formation of the palladium pi-allyl complex. Oxidation of 2-methyl-2-butanol with tetraaquapalladium(II) ions gives the isomeric palladium pi-allyl complexes [Pd(eta(3)-(CH3)(2)CCHCH2)bpy]ClO4 and [Pd(eta(3)-(CH2C(CH3)CHCH3))bpy]ClO4, which were isolated using 2,2'-bipyridyl and characterized by H-1 and C-13 NMR spectroscopy.