摘要:
Two new dinuclear. palladium complexes, [Pd2Me2Cl2(dmpm)(2)] (4) and [PdMe(Cl)(dmpm)(2)PdCl2] (5), have been prepared and their structures determined by single-crystal X-ray analysis. 5 is an interesting example of a complex with both a cis-PdCl2 center and a trans-MePdCl center, within the same molecule. The reactivity of 4, as well as the previously reported, complexes [Pd2Me2Cl2(dppm)(2)] (1), [Pd-2(mu-CH2)Cl-2(dppm)(2)] (2), and [Pd2Me4(pmpm)(2)] (3), toward, silica have been investigated. The complexes react readily with either, dichloromethane or benzene suspensions of silica to give chemisorbed species, presumably by reaction of the Pd-Me group,with, the O-H bond of the surface silanol groups, in the case of 1, 3 and 4, and protonation of the methylene bridge, in the case of 2. The complexes containing the more basic phosphine, dmpm, gave much higher palladium loadings, (wt % Pd 1.37-2.47) on silica, compared to the dppm complexes (wt % Pd 0.55-0.80). The molecular and grafted materials were initially tested as catalysts for the cyclization of 6-aminohex-1-yne to give 2-methyl-1,2-dehydropiperidine. The silica/dmpm complexes were found to be the most active catalysts for this reaction and were also tested for the cyclization of 5-phenyl-4-pentyn-1-amine.