Synthesis and characterization of, and dynamic processes occurring in, highly active Pd catalyst for alkyne and alkene hydroesterification

摘要

Chapter one reviews the literature surrounding three main areas of interest relevant to the research carried out. These areas include industrial process for the synthesis of methyl methacrylate, the carbonylation of alkynes and alkenes. In addition, review effect of the ligands and counterion on the catalyst system, and dynamic process and NMR of the catalyst. Chapter two outlines simple, generic procedures to Pd-‘chelate-monodentate’ complexes and investigates the coordination chemistry and hemilability of such complexes. In addition, an explanation of the organometallic chemistry of the Pd-‘chelate-monodentate’ complexes and synthesis of these complexes illustrates the possibility of nitrogen playing a role in proton relay. Also, introduces the variable temperature spectra of a [Pd(ҡ2-Ph2Ppy)(ҡ1-Ph2Ppy)2] [CH3SO3]2 (6), and [Pd(ҡ2-Ph2Ppy)(ҡ1-Ph2Ppy)Cl][X] (3[X]), (X = Cl, OTf, BF4), uses a computer program to simulate gNMR discusses the associative mechanism of exchange in Pd-‘chelate-monodentate’ complexes. Finally, details the experimental procedures undertaken in the above work. Chapter three illustrates how can preparation of the new alkanesulfonic acids (R = C8, C9, C11, C14, C16, C18) which use instead of methanesulfonic acid in hydroesterification of alkene process. In terms of follow the two strategies, first strategy depends on synthesis of silver alkanesulfonate salts from interaction of sodium alkanesulfonate salts with AgNO3 then reaction with palladium complex. While in the second strategy, free alkanesulfonic acid was prepared in situ, via reaction of HBF4 with a series of sodium alkanesulfonate salts (R = C8, C9, C11, C14, C16, C18), then added to palladium complex in a sapphire tube of HPNMR spectroscopy for studies and confirm steps of the catalytic cycle. Chapter four draws on the conclusions derived from the above work and relates it to work previously carried out in the field.