Synthesis, characterization, and applications of late transition metal complexes containing iminophosphinite chalcogenide ligands

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The proposed research program is designed to study late transition metal-catalyzed functionalizations of alkenes, which are important chemical processes in both academic and industrial settings.  The efficiency of these types of processes is greatly influenced by the nature of ancillary ligands to the metal centers.  Therefore it is critical to design and employ ligands that can be easily tuned to meet specific electronic and steric demand.Specifically, the program is aimed at palladium catalyzed alkene oxidation (such as Wacker reaction) whose mechanism is still a topic of debate after many years of investigation.  The scope of the ligands in alkene oxidation chemistry is rather limited as many common organic ligands are oxidized or decomposed under oxidizing conditions.  The work focuses on the rational design, synthesis, characterization and application of novel bidentate and/or potentially hemilabile ligands such as iminophosphinites and their chalcogenides.  These ligands can be prepared from readily available starting materials such as aminophenol and salicylaldehyde.  The ligands contain both hard (N or O) and soft (P, S, or Se) donors which interact with metal centers differently and may lead to improved catalytic properties.  The relationship between the reactivity of platinum and palladium complexes and the choice of iminophosphinites and chalcogenides will be systematically investigated.  The study will enhance the understanding of mechanisms in important chemical processes, thus allow the design and synthesis of more efficient catalytic systems.  It will also provide an excellent opportunity for the training of undergraduate students with important synthetic and analytical skills.