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

拟议的研究计划旨在研究后过渡金属催化的烯烃功能化，这在学术和工业环境中都是重要的化学过程。这些类型的过程的效率在很大程度上受到金属中心辅助配体的性质的影响。因此，设计和使用能够容易地调节以满足特定电子和空间需求的配体是至关重要的。具体地，该计划针对钯催化的烯烃氧化(如Wacker反应)，经过多年的研究，其反应机理仍然是一个有争议的话题。由于许多常见的有机配体在氧化条件下被氧化或分解，因此在烯烃氧化化学中配体的范围相当有限。工作重点是新型双齿和/或潜在的半亲配体的合理设计、合成、表征和应用。这些配体可以由氨基酚和水杨醛等容易获得的原料制备。这些配体既有硬的(N或O)，也有软的(P，S，P或Se)与金属中心以不同方式相互作用并可能导致催化性能改善的施主。此外，将系统地研究铂和钯配合物的反应性与亚胺膦和硫系化合物的选择之间的关系。这项研究将增进对重要化学过程中机理的理解，从而允许设计和合成更高效的催化体系。此外，它还将为培养具有重要合成和分析技能的本科生提供极好的机会。

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.