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

提出的研究计划旨在研究晚期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。这类过程的效率很大程度上受金属中心的辅助配体性质的影响。因此，设计和使用易于调谐以满足特定电子和空间需求的配体是至关重要的。具体来说，该计划是针对钯催化烯烃氧化（如瓦克反应），其机制仍是一个争论多年的研究课题。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，配体的研究范围相当有限。本研究的重点是新型双齿和/或潜在半可溶配体的合理设计、合成、表征和应用，如亚磷膦及其硫属化合物。这些配体可以由易于获得的起始材料如氨基酚和水杨醛制备。该配体包含硬（N或O）和软（P， S或Se）给体，它们与金属中心的相互作用不同，可能导致催化性能的改善。本文将系统地研究铂和钯配合物的反应性与亚膦酸盐和硫属化合物的选择之间的关系。这项研究将加强对重要化学过程机制的理解，从而允许设计和合成更有效的催化系统。它也将为培养具有重要综合和分析技能的本科生提供一个极好的机会。

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.