Unsupported Z-ligands as key Initiators of New Catalytic Processes

在化学系化学结构、动力学和机理B(CSDM-B)和化学催化计划的支持下，北卡罗来纳大学教堂山分校的Michel R.Gagné教授正在研究与金属配合物配位的配体的基本结构。改变金属-配位键性质的目标将使发现新的催化反应成为可能。催化是支撑所有工业化学转化的基石技术，因此具有巨大的全球经济影响。Gagné项目可能会发现配体的全新行为方式，从而使新的催化反应成为可能，并对学术界和工业界的有机金属化学领域产生影响。一个重点领域将是激活C-O键；这些键在生物可再生碳资源中普遍存在。Gagné小组将研究无载体配体的基本反应性，这些配体的反应性，但也可能是其结构可以描述为Z-类。配基的Z-标号并不常见，它是为那些充当亲电体的配基保留的。在这样的配体上加入亲核试剂会以一种还原金属的方式裂解M-Z键，并将实现额外的下游化学作用。具体的重点将是作为硅、硅离子(和还原金属)来源的金属-硅络合物，以及作为碘(I+)离子和还原金属来源的金属-碘化物络合物。金属氧化态和支持配体对推定的Z配体的结构和反应性的作用是最重要的。该奖项反映了NSF的法定使命，并通过使用基金会的智力优势和更广泛的影响审查标准进行评估，被认为值得支持。

With the support of the Chemical Structure, Dynamics, and Mechanisms B (CSDM-B) and Chemical Catalysis Programs in the Division of Chemistry, Professor Michel R. Gagné of the University of North Carolina at Chapel Hill is studying the fundamental structure of ligands that coordinate to metal complexes. The goal of changing the properties of metal-ligand bonds will enable new catalytic reactions to be discovered. Catalysis is a cornerstone technology that underpins all industrial chemical transformations and is therefore of enormous global economic impact. The Gagné project could potentially uncover entirely new ways for ligands to behave, which would consequently enable new catalytic reactions and have impact across the field of organometallic chemistry in both academia and industry. One focus area will be on activating C–O bonds; these are ubiquitous in biorenewable sources of carbon.The Gagné group will study the fundamental reactivity of unsupported ligands whose reactivity, but also perhaps whose structure can be described as Z-like. The Z-designation for a ligand is not common and is reserved for those ligands that act as electrophiles. The addition of a nucleophile to such a ligand cleaves the M-Z bond in a manner that reduces the metal and will enable additional downstream chemistry. The specific focus will be on metal-silicon complexes that act as sources of silylium, Si+ ions (and reduced metal), along with metal-iodide complexes that act as sources of iodonium (I+) ions and reduced metal. The role of metal oxidation state and supporting ligands on the structure and reactivity of the putative Z ligand are of paramount interest.This award reflects NSF's statutory mission and has been deemed worthy of support through evaluation using the Foundation's intellectual merit and broader impacts review criteria.