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）和化学催化项目的支持下，Michel R.位于查佩尔山的北卡罗来纳州大学的加涅正在研究与金属配合物配位的配体的基本结构。改变金属-配体键的性质的目标将使新的催化反应被发现。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行为的全新方式，从而实现新的催化反应，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;这些在生物可再生的碳源中无处不在。Gagné小组将研究无支撑配体的基本反应性，其反应性，但也可能其结构可以描述为Z-样。配体的Z-命名并不常见，并且保留用于充当亲电子试剂的那些配体。将亲核试剂添加到这样的配体以还原金属的方式切割M-Z键，并将实现额外的下游化学。具体的重点将放在金属-硅络合物，作为硅鎓，Si+离子（和还原金属）的来源，沿着金属碘化物络合物，作为碘鎓（I+）离子和还原金属的来源。该奖项反映了NSF的法定使命，并已被认为是值得通过使用基金会的智力价值和更广泛的影响审查标准进行评估的支持。

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.