Synthesis, Reactivity, and Photochemistry of Late Transition Metal Complexes Featuring Carbenium-based Ambiphilic Ligands

在化学系化学合成计划的支持下，德克萨斯州农工大学化学系的François Gabbaiti教授将研究一个新的配体家族，该家族含有位于金属结合位点旁边的带正电荷的碳单元。 配体是分子化合物，旨在保持金属原子并影响其进行和加速化学反应的能力。这些对广泛的化学工业至关重要。 因此，设计新的配体，可以有目的地改善金属的反应性是一个重要的调查路线。 在这项研究中制备的新配体被设计为允许带正电荷的碳单元接近或联合收割机与金属原子，增强其反应性。 接下来，配体-金属络合物将被开发成太阳能燃料的平台，从而影响新能源存储策略的研究。 此外，该项目将提供指导，以不同的高中学生和目前的化学知识，以K-6年级的学生在双向双语课程结合母语英语和西班牙语。这个项目从Gabbavirk团队在得克萨斯州A M将调查的合成和配位化学的两亲性配体具有定位旁边的膦或卡宾基金属结合位点的碳正离子。 这些配体与后过渡金属如镍、钯、铂和金的配位提供了一类络合物，其中后过渡金属通过在金属和碳鎓单元之间形成电荷转移或静电相互作用而被电子耗尽。 这些非典型的相互作用将使用结构，光谱和计算工具的特点。 从这些研究中获得的知识有望为金属-配体相互作用的微调提供一个框架，并为有机金属化学家提供新的方法来影响后过渡金属中心的反应性。如果成功的话，这些研究将为卤素光还原消除化学和亲碳催化带来新的机会。该奖项反映了NSF的法定使命，并通过使用基金会的知识价值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 Synthesis program of the Division of Chemistry, Professor François Gabbaï of the Department of Chemistry at Texas A&M University will investigate a new family of ligands containing a positively charged carbon unit positioned next to a metal-binding site. Ligands are molecular compounds designed to hold metal atoms and influence their ability to carry out and accelerate chemical reactions. These are essential to a broad range of chemical industries. Designing new ligands that can purposefully ameliorate the reactivity of metals is thus an important line of inquiry. The new ligands prepared in this research are designed to allow for a positively charged carbon unit to approach or combine with a metal atom, enhancing its reactivity. Next, the ligand-metal complexes are to be developed into platforms for the generation of solar fuels, thus impacting research on new energy storage strategies. In addition, the project will provide mentorship to diverse high school students and and present chemical knowledge to K-6 grade students in two-way dual language programs integrating native English and native Spanish.This project from the Gabbaï team at Texas A & M will investigate the synthesis and coordination chemistry of ambiphilic ligands featuring a carbenium ion positioned next to a phosphine- or carbene-based metal-binding site. Coordination of these ligands to late transition metals such as nickel, palladium, platinum, and gold affords a family of complexes in which the late transition metal is electronically impoverished via the formation of a charge transfer or electrostatic interaction between the metal and the carbenium unit. These atypical interactions will be characterized using structural, spectroscopic, and computational tools. The knowledge derived from these investigations is expected to provide a framework for the fine-tuning of metal-ligand interactions and provide organometallic chemists with new ways to influence the reactivity of late transition metal centers. If successful, these studies will lead to new opportunities in halogen photoreductive elimination chemistry and in carbophilic catalysis.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.