RUI: CAS-SC: Promoting Group-Transfer Reactions at Metal/Main-Group Bonds

在化学系化学合成项目的支持下，马修·T·怀特和他的卡尔顿学院本科生研究小组正在开发具有与硅等重金属非金属元素键合的金属络合物的新应用。这些化合物的设计目的是在主族原子和金属之间提供协同作用。这使得该化合物能够将不同的基团聚集在一起，并使它们之间发生反应。该项目将开发系统，将活性化学碎片附着在廉价且容易获得的底物上，以提供在大宗和精细化学领域都有应用的产品。这种方法还寻求在催化中用富含稀土的金属取代昂贵的稀有金属。该项目将为本科生研究人员提供培训基础，并使与化学合成和X射线结晶学相关的主题扩大到明尼苏达州诺斯菲尔德和明尼苏达州法里堡的高中生。该项目旨在通过探索金属-硅单键和多键作为将反应性氮、卡宾和相关基团转移到有机底物的平台来发展晚期金属/主基团相互作用的化学。初步研究结果表明，这些“电子受阻”键可以实现双位催化，从而使两个位(金属和主族元素)与不同的底物相互作用，使它们结合在一起，但这一策略的普遍性尚未得到证明。这种方法避免了许多催化剂中存在的中毒问题，也为在基团转移催化剂中使用富含稀土的金属，如铁、钴和镍提供了一种独特的方法。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 support from the Chemical Synthesis Program of the Chemistry Division, Matthew T. Whited and his research group of undergraduate students at Carleton College are developing new applications of metal complexes featuring bonds to heavy non-metal elements such as silicon. These compounds are designed to provide synergistic interaction between the main group atom and the metal. This enables the compound to bring together different groups and enable reactions between them. The project will develop systems where reactive chemical fragments are attached to inexpensive and readily abundant substrates to afford products with applications in both that bulk and fine chemical arenas. This approach also seeks to replace expensive, rare metals with earth abundant ones in catalysis. The project will provide a training ground for undergraduate researchers and enable expanded outreach to high school students in Northfield, MN and Faribault, MN on topics related to chemical synthesis and X-ray crystallography.This project seeks to develop the chemistry of late-metal/main-group interactions by exploring metal-silicon single and multiple bonds as platforms for transfer of reactive nitrene, carbene, and related groups to organic substrates. Preliminary findings have shown that these “electronically frustrated” linkages can enable dual-site catalysis whereby the two sites (metal and main-group element) interact with different substrates to bring them together, but the generality of this strategy has not been demonstrated. Such an approach serves to avoid problems of poisoning present in many catalysts and also provides a distinct approach to using earth abundant metals such as iron, cobalt, and nickel in group-transfer 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.