Exploring the Multi-valency of Dirhodium Carboxamidates: From Catalytic Mechanisms of Oxidation to Materials Applications

凭借有机化学和高分子化学项目颁发的这一奖项，Michael Doyle教授将专注于金属化合物化学中的两项基本发现，这两项发现将为化学领域的革命性发展带来令人兴奋的潜力。第一种是用廉价的叔丁基氢过氧化氢(70%在水中)使用这些金属化合物对有机化合物进行化学氧化。第二个是基于他们发现了一类新的含有金属的有机化合物，这些化合物显示出作为新的和未开发的材料的高潜力。这两者都与Rh与连接到连接两个Rh原子的酰胺结构时与第二个Rh结合的独特能力有关。得到的化合物有两个Rh原子，以桨轮的形式连接到四个酰胺结构，它们的独特性质包括能够在低能量输入的情况下被氧化。由于叔丁基氢过氧化氢催化氧化的结果显示了他们的策略相对于替代催化策略的显著优势，其中包括(1)低催化剂负载量(低至0.1mol%)以实现高产品产率，(2)在各种有机化合物中选择性地生成酮，以及(3)在水中发生反应而不破坏催化剂，他们将加深对这些氧化过程的广泛理解。他们将确定氧化的一个或多个特定途径，以及将反应引导到特定途径的方法，以便将应用扩大到包括类固醇和不饱和脂肪酸在内的复杂有机化合物的氧化。具有结构刚性、稳定性和设计灵活性的含Rh有机化合物的发现，以及它们的制备方法，使构建以前未知的有机金属材料成为可能。由于这些材料没有金属-金属键，它们可能是很好的绝缘体；该小组将专注于用这些化合物生产分子导线，努力通过电子转移实现导电性，以便作为绝缘体和导体，它们可能能够开发分子开关。更广泛的影响。这项研究的意义在于对自由基中间体的拦截和产物形成的反应途径的控制有了新的见解，其中许多与生物过程有关。他们通过温和的方法制备的化合物在碳-碳键形成反应中提供了更广泛的有效催化剂选择。含Rh有机化合物是一类新的易获得的有机金属材料，其功能可用于电子学或光学，也可用于开发新的聚合物材料。这项研究提供的教育和培训的多样性使博士后、研究生和本科生参与者受益。

With this award from the Organic and Macromolecular Chemistry Program, Prof. Michael Doyle will focus on two fundamental discoveries in the chemistry of metal compounds that have exciting potential for revolutionary developments in chemistry. The first is chemical oxidations of organic compounds by inexpensive tert-butyl hydroperoxide (70% in water) using these metal compounds. The second is based on their discovery of a new class of metal-containing organic compounds that show high potential as new and unexplored materials. Both are related to the unique ability of rhodium to bind to a second rhodium when connected to amide structures that bridge the two rhodium atoms. The compounds that result have two rhodium atoms connected to four amide structures in the form of a paddlewheel, and their unique properties include an ability to be oxidized with low input of energy. Encouraged by results in catalytic oxidations by tert-butyl hydroperoxide that reveal significant advantages for their strategy over alternative catalytic strategies, among which are (1) low catalyst loading (down to 0.1 mol %) to achieve high product yields, (2) formation of ketones selectively in a variety of organic compounds, and (3) reactions occur in water without destruction of catalyst, they will develop a broad understanding of these oxidative processes. They will determine the specific pathway or pathways for oxidation, as well as methods to direct the reaction to a specific pathway, so that applications can be broadened to oxidations of complex organic compounds that include steroids and unsaturated fatty acids. The discovery of rhodium-containing organic compounds that have structural rigidity, stability, and design flexibility, and a general methodology for their preparation, has made possible the construction of previously unknown organometallic materials. Because these materials do not have a metal-metal bond, they are potentially good insulators; the group will focus on the production of molecular wires with these compounds with efforts to achieve conductance through electron transfer so that, as insulators and conductors, they may be able to develop molecular switches. Broader Impacts. The implications of this research promise new insights into the interception of radical intermediates and control of reaction pathways for product formation, many of which are related to biological processes. The compounds that they prepare by mild methods provide a broader selection of effective catalysts in carbon-carbon bond forming reactions. Rhodium-containing organic compounds are a new class of easily accessed organometallic materials whose function could be of benefit in electronics or optics, as well in the development of new polymeric substances. The variety of education and training afforded by this research benefits postdoctoral, graduate student and undergraduate student participants.