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

获得有机和大分子化学计划的这一奖项后，Michael Doyle教授将专注于金属化合物化学的两项基本发现，这两项发现在化学领域具有令人兴奋的革命性发展潜力。第一种是利用这些金属化合物，通过廉价的叔丁基过氧化氢（水中70%）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金属有机化合物，这些化合物作为新的和未开发的材料显示出很高的潜力。两者都与铑的独特能力有关，当连接到连接两个铑原子的酰胺结构时，铑与第二个铑结合。所得到的化合物有两个铑原子以桨轮的形式连接到四个酰胺结构上，它们的独特性质包括能够以低能量输入被氧化。过氧化叔丁基催化氧化的结果显示了其策略优于其他催化策略的显著优势，其中包括(1)低催化剂负载（低至0.1 mol %）以获得高产物收率，(2)选择性地在各种有机化合物中形成酮，以及(3)在水中发生反应而不破坏催化剂，他们将对这些氧化过程有更广泛的了解。他们将确定氧化的特定途径，以及将反应导向特定途径的方法，从而将应用范围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铑有机化合物的发现，及其制备的一般方法，使构建以前未知的有机金属材料成为可能。因为这些材料没有金属-金属键，它们是潜在的良好绝缘体；该小组将专注于用这些化合物生产分子线，努力通过电子转移实现电导率，这样，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。这项研究的意义为阻断自由基中间体和控制产物形成的反应途径提供了新的见解，其中许多与生物过程有关。他们用温和的方法制备的化合物为碳-碳键形成反应提供了更广泛的有效催化剂选择。含铑有机化合物是一类易于获取的新型有机金属材料，其功能可用于电子或光学以及新型聚合物物质的开发。这项研究提供的各种教育和培训使博士后、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.