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

探索羧酰胺二铑的多价态：从氧化催化机制到材料应用

• 批准号: 0748121
• 负责人: Michael Doyle
• 金额: $ 58.15万
• 依托单位: University of Maryland, College Park
• 依托单位国家: 美国
• 项目类别: Continuing Grant
• 财政年份: 2008
• 资助国家: 美国
• 起止时间: 2008-05-01 至 2012-10-31
• 项目状态: 已结题
• 来源: https://www.nsf.gov/awardsearch/showAward?AWD_ID=0748121&HistoricalAwards=false
• 关键词: Exploring; Multi; valency; Dirhodium; Carboxamidates

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.

凭借有机和高分子化学计划的这一奖项，Michael Doyle教授将专注于金属化合物化学中的两项基本发现，这些发现对化学的革命性发展具有令人兴奋的潜力。 第一种是使用这些金属化合物通过廉价的叔丁基过氧化氢（70%在水中）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。 两者都与铑在连接到桥接两个铑原子的酰胺结构时结合到第二个铑的独特能力有关。由此产生的化合物具有两个铑原子以桨轮的形式连接到四个酰胺结构，并且它们的独特性质包括以低能量输入被氧化的能力。受到叔丁基过氧化氢催化氧化结果的鼓舞，这些结果显示其策略相对于替代催化策略具有显著优势，其中包括（1）低催化剂负载（低至0.1mol%）以获得高产物产率，（2）在多种有机化合物中选择性地形成酮，和（3）反应在水中发生而不破坏催化剂，他们将对这些氧化过程有广泛的了解。 他们将确定氧化的特定途径，以及将反应引导到特定途径的方法，以便将应用扩展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，使得以前未知的有机金属材料的构建成为可能。 由于这些材料没有金属-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导线，努力通过电子转移实现电导，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。 这项研究的影响承诺新的见解拦截自由基中间体和控制反应途径的产品形成，其中许多是有关的生物过程。 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。 含铑有机化合物是一类新的易于获得的有机金属材料，其功能可能在电子学或光学中以及在新聚合物物质的开发中有益。 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。