CAREER: N-heterocyclic Phosphenium Cation-Containing Pincer Ligands: A Chelating Analogue of the Nitrosyl Ligand and its Non-Innocent Behavior

职业：含 N-杂环磷阳离子的钳配体：亚硝酰配体的螯合类似物及其非无害行为

• 批准号: 1148987
• 负责人: Christine Thomas
• 金额: $ 40.94万
• 依托单位: Brandeis University
• 依托单位国家: 美国
• 项目类别: Standard Grant
• 财政年份: 2012
• 资助国家: 美国
• 起止时间: 2012-09-15 至 2017-12-31
• 项目状态: 已结题
• 来源: https://www.nsf.gov/awardsearch/showAward?AWD_ID=1148987&HistoricalAwards=false
• 关键词: CAREER; heterocyclic; Phosphenium; Cation; Containing

With this award from the Chemical Catalysis Program, Professor Christine M. Thomas from Brandeis University will focus on developing a new series of redox non-innocent pincer ligands for use in catalysis. She and her students have developed a new class of tridentate pincer ligand incorporating a central N-heterocyclic phosphenium (NHP) unit. While catalytic applications of N-heterocyclic carbene (NHC) ligands have been explored extensively, their phosphorus analogues NHPs have not been evaluated in transition metal catalysis, and far less is known about their coordination chemistry. Professor Thomas and coworkers have designed an NHP-containing diphosphine pincer ligand as a method to allow more extensive studies into the transition metal chemistry of NHP ligands. Preliminary results from the Thomas' group strongly support an analogy to nitrosyl ligands, and thus the ability of NHPs to function as redox active ligands to support two-electron transformations is a promising avenue. Professor Thomas and her group will be investigating the coordination chemistry of the new NHP-diphosphine ligands with a wide variety of transition metals and exploring two-electron transformations facilitated by the NHP unit. Computational and electrochemical methods will be used to evaluate the redox-induced transformations in NHP complexes and new NHP-containing multidentate ligands will be investigated. Owing to the importance of multi-electron redox transformations in catalysis, the ultimate goal of the proposed research project is to utilize these analogues of both nitrosyls and NHCs to facilitate catalytic transformations such as C-C or C-X bond forming or breaking reactions, transfer hydrogenation, cross-coupling and other sigma-bond activation processes. The designed ligands have the potential to support two-electron redox chemistry at metals that are less prone to undergo two-electron transformations. This includes first row transition metals and early transition metals, both of which are cheaper and more naturally abundant than the traditional noble metals used in catalysis such as platinum, palladium and, rhodium. In addition to specific contributions to catalysis, the PI will use the funds to fostering the development of undergraduates interested in chemistry, and to cultivate and interest in science among K-8 students by working closely with local science museums, schools, and after-school clubs.

凭借化学催化计划的这一奖项，克莉丝汀教授M。来自布兰代斯大学的托马斯将致力于开发一系列新的氧化还原非无辜钳形配体用于催化。 她和她的学生开发了一类新的三齿钳形配体，其中包含一个中心N-杂环膦（NHP）单元。虽然N-杂环卡宾（NHC）配体的催化应用已经被广泛探索，但是它们的磷类似物NHP在过渡金属催化中还没有被评估，并且关于它们的配位化学知之甚少。托马斯教授及其同事设计了一种含NHP的双膦钳形配体，作为一种方法，可以更广泛地研究NHP配体的过渡金属化学。来自托马斯小组的初步结果强烈支持与亚硝酰基配体的类比，因此NHP作为氧化还原活性配体以支持双电子转化的能力是一种有希望的途径。托马斯教授和她的小组将研究新的NHP-双膦配体与各种过渡金属的配位化学，并探索由NHP单元促进的双电子转化。计算和电化学方法将被用来评估氧化还原诱导的转换NHP配合物和新的NHP含多齿配体将进行调查。由于多电子氧化还原转化在催化中的重要性，拟议的研究项目的最终目标是利用这些亚硝基和NHC的类似物来促进催化转化，如C-C或C-X键形成或断裂反应，转移氢化，交叉偶联和其他σ键活化过程。所设计的配体具有在不太容易经历两电子转换的金属上支持两电子氧化还原化学的潜力。 这包括第一行过渡金属和早期过渡金属，这两种金属都比催化中使用的传统贵金属如铂、钯和铑更便宜且更天然丰富。 除了对催化的具体贡献外，PI还将利用这笔资金促进对化学感兴趣的本科生的发展，并通过与当地科学博物馆，学校和课后俱乐部密切合作，培养K-8学生对科学的兴趣。