Studies on the Chemistry of Platinum Group Element Complexes Relating to Catalysis

铂族元素配合物催化相关化学研究

• 批准号: 9729311
• 负责人: Richard Eisenberg
• 金额: $ 41.8万
• 依托单位: University of Rochester
• 依托单位国家: 美国
• 项目类别: Standard Grant
• 财政年份: 1998
• 资助国家: 美国
• 起止时间: 1998-03-01 至 2000-12-31
• 项目状态: 已结题
• 来源: https://www.nsf.gov/awardsearch/showAward?AWD_ID=9729311&HistoricalAwards=false
• 关键词: Studies; Chemistry; Platinum; Group; Element

In this project, which is supported by the Inorganic, Bioinorganic and Organometallic Chemistry program, Dr. Richard Eisenberg of the University of Rochester will continue his studies on the chemistry of platinum group element complexes relating to homogeneous catalysis and bond activation. Part one of the project is a continuation of mechanistic studies involving applications of parahydrogen induced polarization (PHIP) to new organometallic systems. This method can permit the detection of new hydride intermediates and may help elucidate the mechanism of hydrogen addition. The activation of hydrogen by oxidative addition to a variety of metal centers will be investigated, including rhodium and iridium complexes capable of intramolecular C-H and C-C activation and tantalocene hydrides. The addition of hydrogen to metal-nonmetal multiple bonds contained in alkylidene, alkylidyne, imido and sulfido complexes will also be studied in an effort to provide proof for a concerted 4-center addition. Catalytic reactions that will be investigated by PHIP include asymmetric hydrogenation and hydroformylation. Part two of the project focuses on the bond activation and catalytic reactions of organometallic systems that exhibit electrophilic or radical character. Cationic diphosphine complexes of Ir(III) and complexes with specifically designed tetradentate ligands will be synthesized. These complexes will have two adjacent labile sites for substrate binding, activation, and coupling. Related electrophilic complexes of Pt and Pd with new diimine and diamine ligands will also be studied. These and related complexes will be screened for reactivity in reactions that include H/D exchange, isomerizations, C-H bond activation, and olefin polymerizataion. Bond activation by odd electron complexes will be studied with new d7 Rh(II) and Ir(II) Schiff base complexes that contain tetradentate N and S donor ligands. The metalloradical reactions that will be studied most extensively are those involving C-H activation of methane, toluene, alkanes, and zylenes, and radical driven polymerizations. A program of research on the chemistry of platinum group element compounds relating to homogeneous catalysis and bond activation will be conducted. Platinum group element complexes include the most widely used catalysts in industry today, and developments in the past decade, particularly with regard to asymmetric catalysis and polymerization catalysis, suggest that this role will increase in the future. This program will advance our understanding of the fundamental transformations that take place at the metal and will help in the design of new important catalysts for the chemical and pharmaceutical industry.

在这个项目中，这是由无机，生物无机和 有机化学项目，理查德艾森伯格博士的大学 罗切斯特将继续研究铂族化合物 与均相催化和键活化有关的元素络合物。 该项目的第一部分是机械研究的继续 涉及仲氢诱导极化（PHIP）在新的 有机金属体系 这种方法可以检测新的 氢化物中间体，并可能有助于阐明氢的机制 的增订条文 通过氧化加成使氢活化， 将研究金属中心的数量，包括铑和铱 能够分子内C-H和C-C活化的复合物， 二茂钽 金属-非金属加氢 亚烷基、亚烷基、亚氨基和硫基中含有多重键 复合物也将被研究，以努力提供证据， 协同的4中心加成。 催化反应， 包括不对称氢化， 水蒸气 该项目的第二部分侧重于债券激活 和有机金属体系的催化反应， 亲电子或激进的特点。 阳离子双膦配合物 Ir（III）和具有特别设计的四齿配体的配合物 将被合成。 这些复合物将有两个相邻的不稳定位点 用于底物结合、活化和偶联。 相关亲电性 铂和钯与新的二亚胺和二胺配体的络合物也将被 研究了 这些和相关的复合物将被筛选的反应性， 包括H/D交换，异构化，C-H键活化， 和烯烃聚合。 奇电子络合物的键活化 将使用新的d 7 Rh（II）和Ir（II）Schiff碱配合物进行研究， 含有四齿N和S供体配体。 金属自由基 将被广泛研究的反应是那些涉及C-H 甲烷、甲苯、烷烃和苯的活化，以及自由基驱动 聚合。 铂族元素化学研究计划 涉及均相催化和键活化的化合物将被 进行。 铂族元素络合物包括最广泛使用的 当今工业中的催化剂，以及过去十年的发展， 特别是关于不对称催化和聚合 催化剂，表明这一作用将在未来增加。 这 该计划将促进我们对基本转变的理解， 这将有助于设计新的重要的 用于化学和制药工业的催化剂。