Ketene Complexes: Structure, Bonding, Catalysis, and Interconversion with Carbene Complexes

烯酮配合物：结构、键合、催化以及与卡宾配合物的互变

• 批准号: 0112223
• 负责人: Douglas Grotjahn
• 金额: $ 29.3万
• 依托单位: San Diego State University Foundation
• 依托单位国家: 美国
• 项目类别: Standard Grant
• 财政年份: 2001
• 资助国家: 美国
• 起止时间: 2001-08-01 至 2004-07-31
• 项目状态: 已结题
• 来源: https://www.nsf.gov/awardsearch/showAward?AWD_ID=0112223&HistoricalAwards=false
• 关键词: Ketene; Complexes; Structure; Bonding; Catalysis

Dr. Douglas B. Grotjahn, Chemistry Department, San Diego State University, is supported by the Inorganic, Bioinorganic, and Organometallic Chemistry Program of the Chemistry Division for research into the chemistry of metal ketene complexes. Metal-ketene complexes are important intermediates in unique bond-forming reactions starting from carbene complexes and they allow rapid access to a variety of organic products, many of which would require multistep syntheses using standard organic reactions. However, nearly all of these processes are stoichiometric in the metal complex. The goal of the project is to develop catalytic reactions that are likely to become attractive synthetic organic procedures. To achieve this, new ketene complexes will be prepared and catalytic systems developed from them. Specifically, unusually stable Ir and Rh ketene complexes will be prepared, metal-ketene bonding within them will be characterized by X-ray diffraction and IR and NMR spectroscopy, the thermodynamic and kinetic relationships between(C,C)and (C,O) linkage isomers will be delineated, and the interconversion of carbene-CO and ketene complexes will be studied. Using these data, catalytic carbon-carbon bond-forming reactions involving ketene or carbene complexes as intermediates will be developed.The proposed research will contribute to the fields of organometallic and organic chemistry and catalysis, relevant to both organic synthesis and industrial chemistry. Ultimately, more convenient, less-toxic large scale synthetic preparations of organic compounds will be possible. In addition to the basic science, underrepresented minority and undergraduate students will be trained during the course of the project.

圣地亚哥州立大学化学系的 Douglas B. Grotjahn 博士得到化学系无机、生物无机和有机金属化学项目的支持，从事金属烯酮络合物化学研究。金属-乙烯酮络合物是从卡宾络合物开始的独特成键反应中的重要中间体，它们可以快速获得各种有机产品，其中许多产品需要使用标准有机反应进行多步合成。然而，几乎所有这些过程在金属配合物中都是化学计量的。该项目的目标是开发可能成为有吸引力的合成有机程序的催化反应。为了实现这一目标，将制备新的乙烯酮配合物并由此开发催化系统。具体来说，将制备异常稳定的Ir和Rh乙烯酮配合物，其中的金属-乙烯酮键合将通过X射线衍射、红外和核磁共振光谱进行表征，以及(C,C)和(C,O)之间的热力学和动力学关系将描述连接异构体，并研究卡宾-CO和烯酮配合物的相互转化。利用这些数据，将开发涉及乙烯酮或卡宾配合物作为中间体的催化碳-碳键形成反应。拟议的研究将为有机金属和有机化学和催化领域做出贡献，与有机合成和工业化学相关。最终，更方便、毒性更小的有机化合物的大规模合成制备将成为可能。除了基础科学外，项目期间还将对少数族裔和本科生进行培训。