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博士得到了金属酮化学化学研究化学研究部的无机，生物促和有机化化学计划。金属酮络合物是从碳烯络合物开始的独特键形成反应中的重要中间体，它们允许快速进入各种有机产品，其中许多需要使用标准有机反应进行多步合成。但是，几乎所有这些过程在金属络合物中都是化学计量的。该项目的目的是开发可能成为有吸引力的合成有机过程的催化反应。为了实现这一目标，将准备新的酮复合物，并从中开发出催化系统。具体而言，将准备异常稳定的IR和RH酮复合物，其中的金属键酮键合的特征是X射线衍射以及IR和NMR光谱，（C，C）和（C，O）链接异构体之间的热力学和动力学关系将被描绘，以及Carbene-Co和Carbene-Cosexs的相互作用。使用这些数据，将开发涉及酮或碳烯复合物作为中间体的催化碳碳键形成反应。拟议的研究将有助于有机化和有机化学和催化，与有机合成和工业化学有关。最终，有机化合物的更方便，更抗毒的大规模合成制剂将有可能。除了基础科学外，在项目过程中将接受代表性不足的少数群体和本科生的培训。