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

道格拉斯博士B。Grotjahn，化学系，圣地亚哥州立大学，是由无机，生物无机和有机化学计划的化学部的研究到金属乙烯酮络合物的化学支持。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，并且它们允许快速获得各种有机产物，其中许多需要使用标准有机反应的多步合成。然而，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，将制备新的乙烯酮络合物，并从它们开发催化体系。具体而言，异常稳定的Ir和Rh烯酮配合物将被制备，金属-烯酮键合在他们将其特征在于通过X-射线衍射和IR和NMR光谱，（C，C）和（C，O）键异构体之间的热力学和动力学关系将划定，和卡宾-CO和烯酮配合物的相互转化将被研究。利用这些数据，将开发以乙烯酮或卡宾配合物为中间体的催化碳-碳键形成反应，为有机金属化学、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、毒性更低的有机化合物的大规模合成制备将成为可能。除了基础科学之外，在项目过程中还将培训代表性不足的少数民族学生和本科生。

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.