Mechanisms of Reaction of Organometallic Radicals and Insertion Reactions

加州大学圣地亚哥分校的威廉·C·特罗格勒将研究17电子有机金属自由基的合成、结构和反应机理，这是无机化学、生物无机化学和金属有机化学计划的一部分。其目标是开发新的化学转化催化剂，可应用于特种化学品和药物化合物的合成。该项目的另一个重点是研究后过渡金属配合物作为激活氮-氢和氧-氢键的可能试剂，以便促进不饱和有机化合物(如烯烃)分别插入金属-氮和金属-氧键。这一领域还旨在更好地确定氨、胺和醇与碳-碳双键的催化加成反应的要求。该项目的第一部分将使用的化合物是中性的富含电子的18电子络合物，可以通过电化学氧化得到稳定的或短寿命的阳离子自由基。它们的代表是二羰基(烯烃)环丁二烯铁、(叔膦)(烯烃)环戊二烯基钴和双(烯烃)环戊二烯基铑。第二部分研究中使用的化合物将主要来自铂族金属。

William C. Trogler of the University of California at San Diego will study the synthesis, structure and reaction mechanisms of 17-electron organometallic radicals as part of this project within the Inorganic, Bioinorganic and Organometallic Chemistry Program. The goal is to develop catalysts for new chemical transformations that could be applied to the synthesis of specialty chemicals and medicinal compounds. Another thrust of the project is the investigation of late transition metal coordination complexes as possible reagents for the activation of nitrogen-hydrogen and oxygen-hydrogen bonds in order to facilitate insertion of unsaturated organic compounds such as olefins into the metal-nitrogen and metal-oxygen bonds, respectively. This area is also aimed at better defining the requirements for catalytic addition of ammonia, amines and alcohols to carbon-carbon double bonds. Compounds to be employed in the first part of the project are neutral electron rich 18-electron complexes which can be electrochemically oxidized to give stable or short-lived cationic radicals. Representative of these are dicarbonyl(olefin)cyclobutadieneiron, (tertiary- phosphine)(olefin)cyclopentadienylcobalt and bis(olefin)cyclopentadienylrhodium. Compounds employed in the second part of the study will be mainly from the platinum group of metals.