Synthesis and Reactivity of Metallaradicals

该奖项由化学部无机、生物无机和有机金属化学项目颁发，支持特拉华大学化学系Klaus Theopold博士对顺磁性有机金属铬和钒化合物的反应化学研究。首先，研究了由各种配体配位的铬钒顺磁性烷基的合成。这项工作的重要目标是烯烃聚合单分子催化剂的合成和结构表征。二是发展高氧化态铬化学。这将包括有和没有cp配体的氧烷基的探索，以及o2驱动氧化催化剂的制备。最后，新的配体，包括双齿碳烯，将用于支持顺磁性有机金属。这个项目是基础性的，但将对商业催化剂的开发产生实际影响。这项工作将研究如何氧原子转移和氢是从碳氢化合物中提取发生在目前使用的六价铬催化剂。此外，将开发比目前使用的催化剂更环保的替代催化剂。本科生和研究生将体验多样化的研究文化，并将获得化学和制药公司高需求的合成化学的强大背景。

This award from the Inorganic, Bioinorganic and Organometallic Chemistry Program of the Chemistry Division supports Dr. Klaus Theopold, Chemistry Department, University of Delaware, for research into the reaction chemistry of paramagnetic organometallic chromium and vanadium compounds. First, the synthesis of paramagnetic alkyls of chromium and vanadium coordinated by various nacnac-ligands will be developed. Important goals of this effort are the synthesis and structural characterization of single molecule catalysts for olefin polymerization. Secondly, high oxidation state chromium chemistry will be developed. This will include an exploration of oxo alkyls both with and without Cp-ligands, and the preparation of catalysts for O2-driven oxidation. Finally, new ligands, including bidentate carbenes, will be utilized to support paramagnetic organometallics. This project is fundamental in nature but will have practical impact on commercial catalyst development. The work will examine how oxygen atom transfers to and hydrogen is abstracted from hydrocarbons takes place with presently employed hexavalent chromium catalysts. Additionally, alternative catalysts that are more environmentally benign than those now used will be developed. Undergraduate and graduate students will experience a varied research culture and will gain a strong background in synthetic chemistry which is in high demand in chemical and pharmaceutical companies.