Synthesis and Reactivity of Metallaradicals

该奖项来自化学部无机、生物无机和有机化学项目，支持特拉华州大学化学系的Klaus Theopold博士研究顺磁性有机金属铬和钒化合物的反应化学。首先，将开发由各种nacnac配体配位的铬和钒的顺磁性烷基化合物的合成。这一努力的重要目标是用于烯烃聚合的单分子催化剂的合成和结构表征。第二，发展高氧化态铬化学。这将包括探索含和不含Cp-配体的氧代烷基，以及制备用于O2驱动氧化的催化剂。最后，新的配体，包括双齿卡宾，将被用来支持顺磁性有机金属。该项目本质上是基础性的，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与目前采用的六价铬催化剂。此外，将开发比现在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到不同的研究文化，并将获得合成化学的强大背景，这是在化学和制药公司的高需求。

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.