Organometallic Chemistry of Open-Shell Systems

通过这一奖项，无机、生物无机和有机金属计划支持马里兰大学学院公园化学系Rinaldo Poli博士对奇电子有机金属化合物的研究。Poli博士将制备包含15或17个电子的钼、铬、钒和钨的新型有机金属化合物，并使用EPR和其他方法研究它们的反应性。将确定在有机金属体系中稳定这些“开层”的配对能和轨道裂解，从而加深对催化循环中的反应中间体的理解。大多数稳定的有机金属化合物含有18个价电子，或在某些情况下包含16个价电子，并且不会表现出各种各样的氧化态。通过研究具有奇数个电子和容纳更多种类的配体的物种，将获得关于自旋配对在反应动力学中所起作用的信息。这些信息将对设计可用作有机合成新催化剂的活性物种有价值。

With this award, the Inorganic, Bioinorganic, and Organometallic Program supports research on odd-electron organometallic compounds by Dr. Rinaldo Poli of the Chemistry Department, University of Maryland at College Park. Dr. Poli will prepare new organometallic compounds of molybdenum, chromium, vanadium, and tungsten which contain 15 or 17 electrons and investigate their reactivity using EPR and other methods. Pairing energies and orbital splittings for the stabilization of these `open shells` in organometallic systems will be determined, thus increasing understanding of reactive intermediates in catalytic cycles. Most stable organometallic compounds contain 18 valence electrons, or in some instances 16, and do not exhibit a wide variety of oxidation states. By investigating species which have an odd number of electrons and accommodate a wider variety of ligands, information on the role of spin pairing in reaction kinetics will be obtained. This information will be valuable in the design of reactive species which may serve as new catalytic agents for organic synthesis.