Establishing Bonding and Reactivity in Organometallic Uranium Species

该项目由化学部化学合成计划资助。普渡大学的苏珊娜·巴特教授研究铀的有机金属化学。有机金属化学是研究含有金属-碳键的化合物，药物，材料和精细化学品的许多进展都基于有机金属化学。虽然铀的行为已经研究了很多年，但其有机金属化学仍然非常有限。一般来说，金属可以与碳形成一个、两个或三个化学键。本研究制备含铀碳双键的化合物，并研究其反应性。在这些发现的基础上，还制备了具有铀、硅和铀-氮双键的化合物。这些研究为今后开发铀的新应用奠定了基础。此外，该项目还对本科生和研究生进行铀化学方面的培训。这一点非常重要，因为铀化学工作人员正在老化，目前很少有年轻科学家接受该领域的培训。巴特教授和她的学生还为高中教师组织了一个科学夏令营，他们的目标是通过动手活动和设计新的演示，为教师提供铀化学的新技能。使用空间体积大的氢化三（二甲基吡唑基）硼酸盐作为支持配体，形成双（烷基）铀作为配体，制备铀-亚烷基，-硅烯，和-亚氨基配合物。这些化合物的特征在于使用多种分析技术，包括多核NMR，红外和电子吸收光谱，以及X射线晶体学和计算方法。铀氮键的强度进行了评估，使用氢原子转移的研究，铀氮多重键的键强度进行了评估和f-轨道的多重键的作用进行了理论研究。一个推广计划介绍了锕系元素化学到科学夏令营。

This project is funded by the Chemical Synthesis program of the Chemistry Division. Professor Suzanne Bart, Purdue University, studies the organometallic chemistry of uranium. Organometallic chemistry is the study of compounds that contain metal-carbon bonds and many advances in pharmaceuticals, materials, and fine chemicals are based on organometallic chemistry. While the behavior of uranium has been studied for many years, its organometallic chemistry remains quite limited. In general, metals can form one, two, or three chemical bond to carbon. This study prepares compounds containing uranium carbon double bonds and investigates their reactivity. Building on these findings compounds with uranium silicon and uranium-nitrogen double bonds also are prepared. These studies lay the ground work for the future development of new applications for uranium. In addition, the project trains undergraduate and graduate students in uranium chemistry. This is extremely important as the uranium chemistry workforce is aging and very few young scientists currently receive training in the field. Prof. Bart and her students also organize a science summer camp for high school teachers where they aim to give the teachers new skills in uranium chemistry through hands on activities and the design new demonstrations. Using sterically bulky hydrotris(dimethylpyrazoly)borate as supporting ligands, uranium bis(alkys) are formed as used as synthons to prepare uranium-alkyledene, -silene, and -imido complexes. These compounds are characterized using multiple analytical techniques, including multinuclear NMR, infrared, and electronic absorption spectroscopies, as well as X-ray crystallography and computational methods. The strength of the uranium-nitrogen bonds is assessed using hydrogen atom transfer studies the bond strength of the uranium-nitrogen multiple bonds are assessed and the role of f-orbitals in the multibonds is examined theoretically. An outreach program introduces actinide chemistry into a science summer camp.