The Singlet Diradical Character of Multiple Bonded Compounds of the Heavier Group 13 and 14 Elements

加州大学戴维斯分校化学系Phillip Power博士在无机化学、生物无机化学和金属有机化学计划的支持下，探索RMMR(M=Al-Tl或Si-Pb)类型的多键较重主族化合物的单重态双自由基特征。将制备一系列新的电子修饰的三苯基、酰胺、磷化物、芳氧基和硫酸盐配体，并用于形成RMMR和杂元素RMM‘R’络合物。将用各种试剂研究这些物种的化学，以确定是否会遇到双自由基行为。此外，新化合物将通过各种技术进行表征，包括X射线结晶学、溶液和固态异核核磁共振光谱、Moessbauer光谱、电化学和计算研究。这些结果将被用来关联成键和电子变化，这些变化很难用传统的价态、轨道重叠、杂化和键序来描述。这一研究将促进对较重主族元素成键的基本理解。例如，多个键在碳的化学中起着极其重要的作用。然而，较重的同系物不容易形成多个键。该项目旨在研究硅、锗、锡和铅等元素的多个键的性质和化学性质。研究生、本科生和博士后助理将在前沿的合成无机化学项目中获得出色的培训和研究经验。

Dr. Phillip Power, Chemistry Department, University of California - Davis, is supported by the Inorganic, Bioinorganic, and Organometallic Chemistry Program to explore the singlet diradical character of multiple bonded heavier main group compounds of the type RMMR (M = Al-Tl or Si-Pb). A range of new electronically modified terphenyl, amide, phosphide, aryloxide and thiolate ligands will be prepared and used to form RMMR and heteroelement RMM'R' complexes. The chemistry of these species will be investigated with a variety of reagents in order to determine if diradical behavior is encountered. In addition, the new compounds will be characterized by a variety of techniques including X-ray crystallography, solution and solid state heteronuclear NMR spectroscopy, Moessbauer spectroscopy, electrochemical and computational studies. These results will be used to correlate bonding and electronic changes that are difficult to describe in traditional terms of valency, orbital overlap, hybridization and bond order.This research will advance the fundamental understanding of the bonding of the heavier main group elements. Multiple bonds play an exceedingly important role in the chemistry of, e.g., carbon. However, heavier cogeners do not easily form multiple bonds. This project is aimed at investigating the nature and chemical properties of multiple bonds of such elements as silicon, germanium, tin, and lead. Graduate students, undergraduate students and postdoctoral associates will receive excellent training and research experiences in a forefront synthetic inorganic chemistry program.