Cleavage and Formation of C-S and C-N Bonds in Heterocyclic Compounds by Homogeneous Transition Metal Complexes

无机化学、生物无机化学和金属有机化学计划的这一奖项支持罗切斯特大学的威廉·D·琼斯教授开发新的加氢脱硫技术和合成应用，以裂解和形成噻吩类和含过渡金属碎片的含氮杂环化合物中的C-S和C-N键。其目的是：(1)提供关于这些强的和/或受阻的C-X键(X=S，N)裂解的基本信息，(2)提供C-X键裂解的机理(S)的信息，(3)研究含硫和含氮的有机化合物与金属结合的结构基元，(4)了解金属巯基和硫化物的化学，它们的相互转化，以及它们的能力，以及(5)开发C-S和C-N键的催化体系。有待探索的新概念包括确定电子效应对键断裂的影响，以及使用支撑体系进行催化。本科生和研究生都将接受使用无机、有机、分析和物理概念的高级培训。罗切斯特大学与汉普顿大学有一个联合项目，以吸引来自汉普顿硕士项目中代表性不足群体的学生直接进入罗切斯特博士项目。这项科学工作的目的是更好地了解如何脱除碳氢燃料中仍存在的最具抵抗力的多烷基二苯并噻吩类化合物。这一知识将有助于满足美国环保局关于燃料低硫排放的新标准。这项工作的另一个影响是开发了合成含氮杂环的新路线，含氮杂环是许多生物重要化合物的基本构件。

This award in the Inorganic, Bioinorganic and Organometallic Chemistry Program supports research by Professor William D. Jones at the University of Rochester to develop new hydrodesulfurization techniques and synthetic applications for the cleavage and formation of C-S and C-N bonds in thiophenes and heterocyclic nitrogen containing compounds with transition metal fragments. The objectives are to: (1) provide basic information about the requirements for the cleavage of these strong and/or hindered C-X bonds (X = S, N), (2) provide information about the mechanism(s) for C-X bond cleavage, (3) examine structural motifs for the binding of sulfur- and nitrogen-containing organic compounds to metals, (4) understand the chemistry of metal sulfhydryl and sulfido compounds, their interconversion, and their lability, and (5) develop catalytic systems for manipulation of C-S and C-N bonds. New concepts to be explored include the determination of electronic effects on bond cleavage and the use of supported systems for catalysis. Both undergraduate and graduate students will be trained at an advanced level to use the concepts of inorganic, organic, analytical, and physical. The University of Rochester has a joint program with Hampton University to attract students from underrepresented groups from the Hampton M.S. program directly into the Rochester Ph.D. program. The scientific work is aimed at a better understanding of how to desulfurize the most resistant polyalkylated dibenzothiophenes still found in hydrocarbon fuels. This knowledge will help in meeting the new EPA standards for low sulfur emissions from fuels. Another impact of the work is in developing new synthetic routes to nitrogen-containing heterocycles, a fundamental building block in many biologically important compounds.