Studies of Carbon-Sulfur Bond Cleavage by Homogeneous Transition Metal Complexes

在本项目中，将使用均相有机金属络合物来探索噻吩硫醚、烷基硫化物和相关的含硫衍生物的脱氢硫化机理。初步实验表明，在噻吩基C-S键上插入了一个Rh络合物，从而为C-S键断裂前的初始相互作用提供了一个模型。将阐明中间体的结构，并确定控制反应活性和选择性的动力学和热力学参数。新的配合物将被研究，它们不仅打破了C-S键，而且还有可能进行进一步的化学操作，从而完全消除分子中有机部分的硫。被检查的金属中心包括Rh、Re和Mo。%在这个项目中，罗切斯特大学的William D.Jones博士将在相对较低的温度下，研究在均匀条件下从一些有机分子中脱除硫的机理。这些研究将对从石油燃烧(酸雨)造成的空气污染到工业过程和催化转化器中的催化剂中毒等一系列问题产生影响。

In this project homogeneous organometallic complexes will be used to explore the mechanistic pathways for the dehydrosulfurization of thiophene, alkyl sulfides, and related sulfur containing derivatives. Preliminary experiments demonstrate that a rhodium complex inserts into the thiophene C-S bond, thus providing a model for the initial interaction prior to C-S bond cleavage. The structures of the intermediates will be elucidated and the kinetic and thermodynamic parameters that control the reactivity and selectivity will be determined. New complexes will be examined that not only break C-S bonds, but also have the potential to do further chemistry resulting in the total elimination of sulfur from the organic portion of the molecule. Metal centers to be examined include rhodium, rhenium, and molybdenum. %%% In this project in the Inorganic, Bioinorganic, and Organometallic Chemistry Program, Dr. William D. Jones of the University of Rochester will study the mechanisms of removal of sulfur from a number of organic molecules under homogeneous conditions at relatively low temperatures. The studies will have an impact on problems ranging from air pollution due to oil combustion (acid rain) to catalyst poisoning in industrial processes and in catalytic converters.