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

在本项目中，均相有机金属配合物将用于探索噻吩、烷基硫化物和相关含硫衍生物脱氢硫化的机理途径。初步实验表明，铑配合物插入到噻吩的C-S键中，从而为C-S键断裂之前的初始相互作用提供了模型。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。新的配合物将被检查，不仅打破C-S键，而且有可能做进一步的化学反应，导致硫从分子的有机部分完全消除。要检查的金属中心包括铑、铼和钼。在这个无机、生物无机和有机金属化学项目中，罗切斯特大学的William D. Jones博士将研究在相对低温的均匀条件下从许多有机分子中去除硫的机制。这些研究将对一系列问题产生影响，从石油燃烧引起的空气污染（酸雨）到工业过程和催化转化器中的催化剂中毒。

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.