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

9421727罗彻斯特大学琼斯大学化学系威廉·D·琼斯博士由化学部无机化学、生物无机化学和有机金属化学项目支持，探索噻吩类及相关含硫衍生物加氢脱硫的机理途径。这些研究将包括物理有机金属实验，旨在探索碳-硫键断裂步骤的性质。将阐明所涉及的中间体的结构，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。取代的二苯并硫烯类化合物将被详细研究，这些化合物被证明是最难脱硫的。将评估几个双核金属系统的加氢脱硫活性。石油精炼是当今世界上正在进行的规模最大的化学过程之一。硫是所有原油中的次要成分，在燃烧过程中会转化为对环境有害的二氧化硫，它的脱除是精炼过程中的一个重要步骤(称为加氢脱硫或HDS)。虽然在试图了解HDS过程的显著特征方面已经做了大量工作，但仍有许多问题有待回答。在该项目中，将研究金属物种如何与原油中发现的含硫化合物相互作用的细节。这将为改进工业流程的设计和获得新的更有效的脱硫剂提供所需的背景信息。

9421727 Jones University of Rochester Dr. William D. Jones, Chemistry Department, University of Rochester, is supported by the Inorganic, Bioinorganic, and Organometallic Chemistry Program of the Chemistry Division to explore the mechanistic pathways for the hydrodesulfurization of thiophene and related sulfur containing derivatives. The studies will involve physical organometallic experiments designed to probe the nature of the carbon-sulfur bond breaking step. The structures of intermediates that are involved 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. Substituted dibenzothiopenes will be examined in some detail, these compounds prove the most difficult to desulfurize. Several binuclear metal systems will be assessed for HDS activity. The refining of petroleum is one of largest scale chemical processes being carried out in the world today. The removal of sulfur, a minor constituent in all crude oils which is converted to environmenally harmful sulfur dioxide during combustion, is an important step (called hydrodesulfurization or HDS) in the refining procedure. While a great deal of work has been done in trying to understand the salient features of the HDS process, many questions remain to be answered. In the project the details of how metal species interact with the sulfur containing compounds found in crude oil will be investigated. This will provide the background information needed to improve the design of the industrial process and to obtain new more efficient catalysts for sulfur removal.