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Role of Metal Sulfides in Carbon-Heteroatom Bond Cleavage

金属硫化物在碳-杂原子键断裂中的作用

基本信息

批准号：
9104521
负责人：
Mary Rakowski DuBois
金额：
$ 25.64万
依托单位：
University of Colorado at Boulder
依托单位国家：
美国
项目类别：
Continuing Grant
财政年份：
1991
资助国家：
美国
起止时间：
1991-07-01 至 1995-12-31
项目状态：
已结题

来源：
https://www.nsf.gov/awardsearch/showAward?AWD_ID=9104521&HistoricalAwards=false
关键词：
Role Metal Sulfides Carbon Heteroatom

项目摘要

Dr. Mary Rakowski-DuBois of the Chemistry Department, University of Colorado at Boulder, is supported by the Inorganic, Bioinorganic, and Organometallic Chemistry Program for investigation of C=O, C-S, and C-N bond cleavage reactions promoted by transition metal complexes containing sulfide ligands. In the case of C=O, for example, it is expected that carbon monoxide would insert into an SH bond of an SH ligand which serves as a bridge for a molybdenum dimer. The formylthiolate thus produced is susceptible to reductive cleavage of the C=O bond by hydrogen. This could model a first step of the conversion of CO to methane, a reaction not commonly promoted by transition metal complexes, and here promoted by bonding to sulfur rather than to the metal. This study might provide insight into the mechanism of CO reduction catalyzed by heterogeneous molybdenum sulfides. In studies of C-N bond cleavage by hydrogen, the sulfided metal complexes would serve as models of the heterogeneous catalysts used in commercial HDN (hydrodenitrogenation) processes. In addition to the reactions described above, novel complexes containing Ir, Rh, Re, Mo, and Mo-Cr and a variety of sulfur- and nitrogen-containing ligands will be prepared. %%% This project is expected to provide insight into the reactions of transition metal complexes with small molecules, which are important in the use of such complexes as heterogeneous and homogeneous catalysts. Specifically, these studies may provide information pertinent to understanding the behavior of commercial heterogeneous catalysts used for hydrodenitrogenation.

化学系的玛丽·拉科夫斯基-杜波依斯博士位于博尔德的科罗拉多大学由无机，生物无机和有机化学课程用于研究C=O、C-S和C-N键断裂反应含硫化物的过渡金属配合物促进的配体。例如，在C=O的情况下，预计一氧化碳会插入SH配体的SH键中其用作钼二聚体的桥。的由此产生的甲酰基硫醇盐易于还原， C=O键被氢裂解。这可能是第一个在将CO转化为甲烷的步骤中，不通常由过渡金属络合物促进，通过与硫键合而不是与金属键合来促进。这这项研究可能有助于深入了解CO还原的机理由多相硫化钼催化。研究中 C-N键被氢裂解，硫化金属络合物将作为模型的非均相催化剂用于商业HDN（加氢脱氮）方法。除了上述反应，含有Ir的新型配合物， Rh、Re、Mo和Mo-Cr以及各种硫-和将制备含氮配体。 %%% 该项目预计将提供深入了解反应过渡金属配合物与小分子，重要的是，在使用这种复合物时，均相催化剂具体而言，这些研究可以提供与理解行为相关的信息商业非均相催化剂用于加氢脱氮