Hydrides and Thiolates as Compatible Ligands in Transition Metal Complexes. Heterolytic Bond Activations

氢化物和硫醇盐作为过渡金属配合物中的相容配体。

• 批准号: 9109579
• 负责人: Marcetta Darensbourg
• 金额: $ 27.3万
• 依托单位: Texas A&M Research Foundation
• 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 1994-12-31
• 项目状态: 已结题
• 来源: https://www.nsf.gov/awardsearch/showAward?AWD_ID=9109579&HistoricalAwards=false
• 关键词: Hydrides; Thiolates; Compatible; Ligands; Transition

This award in the Inorganic, Bioinorganic and Organometallic Program is made to Dr. Marcetta Y. Darensbourg of the Chemistry Department, Texas A&M University, for fundamental work on the chemistry of transition metal complexes containing both hydrogen and sulfur-containing ligands. The goal of the research is to find direct evidence for some of the individual steps in S-H, C-S and C-H activation by nickel, iron, and cobalt. Specifically Darensbourg plans to investigate the mechanism of four types of reactions: metal hydrides with organosulfur reagents; dihydrogen release from hydrido-thiolate complexes of iron and nickel; oxidation-reduction of sulfur-bound nickel complexes with various ligand environments; and transition metal promoted heterolysis of metal-proximate C-H bonds. In the studies of sulfur-bound nickel complexes, dependence of the oxidation potential and of the oxidative addition of hydrogen on the presence of sulfur and phosphorus ligands will be investigated. %%% The results of these experiments are relevant to the action of hydrogenase enzymes in methanogenic bacteria and heterogeneous hydrodesulfurization catalysts, in which reaction mechanisms involving simultaneous bonding of sulfur and hydrogen have been proposed.

该无机、生物无机和有机金属项目奖项授予德克萨斯农工大学化学系的 Marcetta Y. Darensbourg 博士，以表彰其在含有氢和含硫配体的过渡金属配合物化学方面的基础工作。 该研究的目标是找到镍、铁和钴活化 S-H、C-S 和 C-H 中某些单独步骤的直接证据。 具体来说，达伦斯堡计划研究四种反应的机理：金属氢化物与有机硫试剂；从铁和镍的氢化硫醇络合物中释放出氢气；硫结合镍络合物在各种配体环境下的氧化还原； 过渡金属促进金属邻近的C-H键的异解。 在硫结合镍配合物的研究中，将研究氧化电位和氢的氧化加成对硫和磷配体存在的依赖性。 %%% 这些实验的结果与产甲烷细菌和非均相加氢脱硫催化剂中氢化酶的作用有关，其中提出了涉及硫和氢同时键合的反应机制。