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

德克萨斯农工大学化学系的Marcetta Y. Darensbourg博士在含氢和含硫配体的过渡金属配合物的化学方面所做的基础工作获得了无机、生物无机和有机金属项目的奖项。这项研究的目的是为镍、铁和钴活化S-H、C-S和C-H的某些单独步骤找到直接证据。具体来说，Darensbourg计划研究四种反应的机理：金属氢化物与有机硫试剂；铁、镍氢化物硫代配合物的二氢释放不同配体环境下硫结合镍配合物的氧化还原反应过渡金属促进了金属-近碳氢键的杂解。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。这些实验结果与产甲烷菌中加氢酶的作用和多相加氢脱硫催化剂有关，并提出了硫和氢同时结合的反应机理。

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.