RUI: Synthesis and Reactivity of Tetrahedral Nickel Thiolate Complexes

丹尼尔·拉比诺维奇博士，北卡罗来纳大学夏洛特分校化学系，由化学部无机、生物无机和有机金属计划支持，研究四面体硫代镍络合物。该项目的目标是开发[NiFe]氢酶中镍位置的模型，[NiFe]氢酶是一组细菌金属酶，可催化二氢可逆氧化为质子。为了获得与[NiFe]氢酶活性中心结构非常相似的物种的数据，我们将合成和表征一系列具有单端硫代基团的四面体镍配合物。为了稳定这些化合物，将使用空间要求很高的三脚架辅助配体。这些络合物的反应性将从质子化和烷基化反应、氧化还原化学和硫代酯的产生方面进行研究。本项目中研究的化合物具有重要意义，因为它们与生物体系中镍的性质有关。这项研究的结果将加深我们对[NiFe]氢酶分子几何结构和反应活性之间关系的理解。这个项目将为不同背景、兴趣和能力的学生提供有意义的研究体验。这将包括高中生、本科生和硕士研究生。其中一些学生将是妇女和/或来自代表人数不足的群体。

Dr. Daniel Rabinovich, Chemistry Department, University of North Carolina - Charlotte, is supported by the Inorganic, Bioinorganic, and Organometallic Program of the Chemistry Division to study Tetrahedral Nickel Thiolate Complexes. The goal of the project is to develop models of the nickel site in [NiFe] hydrogenases, a group of bacterial metalloenzymes that catalyze the reversible oxidation of dihydrogen to protons. In order to obtain data on species that closely resemble the architecture of the active site in [NiFe] hydrogenases a series of tetrahedral nickel complexes having a single terminal thiolate group will be synthesized and characterized. In order to stabilize these compounds, sterically demanding tripodal ancillary ligands will be employed. The reactivity of these complexes will be studied with regards to protonation and alkylation reactions, redox chemistry, and the production of thioesters. The compounds studied in this project are significant because of their relevance to the properties of nickel in biological systems. The results of the research will refine our understanding of the relationship between molecular geometry and reactivity in [NiFe] hydrogenases. This project will provide a meaningful research experience to students with a variety of backgrounds, interests, and abilities. This will include high school, undergraduate, and masters level students. A number of these students will be women and/or from underrepresented groups.