RUI: Synthesis and Reactivity of Tetrahedral Nickel Thiolate Complexes

夏洛特北卡罗来纳州大学化学系的丹尼尔·拉比诺维奇博士得到化学系无机、生物无机和有机物项目的支持，研究四面体镍硫醇盐络合物。该项目的目标是开发[NiFe]氢化酶中镍位点的模型，[NiFe]氢化酶是一组催化二氢可逆氧化为质子的细菌金属酶。为了获得与[NiFe]氢化酶中活性位点的结构非常相似的物种的数据，将合成和表征一系列具有单个末端硫醇盐基团的四面体镍络合物。为了稳定这些化合物，将采用空间要求高的三脚架辅助配体。这些配合物的反应性将研究与质子化和烷基化反应，氧化还原化学，和生产硫酯。该项目中研究的化合物具有重要意义，因为它们与生物系统中镍的性质有关。研究结果将完善我们对[NiFe]氢化酶中分子几何结构和反应性之间关系的理解。该项目将为具有各种背景，兴趣和能力的学生提供有意义的研究经验。这将包括高中，本科和硕士水平的学生。其中一些学生将是妇女和/或来自代表性不足的群体。

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.