Coordination and Bioinorganic Chemistry with Sulfur Ligands

特拉华大学化学系Charles G.Riordan博士在无机、生物无机和有机金属计划的支持下，开发均相的镍配位络合物，在温和的条件下激活氧气。一系列由聚硫醚硼配体支撑的单价镍络合物将被允许与O2反应生成热敏的还原氧中间体。这些中间体的分子结构和电子结构将用低温光谱分析技术进行研究，包括紫外可见光谱、共振拉曼光谱、X射线吸收光谱和X射线衍射分析。这些结果将被用密度泛函理论来解释，以定义镍-氧物种的反应图景，以建立几何和电子结构函数关联。随之而来的实验将探索相关底物的镍基活化，例如元素硫、磷和双氮烯，RN=NR。有机底物的选择性氧化通常会增加它们在化学和制药领域的用途。利用氧气的氧化是一种有吸引力的、对环境负责的方法。这种方法的灵感来自于对金属蛋白利用氧气合成新分子的活性和化学选择性的评价。研究结果将对工业和生物氧化过程产生广泛影响。广泛的研究经验将为学生在有机和无机合成、物理测量以及无机化学的动力学和机械方面提供出色的智力和技术培训。这一经历将为学生在行业或学术界的职业生涯做好准备。

Dr. Charles G. Riordan, Chemistry Department, University of Delaware is supported by the Inorganic, Bioinorganic, and Organometallic Program to develop develop homogeneous, coordination complexes of nickel that activate dioxygen under mild conditions. A series of monovalent nickel complexes supported by poly(thioether)borato ligands will be allowed to react with O2 to generate thermally-sensitive, reduced oxygen intermediates. The molecular and electronic structure of these intermediates will be studied using low temperature spectroscopic techniques including UV-visible, resonance Raman, X-ray absorption and X-ray diffraction analyses. These results will be interpreted using density functional theory to define the reaction landscape of the nickel-oxygen species to establish geometric- and electronic-structure function correlations. Concomitant experiments will explore nickel-based activation of relatedsubstrates, e.g. elemental sulfur, phosphorous and diazenes, RN=NR.Selective oxidation of organic substrates generally increases their utility in the chemical and pharmaceutical arenas. Oxidations employing O2 represent attractive and environmentally responsible approaches. The approach is inspired by an appreciation of the activity and chemical selectivity with which metalloproteins utilize dioxygen to synthesize new molecules. Outcomes from the studies will have broad implications to industrial and biological oxidation processes. The breadth of the research experience will provide excellent intellectual and technical training for students in organic and inorganic synthesis, physical measurements and kinetic and mechanistic aspects of inorganic chemistry. The experience will prepare students for careers in either industry or academia.