Coordination and Bioinorganic Chemistry with Sulfur Ligands

特拉华大学化学系Charles G. Riordan博士得到了无机、生物无机和有机金属项目的支持，开发出在温和条件下激活二氧的均匀、配位镍配合物。一系列由聚硫醚硼配体支撑的一价镍配合物将被允许与O2反应生成热敏的、还原的氧中间体。这些中间体的分子和电子结构将使用低温光谱技术进行研究，包括紫外可见、共振拉曼、x射线吸收和x射线衍射分析。这些结果将使用密度泛函理论来解释，以定义镍氧物种的反应景观，以建立几何和电子结构函数相关性。伴随的实验将探索相关底物的镍基活化，例如单质硫、磷和重氮，RN=NR。有机底物的选择性氧化通常增加了它们在化学和制药领域的用途。利用O2氧化是一种有吸引力且对环境负责的方法。这种方法的灵感来自于对金属蛋白利用二氧合成新分子的活性和化学选择性的认识。这些研究的结果将对工业和生物氧化过程产生广泛的影响。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理方面提供优秀的智力和技术培训。这段经历将为学生在工业界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.