Coordination and Bioinorganic Chemistry with Sulfur Ligands

Charles G.博士Riordan，化学系，特拉华州的大学是由无机，生物无机和有机物计划的支持，开发开发均匀，镍的配位络合物，在温和的条件下激活分子氧。一系列由聚（硫醚）硼酸根配体支撑的单价镍络合物将被允许与O2反应以生成热敏的、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，包括紫外-可见光，共振拉曼，X-射线吸收和X-射线衍射分析进行研究。这些结果将被解释使用密度泛函理论来定义镍-氧物种的反应景观，以建立几何和电子结构功能的相关性。伴随的实验将探索镍基活化的relatedsubstrates，例如元素硫，磷和二氮烯，RN=NR。有机底物的选择性氧化通常会增加其在化学和制药领域的效用。采用O2的氧化代表有吸引力的和对环境负责的方法。该方法的灵感来自于金属蛋白利用分子氧合成新分子的活性和化学选择性。研究结果将对工业和生物氧化过程产生广泛的影响。研究经验的广度将为学生提供有机和无机合成，物理测量以及无机化学的动力学和机械方面的优秀智力和技术培训。该经验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.