XAS STUDIES OF INTERMEDIATES IN REACTIONS OF CU(I) AND O2

本子项目是利用由NIH/NCRR资助的中心赠款提供的资源的众多研究子项目之一。子项目和研究者（PI）可能已经从另一个NIH来源获得了主要资金，因此可以在其他CRISP条目中表示。列出的机构是中心的，不一定是研究者的机构。多种酶利用铜来激活氧并介导一系列的氧反应。小的合成分子提供了一种以详细和系统的方式探索Cu/O2化学基本问题的方法。Cu k边缘的XAS已被证明是Cu/O2化学中越来越强大的技术，因为它能够探测诸如Cu氧化态，Cu-Cu距离以及Cu在固溶状态下的配位几何等重要变量。我们提出了一系列的实验，旨在了解不同条件下Cu: O2的核反应性，配体对Cu/O2形成的结构的影响，以及这些物种的结构-反应性相关性等基本问题。由于这些小分子作为酶活性位点模型，本研究提出的工作解决了铜对O2的生物无机活化以及金属/O2化学中的几个更基本的问题。

This subproject is one of many research subprojects utilizing the resources provided by a Center grant funded by NIH/NCRR. The subproject and investigator (PI) may have received primary funding from another NIH source, and thus could be represented in other CRISP entries. The institution listed is for the Center, which is not necessarily the institution for the investigator. A variety of enzymes use copper to activate O2 and to mediate a range of O2 reactivities. Small synthetic molecules offer a means of probing fundamental issues of Cu/O2 chemistry, in a detailed and systematic way. XAS at the Cu K-edge has proven to be an increasingly powerful technique in Cu/O2 chemistry, for its ability to probe such important variables as Cu oxidation state, Cu-Cu distance, as well as Cu coordination geometry, in the solid or solution state. We propose a series of experiments directed at understanding such basic issues as the nuclearity of Cu : O2 reactivity under different conditions, ligand effects on the structure of the Cu/O2 species which form, and structure-reactivity correlations in these species. Because these small molecules serve as enzyme active site models, work proposed in this study addresses bioinorganic activation of O2 by copper as well as several more fundamental issues in metal/O2 chemistry.