XAS STUDIES OF A METHANE HYDROXYLATING BINUCLEAR MODEL COMPLEX

甲烷羟基化双核模型复合物的XAS研究

• 批准号: 7370490
• 负责人: BRITT HEDMAN
• 金额: $ 0.43万
• 依托单位: STANFORD UNIVERSITY
• 依托单位国家: 美国
• 财政年份: 2006
• 资助国家: 美国
• 起止时间: 2006-03-01 至 2007-02-28
• 项目状态: 已结题
• 来源: https://reporter.nih.gov/project-details/7370490
• 关键词: XAS; STUDIES; METHANE; HYDROXYLATING; BINUCLEAR

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 new binuclear iron model complex has been synthesized and characterized, which converts methane into methanol with high efficiency. The relative instability and short lifetime of its catalytic intermediate has thus far precluded obtaining structural data on this intermediate. It is proposed here to utilize x-ray absorption spectroscopy (edge and EXAFS) to address the electronic and geometric structure. The intermediate is thought to contain a mixed-valent site, specifically considered to be comprised of a six-coordinate ferrous center bridged to a six-coordinate ferryl-oxo moiety. Through prudent use of information obtained from data of the catalytic precursor and decay product, as well as from additional specific model complexes, the relative contributions of this mixture to the pre-edge, edge and EXAFS data of the intermediate will be separated, as described in the proposal. The characterization of this complex has several important implications: in the industrial conversion of methane to methanol, as an inorganic model complex, and as a model of the methanol-converting active site of methane monooxygenase.

该子项目是利用NIH/NCRR资助的中心赠款提供的资源的许多研究子项目之一。子弹和调查员（PI）可能已经从其他NIH来源获得了主要资金，因此可以在其他清晰的条目中代表。列出的机构适用于该中心，这不一定是调查员的机构。已经合成和表征了一种新的双核铁模型复合物，该复合物以高效率将甲烷转化为甲醇。迄今为止，其催化中间体的相对不稳定性和短寿命已无法在该中间体上获得结构数据。这里建议利用X射线吸收光谱（边缘和EXAFS）来解决电子和几何结构。中间体被认为包含一个混合物位置，被认为是由六个坐标的亚铁中心组成的，桥接到六坐标的Ferryl-oxo部分。通过谨慎使用从催化前体和衰减产物的数据以及其他特定模型复合物中获得的信息，该混合物对中间体的前边，边缘和EXAFS数据的相对贡献将被分开，如提案中所述。该复合物的表征具有几个重要的含义：在甲烷向甲醇的工业转化中，作为无机模型复合物，以及作为甲烷单氧酶的甲醇转化活性位点的模型。