Photochemical Generation, Kinetics and Chemistry of Transition Metal Nitrosyl Linkage Isomers

该奖项在无机，生物无机和有机化学计划支持博士托马斯Bitterwolf，化学系，爱达荷州大学，研究金属结合亚硝酰基配体及其链接异构体使用冷冻基质方法和时间分辨红外（IR）技术的研究。多年来，已知NO配体通过氮或氧结合金属。最近，它的能力绑定金属在一个侧面的方式已被证明。此外，时间分辨晶体学和红外光谱研究表明，在有机金属和配位化合物中的亚硝酰基配体可以进行光化学键异构化。本研究将建立一个理解的因素，导致形成和稳定的亚硝酰键异构体通过检查几类化合物代表了一系列的配体类型和电子计数。其中包括：[CpMn（CO）2NO]阳离子;[Fe（CO）3NO]阴离子;胭脂红的盐，[Fe 2（NO）4（S）2]二价阴离子，和黑的盐，[Fe 3（NO）7（S）]阴离子; Co（II）（salen）（NO）和Co（II）（acacen）（NO）; Fe（S2CNR 2）2（NO）;和CpM（NO）2X，其中M = Cr、Mo或W，X是各种阴离子物质。冷冻有机基质方法将用于识别那些类别的化合物，侧键连接异构体形成后，光解和时间分辨红外光谱将用于研究的链接异构体的松弛动力学回到终端亚硝酰基形式。从这些数据中，热力学活化参数将被导出。该项目的最后一部分将利用时间分辨红外光谱和其他闪光动力学方法来检查几个反应，其中侧键连接异构体可能参与。一氧化氮在细胞间通讯、平滑肌松弛和细胞毒性免疫反应中起着介导作用。人们对鉴定在生物系统中释放氮氧化物的化合物有很大的兴趣。这些材料的优化需要更详细地了解氮氧化物释放的机制。本研究将确定附着在金属上的NO基团释放的细节。这些研究将与太平洋西北国家实验室合作进行。这将为从事该项目的博士后，研究生和本科生提供极好的经验。高中教师和美国原住民高中学生将接触到该项目通过PI的参与默多克基金会合作伙伴在科学计划。

This award in the Inorganic, Bioinorganic and Organometallic Chemistry program supports research by Dr. Thomas Bitterwolf, Chemistry Department, University of Idaho, to study metal bound nitrosyl ligands and their linkage isomers using both frozen matrix methods and time-resolved infrared (IR) techniques. For many years the NO ligand has been known to bind metals through either the nitrogen or oxygen. Recently its ability bind a metal in a side-on fashion has been demonstrated. In addition, time resolved crystallographic and infrared studies have shown that nitrosyl ligands in organometallic and coordination compounds can undergo photochemical linkage isomerizations. This study will build an understanding of the factors that lead to the formation and stabilization of nitrosyl linkage isomers by examining several classes of compounds representing a range of ligand types and electron counts. These include: [CpMn(CO)2NO] cation; [Fe(CO)3NO] anion; salts of Roussin's red, [Fe2(NO)4(S)2] dianion, and black, [Fe3(NO)7(S )] anion; Co(II)(salen)(NO) and Co(II)(acacen)(NO); Fe(S2CNR2)2(NO); and CpM(NO)2X, where M = Cr, Mo or W and X is a variety of anionic species. Frozen organic matrix methods will be used to identify those classes of compounds for which side bonded linkage isomers are formed upon photolysis and time-resolved IR spectroscopy will be used to study the kinetics of relaxation of the linkage isomers back to the terminal nitrosyl form. From these data, the thermodynamic activation parameters will be derived. The final portion of the project will utilize time-resolved IR and other flash kinetics methods to examine several reactions in which side bonded linkage isomers may be involved. Nitrogen oxide plays a mediating role in intercellular communication, smooth muscle relaxation, and cytotoxic immune response. There is a great interest in identifying compounds that will liberate nitrogen oxide in biological systems. Optimization of these materials requires a more detailed understanding of the mechanism of nitrogen oxide liberation. This study will determine the details of the release of NO groups that are attached to metals. The studies will be carried out in partnership with the Pacific Northwest National Laboratory. This will give an excellent experience for the postdoctoral, graduate, and undergraduate students who work on the project. High school teachers and Native American high school students will be exposed to the project through the PI's participation in the Murdock Foundation Partners in Science Program.