Synthetic Entries to Early-Transition Metal Complexes Containing Terminal and Reactive Metal-Ligand Multiple Bonds

这个无机和有机金属化学项目的研究奖支持了印第安纳大学Daniel J. Mindiola教授对高极化金属-配体多键反应行为的研究。对具有N（氮化物）、P（磷化物）、CR2（烷基烯）和CR（烷基炔）等不饱和和饱和分子的过渡金属的瞬态和末端第4和第5基团配合物的动力学和反应性研究，有望揭示金属-配体多键在化学惰性分子（如烷烃、芳烃、N-杂环等许多极难活化和功能化的小分子）活化过程中的作用。结合新的合成策略，通过多电子氧化还原方法，通过结合已知的有机金属转化，或通过修饰配体框架，合成由早期3d金属组成的其他未知金属-配体多键支架，也将揭示前所未有的化学和新的转化。通过制备具有金属配体多键的高价化合物，正在进行的研究有望开发出新的体系，可以掩盖低价金属中心，并催化反应，如甲烷活化和功能化，苯环开环和聚合，氢氟烃的脱氢氟化和n -杂环的功能化。除了化学研究，印第安纳大学布卢明顿分校还成立了一个以学生为基础的分会，目的是招募代表性不足的群体进入物理科学领域。在这些实验室接受训练的学生有望成为新一代化学家的代表，他们可以制备具有特定功能的分子，同时又能节约能源。然而，分子是反应性的，产生更少的废物和改进目前在工业环境中使用的做法。合成和反应，以原子经济的方式，代表了程序的标准目标之一，特别是现在在这个不确定的时代设计替代能源。因此，在学生了解他们的系统如何运作后，他们能够使他们的试剂更有效地实现其设计的特定目标。

This Research award in the Inorganic and Organometallic Chemistry program supports work by Professor Daniel J. Mindiola at Indiana University to understand the behavior of highly polarized and thus reactive metal-ligand multiple bonds. Kinetics and reactivity studies of transient and terminal group 4 and 5 transition metal complexes having N (nitride), P (phosphide), CR2 (alkylidene) and CR (alkylidyne) moieties with unsaturated and saturated molecules are expected to reveal the role of the metal-ligand multiple bond during the activation of chemical inert molecules such as alkanes, arenes, N-heterocycles among many other small molecules that are exceedingly resistant towards activation and functionalization. The combination of new synthetic strategies to synthesize other unknown metal-ligand multiply bonded scaffolds composed of early 3d metals by a multielectron redox approach, by combining known organometallic transformations, or by modification of the ligand framework, will also unmask unprecedented chemistry and new transformations. By preparing high-valent compounds with metal-ligand multiple bonds the research being conducted is expected to develop new systems that can mask low-valent metal centers as well as catalyze reactions such as methane activation and functionalization, benzene ring-opening and polymerization, dehydrofluorination of hydrofluorocarbons, and the functionalization of N-heterocycles. In addition to chemical research a student based chapter developed at Indiana University, Bloomington, has been founded with the purpose of recruiting underrepresented groups into the physical sciences. Students trained in these laboratories are expected to represent a new generation of chemists who can prepare molecules designed to carry a specific function while conserving energy. However, the molecules are reactive, produce less waste and improve upon current practices used in the industrial setting. Synthesis and reactivity, in an atom-economical way, represents one of the program standard goals, especially now during this uncertain era for devising alternative sources of energy. Hence, after students understand how their system operates, they are able to make their reagent more efficient in achieving the specific goal for which it was designed.