Small Molecule Activation and Materials Synthesis

康奈尔大学的Peter Wolczanski博士提议研究 低配位无机/有机金属络合物的化学 通过大体积的硅氧化物、硅酰胺、硅酰亚胺、硫醇盐和乙炔化物配体。 特别是，这些系统的小分子活化化学 将探索，和一类新的金属有机固态材料 将制定一项战略，重点是全面培训 研究生参与。 一个主要目标是产生一个更大的 理解C-H键活化的热力学方面， 将C-H键活化与能量相似的配体“绑定” 替代，并通过测量平衡同位素效应和比较 他们的理论。 此外，将探索C-N键断裂反应， 特别是当它们涉及加氢脱氮过程时。 机械论 这些化合物的氧化加成过程的研究和系统化 系统是一个一般的研究目标， 基于金属自由基的C-H键活化化学和金属有机化合物 包括具有共价网络的固态化合物。 一类独特的无机复合物的化学， 氮，氧，硫和碳取代基将被研究两个 原因 一是这些化合物显示出不寻常和独特的 与其他分子中的C-H和C-N键反应，并具有 对改善工业流程的影响。 另一种是他们 可作为分子前体用于新材料的合成 高复杂性。 这些研究将实验研究置于一个 理论框架，希望基础化学 发现将导致控制反应性的改进方法， 碳氢化合物和设计有趣的材料。

Dr. Peter Wolczanski of Cornell University proposes to investigate the chemistry of low-coordinate inorganic/organometallic complexes supported by bulky siloxide, silamide, silimide, thiolate, and acetylide ligands. In particular, the small molecule activation chemistry of these systems will be explored, and a new class of metal-organic solid state materials will be developed, with an emphasis on comprehensive training of the graduate students involved. A major goal is to generate a greater understanding of the thermodynamic aspects of C-H bond activiation by `tying` C-H bond activations to energetically similar ligand substitutions, and by measuring equilibrium isotope effects and comparing them to theory. Also, C-N bond cleavage reactions will be explored, especially as they relate to HydroDeNitrogenation processes. Mechanistic studies and systemization of oxidative addition processes of these systems is a general research goal, and studies of early transition metallaradical based C-H bond activation chemistry and metal organic solid-state compounds with covalent networks are included. The chemistry of a class of unique inorganic complexes with bonds to nitrogen, oxygen, sulfur, and carbon substituents will be studied for two reasons. One is that these compounds display unusual and unique reactivity with C-H and C-N bonds in other molecules, and have implications for improving industrial processes. The other is that they can be used as molecular precursors in the synthesis of novel materials of high complexity. These studies place experimental studies in a theoretical framework, and it is hoped that the fundamental chemistry discovered will lead to improved methods of controlling the reactivity of hydrocarbons and of designing interesting materials.