Novel Application of Hydrogen Bonding in Inorganic Chemistry

耶鲁大学化学系Robert H.Crabtree博士得到化学部无机、生物无机和有机金属计划的支持，研究发生在常规质子给体、OH或NH基团和非传统受体M-H或B-H键(M=Re、Ir)之间的新型氢键。初步数据显示，这些债券短、强，在MH或BH单位处弯曲。在这个项目中，将合成分子间和分子内的M-H...H-M‘和M-H...M’配合物的例子，并使用光谱和动力学数据分析其中的氢键。将解决的具体问题包括：HF络合物的稳定，通过诱导H键的形成来限制二氢络合物的旋转，扰乱多氢化合物的流动速率，以及增加CO的亲核攻击速率。溶剂变色方法将被用来表征外球氢键相互作用。原子与分子之间的相互作用是决定物质性质的最重要的现象。其中一种相互作用被称为“氢键”。氢键已经知道很多年了，例如，它对冰和液态水的许多性质起到了作用。最近，涉及金属-氢单元的新型氢键被发现。该项目旨在发现这些新型氢键的一般趋势，并开发新的氢键情况，以实现有用的化学转化。

Dr. Robert H. Crabtree, Department of Chemistry, Yale University, is supported by the Inorganic, Bioinorganic, and Organometallic Program of the Chemistry Division for a study of novel types of hydrogen bonding that occur between a conventional proton donor, an OH or NH group, and an unconventional acceptor, an M-H or B-H bond (M = Re, Ir). Preliminary data show that these bonds are short, strong, and bent at the MH or BH unit. During this project examples of inter- and intramolecular M-H...H-M' and M-H...M' complexes will be synthesized and the hydrogen bonding in them analyzed using spectroscopic and kinetic data. Specific issues that will be addressed target include the stabilization of HF complexes, restricting rotation in dihydrogen complexes by inducing H-bond formation, perturbing the fluxionality rates of polyhydrides, and increasing the rate of nucleophilic attack at CO. A solvatochromic method will be evaluated for characterizing outer sphere H-bonding interactions. Interactions between atoms and molecules are the most important phenomena that determine the properties of matter. One type of interaction is called 'hydrogen bonding.' Hydrogen bonding has been known for many years and is responsible, for example, for many of the properties of ice and liquid water. Recently, new types of hydrogen bonds that involve metal-hydrogen units have been discovered. This project aims at discovering general trends in these new types of hydrogen bonds and at developing novel hydrogen bonding situations in order to effect useful chemical transformations.