Novel Application of Hydrogen Bonding in Inorganic Chemistry

氢键在无机化学中的新应用

• 批准号: 9610146
• 负责人: Robert Crabtree
• 金额: $ 43.8万
• 依托单位: Yale University
• 依托单位国家: 美国
• 项目类别: Standard Grant
• 财政年份: 1997
• 资助国家: 美国
• 起止时间: 1997-05-15 至 2002-04-30
• 项目状态: 已结题
• 来源: https://www.nsf.gov/awardsearch/showAward?AWD_ID=9610146&HistoricalAwards=false
• 关键词: Novel; Application; Hydrogen; Bonding; Inorganic

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.

Robert H. Crabtree博士，耶鲁大学化学系，受到化学部无机、生物无机和有机金属项目的支持，研究发生在传统质子供体（OH或NH基团）和非传统质子受体（M = Re, Ir）之间的新型氢键。初步数据显示，这些键短而强，在MH或BH单位弯曲。在这个项目中，分子间和分子内的M-H…H-M'和M-H…合成M′配合物，并用光谱和动力学数据分析其中的氢键。具体的问题包括HF配合物的稳定，通过诱导氢键形成来限制二氢配合物的旋转，干扰多氢化物的流动速率，以及增加CO的亲核攻击速率。将评估一种溶剂致变色方法来表征外球氢键相互作用。原子和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”。人们知道氢键已经很多年了，例如，它是冰和液态水的许多特性的原因。最近，已经发现了包含金属-氢单元的新型氢键。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。