Exploring novel M...C-C agostic interactions

探索新颖的 M...C-C 离奇互动

基本信息

批准号：
EP/E050743/1
负责人：
Andrew Weller
金额：
$ 22.69万
依托单位：
University of Oxford
依托单位国家：
英国
项目类别：
Research Grant
财政年份：
2007
资助国家：
英国
起止时间：
2007 至无数据
项目状态：
已结题

来源：
https://gtr.ukri.org/projects?ref=EP%2FE050743%2F1
关键词：
Exploring novel M...C agostic interactions

项目摘要

Intermolecular and intramolecular interactions can have a significant effect on the properties of a particular compound, for example, in relation to its stability or reactivity. Understanding how an interaction occurs, its relative strength and how it can be altered is extremely important in fundamental structure and bonding terms. While there is a wealth of information available on some of the more common interactions, such as hydrogen bonding, this is not true for all types of interaction. Agostic transition metal...C-C interactions involve the donation of electron density from the carbon-carbon bond to the metal centre, this type of interaction is directly relevant to C-C activation, however, they are extremely rare and not well characterized for any technique.We propose to employ an integrated approach combining synthesis, NMR mapping and theoretical techniques with experimental charge density experiments in order to characterise and tune late transition metal...C-C agostic interactions. Importantly the study incorporates charge density studies which will, for the first time, allow the electronic structure of the interaction to be probed. The results of the study will provide synthetic routes, kinetic and thermodynamic data and experimental visualisation of such agostic interactions. This information will be of fundamental significance to the international chemical community, and will undoubtably be utilized in areas involving C-C activation, such as, novel organic synthesis and industrial applications, such as, petroleum cracking using heterogeneous catalysis.

分子间和分子内相互作用会对特定化合物的性质产生显着影响，例如与其稳定性或反应性有关。了解相互作用如何发生、其相对强度以及如何改变它对于基本结构和键合术语极其重要。虽然关于一些更常见的相互作用（例如氢键）有大量的信息，但并非所有类型的相互作用都是如此。过渡金属...C-C 相互作用涉及从碳-碳键向金属中心提供电子密度，这种类型的相互作用与 C-C 活化直接相关，但是，它们极其罕见，并且对于任何技术都没有得到很好的表征。我们建议采用一种将合成、核磁共振图谱和理论技术与实验电荷密度实验相结合的综合方法，以表征和调整后过渡金属...C-C 不规则相互作用。重要的是，该研究结合了电荷密度研究，这将首次允许探测相互作用的电子结构。研究结果将提供合成路线、动力学和热力学数据以及此类远古相互作用的实验可视化。这些信息对国际化学界具有重要意义，毫无疑问将在涉及C-C活化的领域得到利用，例如新型有机合成和工业应用，例如使用多相催化的石油裂化。