Exploring novel M...C-C agostic interactions

分子间和分子内相互作用可以对特定化合物的性质产生重大影响，例如，与其稳定性或反应性有关。在基本结构和成键方面，了解相互作用是如何发生的，它的相对强度以及它如何被改变是极其重要的。虽然有大量关于一些更常见的相互作用的信息，如氢键，但并不是所有类型的相互作用都是如此。无机化过渡金属...C-C相互作用涉及从碳-碳键向金属中心提供电子密度，这种相互作用与C-C活化直接相关，然而，这种相互作用非常罕见，而且没有任何技术很好地表征它们。我们建议采用合成、核磁共振作图和理论技术与实验电荷密度实验相结合的综合方法来描述和调整后过渡金属...C-C无机化相互作用。重要的是，这项研究纳入了电荷密度研究，这将首次允许探索相互作用的电子结构。这项研究的结果将提供合成路线、动力学和热力学数据以及这种无菌相互作用的实验可视化。这些信息将对国际化学界具有基础性的意义，并无疑将被用于涉及C-C活化的领域，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解。

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.