Exploring novel M...C-C agostic interactions

探索新颖的 M...C-C 离奇互动

• 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

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可能会对特定化合物的特性产生重大影响，例如与其稳定性或反应性有关。了解相互作用的发生方式，其相对强度以及如何改变它在基本结构和键合项中极为重要。尽管有大量有关某些更常见的相互作用（例如氢键）的信息，但对于所有类型的相互作用而言，这并不是如此。 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阿根斯的相互作用。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。该研究的结果将提供合成的途径，动力学数据和热力学数据，并提供此类arepostic相互作用的实验可视化。这些信息对国际化学界具有根本意义，并且无疑将用于涉及C-C激活的区域，例如新型有机合成和工业应用，例如使用异质性催化的石油破裂。

项目成果

Experimental charge density study into C-C s-interactions in a Binor-S rhodium complex.

Binor-S 铑配合物中 C-C s 相互作用的实验电荷密度研究。

• DOI: 10.1039/c1dt10303b
• 发表时间: 2011
• 期刊: 2003)
• 作者: Sparkes HA