Exploring novel M...C-C agostic interactions

探索新颖的 M...C-C 离奇互动

• 批准号: EP/E048994/1
• 负责人: Judith Howard
• 金额: $ 24.88万
• 依托单位: Durham University
• 依托单位国家: 英国
• 项目类别: Research Grant
• 财政年份: 2008
• 资助国家: 英国
• 起止时间: 2008 至 无数据
• 项目状态: 已结题
• 来源: https://gtr.ukri.org/projects?ref=EP%2FE048994%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相关的性质。了解相互作用如何发生，它的相对强度以及如何改变它在基本结构和键合方面非常重要。虽然有丰富的信息提供一些更常见的相互作用，如氢键，这是不正确的所有类型的相互作用。Agostic transition metal. C-C相互作用涉及从碳-碳键到金属中心的电子密度的捐赠，这种类型的相互作用与C-C活化直接相关，然而，它们是极其罕见的，并且对于任何技术都没有很好地表征。核磁共振映射和理论技术与实验电荷密度实验，以调整和调整后过渡金属…C-C agostic相互作用。重要的是，这项研究结合了电荷密度研究，这将是第一次，允许相互作用的电子结构进行探测。该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agostic相互作用的实验可视化。这些信息将对国际化学界具有根本性的意义，并将在涉及C-C活化的领域中得到利用，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。

项目成果

[MeNC5H5]2[TCNE]2 (TCNE = tetracyanoethylene). Single crystal X-ray and neutron diffraction characterization of an exceptionally long 2.8 Å C-C bond

[MeNC5H5]2[TCNE]2（TCNE = 四氰乙烯）。

• DOI: 10.1039/b816817b
• 发表时间: 2009
• 期刊: CrystEngComm
• 影响因子: 3.1
• 作者: Piccoli P

Bond catastrophes in rhodium complexes: experimental charge-density studies of [Rh(C7H8)(P(t)Bu3)Cl] and [Rh(C7H8)(PCy3)Cl].

铑配合物中的键突变：[Rh(C7H8)(P(t)Bu3)Cl] 和 [Rh(C7H8)(PCy3)Cl] 的实验电荷密度研究。

• DOI: 10.1107/s0108768110031496
• 发表时间: 2010
• 期刊: Acta crystallographica. Section B, Structural science
• 作者: Sparkes HA

Supramolecular Dimers of Copper(II) Complexes Resulting from Designed Host-Guest Interactions

由设计的主客体相互作用产生的铜（II）配合物的超分子二聚体

• DOI: 10.1002/ejic.200900857
• 发表时间: 2010
• 期刊: European Journal of Inorganic Chemistry
• 影响因子: 2.3
• 作者: Nayak M

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