C-H activation catalysis: synthetic and reactivity studies underpinning future ultra-fast spectroscopic measurements

C-H活化催化：支撑未来超快光谱测量的合成和反应性研究

• 批准号: 2342061
• 金额: --
• 依托单位: Heriot-Watt University
• 依托单位国家: 英国
• 项目类别: Studentship
• 财政年份: 2019
• 资助国家: 英国
• 起止时间: 2019 至 无数据
• 项目状态: 已结题
• 来源: https://gtr.ukri.org/projects?ref=studentship-2342061
• 关键词: activation; catalysis; synthetic; reactivity; studies

This is a PhD research project in chemistry. This PhD project will continue our investigations into Rh-catalyzed C-H activation. Currently we have a system that upon photoactivation with 400 nm light undergoes intramolecular activation of sp3 centres forming a metallacycle. We will investigate ligand modifications that will build towards the intermolecular activation of alkanes (including building towards the very challenging substrate methane) by tethering the NHC ligand in order to prohibit reactivity with the Rh center, as well as utilizing smaller Me substitution. In addition, we will make comparisons to a related thermally-activated system that undergoes intermolecular arene C-H borylation that we think may proceed via Rh boryls instead of low coordinate Rh complexes. Finally, this work will provide insight into suitable complexes for performing ultra-fast reactivity studies at the Rutherford Appleton Laboratory in future years.

这是一个化学博士研究项目。这个博士项目将继续我们对 Rh 催化的 C-H 活化的研究。目前，我们有一个系统，在 400 nm 光的光活化作用下，sp3 中心发生分子内活化，形成金属环。我们将研究配体修饰，通过束缚 NHC 配体以阻止与 Rh 中心的反应，以及利用较小的 Me 取代，从而实现烷烃的分子间活化（包括构建非常具有挑战性的底物甲烷）。此外，我们还将与进行分子间芳烃 C-H 硼基化的相关热激活系统进行比较，我们认为该系统可能通过 Rh 硼基化合物而不是低配位 Rh 配合物进行。最后，这项工作将为未来几年在卢瑟福阿普尔顿实验室进行超快反应研究提供合适的配合物。

项目成果

Rhodium Indenyl NHC and Fluorenyl-Tethered NHC Half-Sandwich Complexes: Synthesis, Structures and Applications in the Catalytic C-H Borylation of Arenes and Alkanes.

铑茚基 NHC 和芴基束缚 NHC 半夹心配合物：合成、结构及其在芳烃和烷烃催化 C-H 硼基化中的应用。

• DOI: http://dx.10.1002/chem.202102961
• 发表时间: 2021
• 期刊: Chemistry (Weinheim an der Bergstrasse, Germany)
• 作者: Evans KJ

Moving from Fuel to Feedstock : Selective hydrocarbon activation using rhodium and iridium complexes

从燃料转向原料：使用铑和铱络合物选择性碳氢化合物活化

• DOI: http://dx.10.1595/205651323x16765646706676
• 发表时间: 2023
• 期刊: Johnson Matthey Technology Review
• 影响因子: 2.3
• 作者: Morton P

One-step synthesis of heteroleptic rare-earth amide complexes featuring fluorenyl-tethered N-heterocyclic carbene ligands

一步合成芴基 N-杂环卡宾配体杂配稀土酰胺配合物

• DOI: http://dx.10.1016/j.poly.2021.115021
• 发表时间: 2021
• 期刊: Polyhedron
• 影响因子: 2.6
• 作者: Evans K