Catalytic photo-induced oxygen atom transfer using metal oxo complexes

使用金属氧配合物催化光诱导氧原子转移

• 批准号: 2599099
• 金额: --
• 依托单位: University of York
• 依托单位国家: 英国
• 项目类别: Studentship
• 财政年份: 2021
• 资助国家: 英国
• 起止时间: 2021 至 无数据
• 项目状态: 未结题
• 来源: https://gtr.ukri.org/projects?ref=studentship-2599099
• 关键词: Catalytic; photo; induced; oxygen; atom

Background: There is a clear need to develop processes that minimise the consumption of limited energy resources and reduce waste detrimental to the environment. In this context, photocatalysis is showing much promise since it allows light energy to be harnessed to drive catalytic reactions via electron or energy transfer. A fundamental chemical reaction that underpins many processes, both in nature and in industry, is oxygen atom transfer. In principle, the cleanest sources of oxygen atoms are water and air. However, industry often uses hazardous peroxides instead or metal oxides that lead to significant waste, primarily because viable catalysts that can use water or air are yet to be sufficiently developed. Objectives: Our aim is to develop oxygen atom transfer (OAT) catalysts using bioinspired metal complexes that can be activated by light. Preliminary work has shown that OAT is very sensitive to the ligand structure and that light is required for more than one fundamental step in the catalytic cycle. This project will investigate details of the mechanism and explore the scope of the OAT reaction for the conversion of useful substrates. Promising photocatalysts will be inserted into protein scaffolds to confer water solubility, biocompatibility and stereoselectivity.Experimental Approach: Metal complex synthesis and photocatalysis will be supported by detailed structural and spectroscopic studies to understand the structure-property relationships that determine thermodynamic and kinetic phenomena that control the OAT process. Metal complex synthesis will include the development of multidentate ligands with photoactive components and the use of transition metals, such as molybdenum, tungsten and rhenium, which can support reactive metal-oxo functionalities. Protein samples will be provided by PDRAs in the group who are developing protein scaffolds for artificial metalloenzymes. Characterisation will include single-crystal X-ray diffraction, NMR, IR, Raman, UV-Vis spectroscopies and electrochemistry. The catalytic mechanism will be studied using time-resolved spectroscopy with the potential to use international facilities for ultrafast studies. In collaboration, mechanistic and photophysical processes will also be studied theoretically using DFT. Novelty: OAT is a fundamental biological process that has not yet been exploited for chemical synthesis. Photocatalytic OAT using water as both benign solvent and oxygen source would be a significant advance that would have immediate impact and potentially wide application for clean oxidations.

背景：有一个明确的需要，开发过程，以尽量减少有限的能源的消耗和减少对环境有害的浪费。在这种情况下，光催化显示出很大的希望，因为它允许利用光能通过电子或能量转移来驱动催化反应。在自然界和工业中，支撑许多过程的一个基本化学反应是氧原子转移。原则上，氧原子最干净的来源是水和空气。然而，工业经常使用有害的过氧化物或导致大量浪费的金属氧化物，主要是因为可用的水或空气的催化剂尚未得到充分开发。目的：我们的目标是利用可被光激活的生物启发金属配合物开发氧原子转移（OAT）催化剂。初步研究表明，OAT对配体结构非常敏感，催化循环中不止一个基本步骤都需要光。该项目将研究机理的细节，并探索OAT反应转化有用底物的范围。有前途的光催化剂将被插入到蛋白质支架中，以赋予水溶性、生物相容性和立体选择性。实验方法：金属配合物合成和光催化将通过详细的结构和光谱研究来支持，以了解结构-性质关系，这些关系决定了控制OAT过程的热力学和动力学现象。金属配合物的合成将包括开发具有光活性成分的多齿配体和使用过渡金属，如钼、钨和铼，它们可以支持活性金属-氧官能团。蛋白质样品将由小组中正在开发人工金属酶蛋白质支架的PDRAs提供。表征将包括单晶x射线衍射，核磁共振，红外，拉曼，紫外-可见光谱和电化学。催化机理将使用时间分辨光谱进行研究，并有可能使用国际设施进行超快研究。在合作中，机械和光物理过程也将使用DFT进行理论研究。新颖性：OAT是一种基本的生物过程，尚未被用于化学合成。利用水作为良性溶剂和氧源的光催化OAT将是一项重大进展，将对清洁氧化产生直接影响并具有潜在的广泛应用前景。