Highly reactive catalysts for the hydrogenation of poorly reactive substrates

用于氢化反应性差的底物的高反应性催化剂

• 批准号: EP/G063591/1
• 负责人: Matthew Clarke
• 金额: $ 2.29万
• 依托单位: University of St Andrews
• 依托单位国家: 英国
• 项目类别: Research Grant
• 财政年份: 2009
• 资助国家: 英国
• 起止时间: 2009 至 无数据
• 项目状态: 已结题
• 来源: https://gtr.ukri.org/projects?ref=EP%2FG063591%2F1
• 关键词: Highly; reactive; catalysts; hydrogenation; poorly

A good catalyst allows the rate of a chemical reaction to be accelerated enormously, without the catalyst itself being used up in the reaction. The demand for chemical processes to be less harmful to the environment has increased the importance of reactions that utilise tiny amounts of catalyst to promote clean, efficient reactions between two chemicals that do not normally react with each other (at a measurable rate). One potentially important examples of a catalytic reaction is the catalytic reduction of a class of chemicals called carboxylic acid derivatives to alcohols. Alcohols are one of the most important ingredients for drugs, flavours, fragrances and plastics. There are a number of reagents to do this transformation, but most generate waste. More desirable from an economic and ecological point of view is to use a catalyst and molecular hydrogen to accomplish this task, since no waste would be formed. There have been some recent developments in this area with some catalysts showing some promise in this type of reaction. However, further work is required before the catalysts can be considered genuinely effective, This research project requests funds for an international visitor to visit St Andrews and carry out detailed studies measuring the rates of the reactions as a function of catalyst structure, catalyst concentration, activation procedure and investigate the stability of the new catalysts. The project will study new types of catalyst derived from ligands that bind ruthenium by a combination of phosphorus and nitrogen atoms. Novel pre-catalysts will be synthesies during the project, but an attempt to characterise the catalytic intermediates formed during the hydrogenation process will be made. This thorough mechanism-led approach will hopefully enable us to produce the most promising catalyst for this transformation to date. The work will enable future studies that would hopefully lead to an industrially viable process. Such a process would produce less waste and reduce energy, chemical, solvent and water usage in industry relative to the current state-of-the-art.

一个好的催化剂可以大大加快化学反应的速度，而催化剂本身不会在反应中被耗尽。对化学过程对环境危害较小的需求增加了利用微量催化剂促进两种通常不会相互反应的化学品之间清洁，有效反应的重要性（以可测量的速率）。催化反应的一个潜在的重要例子是将一类称为羧酸衍生物的化学品催化还原为醇。酒精是药物、调味品、香料和塑料的最重要成分之一。有许多试剂可以进行这种转化，但大多数都会产生废物。从经济和生态的角度来看，更理想的是使用催化剂和分子氢来完成这一任务，因为不会形成废物。在这一领域有一些最近的发展，一些催化剂在这类反应中显示出一些希望。然而，在催化剂被认为是真正有效之前，还需要进一步的工作，该研究项目要求为国际访问者访问圣安德鲁斯提供资金，并进行详细的研究，测量反应速率作为催化剂结构，催化剂浓度，活化程序的函数，并调查新催化剂的稳定性。该项目将研究由磷和氮原子结合钌的配体衍生的新型催化剂。在项目期间将合成新型前催化剂，但将尝试消除氢化过程中形成的催化中间体。这种彻底的机制主导的方法将有望使我们能够为这一转变产生迄今为止最有希望的催化剂。这项工作将使未来的研究，有望导致一个工业上可行的过程。相对于目前的技术水平，这种方法将产生更少的废物并减少工业中的能量、化学品、溶剂和水的使用。

项目成果

Structural Variations on a Novel Ruthenium Catalyst for the Hydrogenation of Bulky Ketones

用于大体积酮加氢的新型钌催化剂的结构变化

• 发表时间: 2010
• 作者: M L Clarke

Exploring the role of phosphorus substituents on the enantioselectivity of Ru-catalysed ketone hydrogenation using tridentate phosphine-diamine ligands

• DOI: 10.1039/c1cy00253h
• 发表时间: 2011-10
• 期刊: Catalysis Science & Technology
• 影响因子: 5
• 作者: S. Phillips;Kristian H. O. Andersson;N. Kann;Michael T Kuntz;P. Wawrzyniak;M. Clarke