Transition metal chemistry and catalysis

过渡金属化学与催化

• 批准号: 1311-2013
• 负责人: Morris, Robert
• 金额: $ 9.03万
• 依托单位: University of Toronto
• 依托单位国家: 加拿大
• 项目类别: Discovery Grants Program - Individual
• 财政年份: 2015
• 资助国家: 加拿大
• 起止时间: 2015-01-01 至 2016-12-31
• 项目状态: 已结题
• 来源: https://www.nserc-crsng.gc.ca/ase-oro/Details-Detailles_eng.asp?id=568182
• 关键词: Transition; metal; chemistry; catalysis

Hydrogenation catalysts are used by industry to produce fuels, bulk chemicals and fine chemicals including pharmaceuticals, agrochemicals and fragrances. They are usually composed of expensive, rare and toxic platinum metals. Since 2007 our group has discovered and invented sustainable and much cheaper iron catalysts that promise to replace some conventional catalysts used for the asymmetric hydrogenation of ketones and imines for the production of valuable alcohols and amines. For example, certain alcohols can be used for the synthesis of drugs used in chemotherapy, and selected amines, in the synthesis of antidepressants and antibiotics. Cheap iron catalysts might also find application in the energy field in the hydrogenation of carbon dioxide as well as hydrogen storage and evolution. It is proposed to discover further useful catalyst structures and fully understand them so that this replacement process, vital for a greener chemical industry, can be successful. A variety of new, efficient syntheses are proposed that are amenable to high throughput screening of catalysts. Catalysts will be formed from novel and known modules under mild conditions where the iron ion acts as a template. A component of interest is the N-heterocyclic carbene (NHC) donor since this allows catalyst synthesis without the use of toxic phosphine reagents. We have discovered active NHC catalysts for ester hydrogenation that might make obsolete the wasteful use of boron and aluminum reductants. It is important to determine whether the catalysts are homogeneous or heterogeneous. We reported in 2012 the first example of asymmetric catalysis using iron nanoparticles that are formed from a homogeneous solution of iron precursor. We will use state of the art practical and theoretical methods to probe the functioning of our new catalyst systems. This work might also lead to the discovery of catalysts that use sunlight to split water into hydrogen fuel and oxygen and catalysts for the efficient synthesis of polyamides.

加氢催化剂在工业上用于生产燃料、大宗化学品和精细化学品，包括药品、农用化学品和香料。它们通常由昂贵，稀有和有毒的铂金属组成。自2007年以来，我们的团队已经发现并发明了可持续且更便宜的铁催化剂，有望取代用于酮和亚胺不对称氢化的一些传统催化剂，以生产有价值的醇和胺。例如，某些醇可用于合成化学疗法中使用的药物，而选定的胺可用于合成抗抑郁药和抗生素。廉价的铁催化剂也可能在能源领域中应用于二氧化碳的氢化以及氢的储存和释放。 建议发现更多有用的催化剂结构并充分了解它们，以便这种对绿色化学工业至关重要的替代过程能够成功。提出了各种新的、有效的合成方法，这些方法适合于催化剂的高通量筛选。催化剂将在温和的条件下由新的和已知的模块形成，其中铁离子作为模板。 感兴趣的组分是N-杂环卡宾（NHC）供体，因为这允许在不使用有毒膦试剂的情况下进行催化剂合成。 我们已经发现了用于酯氢化的活性NHC催化剂，其可能使硼和铝还原剂的浪费使用过时。 确定催化剂是均相还是非均相非常重要。 我们在2012年报道了第一个使用铁纳米颗粒的不对称催化的例子，这些铁纳米颗粒是由铁前体的均匀溶液形成的。 我们将使用最先进的实践和理论方法来探索我们的新催化剂系统的功能。 这项工作还可能导致发现利用阳光将水分解为氢燃料和氧气的催化剂，以及用于有效合成聚酰胺的催化剂。