First-row metal catalysts for controlled radical reactivity

用于受控自由基反应的第一行金属催化剂

• 批准号: RGPIN-2016-03925
• 负责人: Smith, Kevin
• 金额: $ 2.19万
• 依托单位: University of British Columbia
• 依托单位国家: 加拿大
• 项目类别: Discovery Grants Program - Individual
• 财政年份: 2017
• 资助国家: 加拿大
• 起止时间: 2017-01-01 至 2018-12-31
• 项目状态: 已结题
• 来源: https://www.nserc-crsng.gc.ca/ase-oro/Details-Detailles_eng.asp?id=632670
• 关键词: First; row; metal; catalysts; controlled

With its goals of preventing pollution and reducing consumption of nonrenewable resources, green chemistry represents an important opportunity for synthetic inorganic chemists. There is a growing emphasis on developing catalysts that use readily-available transition metals, operate under mild conditions, and use reactants obtained from renewable resources. A critical frontier of green chemistry research is to discover earth-abundant first-row transition metal cross-coupling catalysts that break carbon-oxygen or carbon-hydrogen bonds instead of relying on halogenated reactants. This field is generally perceived as difficult due to the potential involvement of radical chemistry. The first-row metal complexes relevant to catalysis often have unpaired d-electrons. The catalysts are prone to single-electron reactions that can generate organic radicals, especially for reactions conducted under oxidative conditions. The organic molecules bound to the metal centers can themselves gain or lose single electrons, forming ligand-based radicals.

绿色化学以防止污染和减少不可再生资源的消耗为目标，为合成无机化学家提供了一个重要的机会。 人们越来越重视开发使用容易获得的过渡金属、在温和条件下操作并且使用从可再生资源获得的反应物的催化剂。 绿色化学研究的一个关键前沿是发现地球上丰富的第一行过渡金属交叉偶联催化剂，打破碳-氧或碳-氢键，而不是依赖于卤化反应物。 这个领域通常被认为是困难的，由于自由基化学的潜在参与。 与催化相关的第一排金属配合物通常具有未配对的d电子。 催化剂容易发生单电子反应，产生有机自由基，特别是在氧化条件下进行的反应。 与金属中心结合的有机分子本身可以获得或失去单个电子，形成基于配体的自由基。