Base-Metal Complexes for Challenging Organometallic Transformations

具有挑战性的有机金属转化的贱金属配合物

• 批准号: 261742-2013
• 负责人: Johnson, Samuel
• 金额: $ 3.93万
• 依托单位: University of Windsor
• 依托单位国家: 加拿大
• 项目类别: Discovery Grants Program - Individual
• 财政年份: 2018
• 资助国家: 加拿大
• 起止时间: 2018-01-01 至 2019-12-31
• 项目状态: 已结题
• 来源: https://www.nserc-crsng.gc.ca/ase-oro/Details-Detailles_eng.asp?id=654757
• 关键词: Base; Metal; Complexes; Challenging; Organometallic

This proposal describes approaches to render sustainable 1st-row transition metals, such as nickel and cobalt, as catalysts for applications such as the functionalization of C-H, C-F and C-O bonds. The short term goals of the projects involve identification of new ways to render these metals reactive towards traditionally inert bonds. Approaches to this include using ligand design or identifying new mechanisms for bond activation. The long term goal of each project is the commercial application of these catalytic technologies in fields such as pharmaceutical synthesis and biomass conversion.** The atom-economic relatively green conversion of traditionally inert C-H bonds to functional groups has been achieved by a number of metal-catalyzed systems in the past decades. Complexes of the expensive 3rd-row late transition metals, such as iridium and platinum, are commonly used in these conversions, due to the strong bonds these elements form to both carbon and hydrogen, which aids in cleaving strong C-H bonds. Comparatively, complexes of nickel are at an extreme thermodynamic disadvantage in these reactions, but nickel has the distinct advantage of being on the order of 10000 times cheaper, due to its relative abundance. Our research suggests that not only can nickel complexes also activate strong C-H bonds, they can also perform catalytic C-H bond transformations that are unprecedented and perhaps unique to these systems. Our current goals are to fully understand the mechanism and scope of these reactions.** Similar to C-H bond activation, the activation of C-F and C-O bonds are also problematic for both kinetic and thermodynamic reasons. We hope to do a thorough study of C-F bond activation by nickel complexes to gain insight into how the mechanism and thermodynamic parameters of these reactions are influenced by ancillary ligand choices. The end goal is a rational approach to both C-F bond activation and catalytic C-F bond formation for pharmaceuticals or radionuclide use. The activation of C-O bonds is related to C-F bond activation, and has application in both synthesis and biomass conversion to fuels or fine chemicals.**********

该提案描述了使镍和钴等第一行过渡金属可持续用作C-H、C-F和C-O键官能化等应用的催化剂的方法。这些项目的短期目标包括确定使这些金属对传统惰性键反应的新方法。 这方面的方法包括使用配体设计或确定键活化的新机制。每个项目的长期目标是将这些催化技术商业化应用于药物合成和生物质转化等领域。 在过去的几十年里，许多金属催化体系已经实现了传统惰性C-H键到官能团的原子经济的相对绿色转化。 昂贵的第三行后过渡金属（如铱和铂）的络合物通常用于这些转化中，因为这些元素与碳和氢形成强键，这有助于裂解强C-H键。 相比之下，镍的络合物在这些反应中处于极端的热力学劣势，但是镍由于其相对丰度而具有便宜10000倍的明显优势。 我们的研究表明，镍配合物不仅可以激活强C-H键，还可以进行催化C-H键转化，这是前所未有的，也许是这些系统所独有的。 我们目前的目标是充分了解这些反应的机制和范围。 与C-H键活化类似，C-F和C-O键的活化也由于动力学和热力学原因而存在问题。 我们希望通过镍配合物对C-F键的活化进行深入研究，以了解这些反应的机制和热力学参数如何受到辅助配体选择的影响。 最终目标是为药物或放射性核素的使用提供一种合理的C-F键活化和催化C-F键形成的方法。 C-O键的活化与C-F键的活化有关，并且在合成和生物质转化为燃料或精细化学品中都有应用。