New multifunctional ligation strategies for tuning transition metal reactivity

用于调节过渡金属反应性的新型多功能连接策略

• 批准号: 312624-2008
• 负责人: Turculet, Laura
• 金额: $ 2.7万
• 依托单位: Dalhousie University
• 依托单位国家: 加拿大
• 项目类别: Discovery Grants Program - Individual
• 财政年份: 2010
• 资助国家: 加拿大
• 起止时间: 2010-01-01 至 2011-12-31
• 项目状态: 已结题
• 来源: https://www.nserc-crsng.gc.ca/ase-oro/Details-Detailles_eng.asp?id=457511
• 关键词: New; multifunctional; ligation; strategies; tuning

As stated by the 2007 Priestley Medalist, George M. Whitesides, "almost everything in chemistry is catalyzed." Transition metal catalysts in particular have risen to the challenge of providing solutions for many of the problems of modern synthetic chemistry, specifically with respect to the development of new chemical processes that convert abundant resources into value-added products in an efficient, selective, and environmentally friendly manner. The impact of transition metal catalysis was recognized in the awarding of the 2001 and 2005 Nobel Prizes in Chemistry. The development of such reactive catalysts represents an ongoing challenge that spans a range of chemical disciplines (e.g. organic, inorganic, environmental). Notably, all such breakthroughs are rooted in the fundamental study of transition metal reactivity. In this context, research in the Turculet group targets the preparation of reactive transition metal complexes that exhibit new and/or improved reactivity properties by virtue of their unique construction. Key to this endeavor is the design and synthesis of new ancillary ligands that impart novel structural and electronic characteristics to the ensuing metal complexes. The proposed research seeks to develop the metal chemistry of new ancillary 'pincer'-type ligands that feature previously under-explored, formally anionic heavier main group element donors (e.g. Si, P). Overarching questions that we seek to address in this research include: (i) Can such pincer complexes be prepared, and do they exhibit new or unusual reactivity properties? (ii) Does the replacement of traditionally employed anionic donors (e.g. C, N) with their heavier congeners (e.g. Si, P) in such complexes provide improved reactivity in established catalytic reactions (e.g. transfer hydrogenation)? (iii) Can electron-rich complexes featuring such 'heavier-element' pincer ligands mediate challenging bond activation reactions (e.g. N2, C-H) that are of fundamental importance for the utilization of abundant but unreactive resources? These studies will advance our understanding of how metal-ligand interactions influence reactivity, enabling the design of metal catalysts that can mediate new and increasingly challenging substrate transformations.

正如2007年普里斯特利奖得主乔治M。怀特塞德斯说：“化学中几乎所有的东西都是催化的。特别是过渡金属催化剂已经面临着为现代合成化学的许多问题提供解决方案的挑战，特别是关于以有效，选择性和环境友好的方式将丰富的资源转化为增值产品的新化学工艺的开发。过渡金属催化的影响在2001年和2005年诺贝尔化学奖的颁发中得到了认可。这种反应性催化剂的开发代表了跨越一系列化学学科（例如有机、无机、环境）的持续挑战。值得注意的是，所有这些突破都植根于过渡金属反应性的基础研究。在这方面，Turculet组的研究目标是制备反应性过渡金属络合物，这些络合物凭借其独特的结构表现出新的和/或改进的反应性。 这一奋进的关键是设计和合成新的辅助配体，赋予新的结构和电子特性，随后的金属配合物。拟议的研究旨在开发新的辅助“钳”型配体的金属化学，这些配体具有以前未开发的，形式上阴离子较重的主族元素供体（例如Si，P）。在这项研究中，我们试图解决的主要问题包括：（i）这种钳形配合物可以制备，它们是否表现出新的或不寻常的反应性能？(ii)在这种络合物中，用它们的重同系物（例如Si、P）取代传统上使用的阴离子供体（例如C、N）是否在已建立的催化反应（例如转移氢化）中提供改进的反应性？(iii)富电子复合物具有这样的“钳形元素”钳形配体介导具有挑战性的键活化反应（例如N2，C-H），这对于利用丰富但无反应性的资源至关重要？这些研究将推进我们对金属-配体相互作用如何影响反应性的理解，从而能够设计出能够介导新的且日益具有挑战性的底物转化的金属催化剂。