High-activity base metal catalysts for strong carbon-heteroatom bond activation

用于强碳-杂原子键活化的高活性贱金属催化剂

• 批准号: RGPIN-2016-04848
• 负责人: Stryker, Jeffrey
• 金额: $ 5.46万
• 依托单位: University of Alberta
• 依托单位国家: 加拿大
• 项目类别: Discovery Grants Program - Individual
• 财政年份: 2016
• 资助国家: 加拿大
• 起止时间: 2016-01-01 至 2017-12-31
• 项目状态: 已结题
• 来源: https://www.nserc-crsng.gc.ca/ase-oro/Details-Detailles_eng.asp?id=615337
• 关键词: activity; base; metal; catalysts; strong; activity; base; metal; catalysts; strong

Discovery research in fundamental inorganic and coordination chemistry of the “earth abundant" transition metals - manganese, iron, cobalt, nickel, and copper - is proposed. This program is new to my Discovery Grant proposal, but it is not new to my research group. In 2008, major funding was obtained to create and develop “new-generation” hydrotreatment catalysts for petroleum upgrading. The objective of this industry-funded research is resolutely applied: introduce into industrial practice “process-ready” catalysts for hydrodesulfurization and hydrodenitrogenation of bitumen and other heavy oils, replacing the energy-intensive, unselective, and environmentally compromising catalysts in ubiquitous use today, worldwide. What we proposed we could do was unprecedented, with a central hypothesis unsupported by “prior art” and attributed to no identifiable school of current catalysis research. But the idea actually works. We would like to know how. And we need to know why. Our industrial funding does not extend to fundamental and exploratory investigations beyond those required to make and optimize our initial discoveries. This proposal is about turning discovery into scholarship. We propose the basic science necessary to understand structure, reveal mechanism, and provide a rational basis for iterative improvements in design. We also target a range of other important catalytic processes that currently require “energy-intensive” conditions (typically, high pressure and temperature) or precious metal catalysts, or both. This proposal is about exploring a new concept in designing high-activity catalysts of the earth-abundant transition metals. It is about fundamental research - design, synthesis, structure, bonding, electronic character, reactivity, and mechanism. Over the past fifty years, research in transition metal catalysis has been mostly about ligand design. First-row transition metals are physically small and favour high-spin (paramagnetic) electronic configurations. Ligand lability and structural stability is a serious issue for these elements; most of modern catalysis has adopted polydentate ligands, which stabilize the metal, but limit coordinative unsaturation, inhibiting reactivity and limiting substrate scope. The incorporation of “redox active” ligands also provide key advantages in this area, leading to steady, incremental, improvements in the field. With few exceptions, however, today’s first-row catalysts suffer from poor structural integrity, low activity, and limited substrate scope. In this work, a non-traditional approach to catalyst design is taken, nucleating multiple metals into functional, cooperative units using a single anionic ligand, one per metal. Many metals, one ligand - a “metallocentric” approach to first-row transition metal catalyst design.

提出了“地球丰富”过渡金属的基本无机和协调化学的发现研究 - 锰，铁，钴，镍和铜。该计划是我的发现赠款提案的新事物，但对我的研究小组来说并不是新事物。 2008年，获得了主要资金，以创建和开发用于石油升级的“新一代”水力局催化剂。这项行业资助的研究的目的是明确应用的：将沥青和其他重油的氢化和氢化化催化剂引入工业实践“准备就绪”催化剂中，以取代当今世界上无处不在的无处不在使用的能源密集型，非选择性和环境损害的催化剂。我们提出的要做的事情是前所未有的，一个中心假设不受“先前的艺术”的支持，并且归因于当前催化研究的可识别学校。但是这个想法实际上有效。我们想知道如何。我们需要知道为什么。我们的工业资金并没有扩展到基本和探索性投资，而不是进行和优化我们最初发现所需的投资。该建议是关于将发现变成科学。我们提出了理解结构，揭示机制并为设计迭代改进提供合理基础所必需的基础科学。我们还针对当前需要的其他一系列重要的催化过程。 “能源密集型”条件（通常是高压和温度）或贵金属催化剂，或两者兼而有之。该建议是关于探索在设计地球丰富过渡金属的高活动性催化剂时的新概念。它涉及基础研究 - 设计，合成，结构，键合，电子特征，反应性和机制。在过去的五十年中，过渡金属催化研究主要是关于配体设计的。第一行过渡金属物理上很小，偏爱高旋转（顺磁性）电子构型。对于这些元素而言，配体的劳动力和结构稳定性是一个严重的问题。大多数现代催化剂都采用了稳定金属的多乙酸配体，但限制了坐标不饱和，抑制了反应性和限制底物范围。 “氧化还原活性”配体的掺入还提供了该区域的关键优势，从而导致田间稳定，增量的改进。然而，除少数例外，当今的第一行催化剂的结构完整性不佳，活动较低和底物范围有限。在这项工作中，采用了非传统的催化剂设计方法，使用单个阴离子配体将多种金属定为功能性合作单元，每种金属一种。许多金属，一种配体 - 一种用于第一行过渡金属催化剂设计的“金属中心”方法。