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

提出了“富土”过渡金属锰、铁、钴、镍和铜的基础无机化学和配位化学的发现研究。这个项目对我的探索助学金计划来说是新的，但对我的研究小组来说并不新鲜。2008年，获得了大量资金，用于创造和开发用于石油提质的“新一代”加氢处理催化剂。这项由行业资助的研究的目标是坚决应用于工业实践：将沥青和其他重油加氢脱硫和加氢脱氮的“工艺就绪”催化剂引入工业实践，取代当今世界各地普遍使用的能源密集型、非选择性和环境危害的催化剂。我们提出的我们可以做的是史无前例的，一个中心假说没有得到“现有技术”的支持，并被归因于当前催化研究中没有可识别的流派。但这个想法实际上是可行的。我们想知道是怎么回事。我们需要知道为什么。我们的工业资金不会延伸到基础和探索性调查，而不是那些做出和优化我们最初发现所需的调查。这项提议是关于将发现转化为学术。我们提出了理解结构、揭示机制所必需的基础科学，并为设计中的迭代改进提供合理的基础。我们还瞄准了一系列其他重要的催化过程，这些过程目前需要“能源密集型”条件(通常是高压和高温)或贵金属催化剂，或两者兼而有之。这项建议是关于探索一种新的概念来设计高活性的地球上丰富的过渡金属催化剂。它涉及基础研究的设计、合成、结构、成键、电子性质、反应活性和机理。在过去的五十年里，过渡金属催化的研究主要集中在配体设计上。第一排过渡金属在物理上很小，并且有利于高自旋(顺磁)电子组态。配体的不稳定性和结构稳定性是这些元素的一个严重问题；现代催化大多采用多齿配体，这些配体稳定了金属，但限制了配位不饱和度，抑制了反应活性，限制了底物范围。“氧化还原活性”配体的加入也在这一领域提供了关键优势，导致了该领域的稳定、渐进的改进。然而，几乎没有例外，今天的第一排催化剂结构完整性差，活性低，底物范围有限。在这项工作中，采用了一种非传统的催化剂设计方法，使用单个阴离子配体将多个金属成核成功能协作单元，每个金属一个。许多金属，一种配体，一种以金属为中心的方法来设计第一排过渡金属催化剂。

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.