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

提出了对“地球丰富”的过渡金属-锰、铁、钴、镍和铜-的基础无机和配位化学的发现研究。 这个项目对我的发现补助金提案来说是新的，但对我的研究小组来说并不新鲜。 2008年，获得了大量资金，用于创建和开发用于石油升级的“新一代”加氢处理催化剂。 这项由工业界资助的研究的目标是坚定地应用：将用于沥青和其他重油的加氢脱硫和加氢脱氮的“工艺就绪”催化剂引入工业实践，取代当今世界普遍使用的能源密集型，非选择性和环境危害催化剂。 我们所提出的我们可以做的是前所未有的，一个中心假设不支持“现有技术”，并归因于目前的催化研究没有可识别的学校。 但这个想法实际上是可行的。 我们想知道是如何做到的。 我们要知道原因。 我们的工业资助不会扩展到基础性和探索性研究，除非是做出和优化我们的初步发现所需的研究。 这个提议是关于把发现变成学术。 我们提出了理解结构所必需的基础科学，揭示了机制，并为设计中的迭代改进提供了合理的基础。 我们还针对一系列其他重要的催化工艺，这些工艺目前需要“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。 本项目的目的是探索一种新的概念来设计地球上丰富的过渡金属的高活性催化剂。 它是关于基础研究-设计，合成，结构，键合，电子特性，反应性和机制。 在过去的五十年里，过渡金属催化的研究主要是关于配体设计。 第一行过渡金属物理上很小，有利于高自旋（顺磁）电子配置。 配体不稳定性和结构稳定性是这些元素的严重问题;大多数现代催化都采用多齿配体，其稳定金属，但限制配位不饱和度，抑制反应性并限制底物范围。“氧化还原活性”配体的掺入也在该领域提供了关键优势，导致该领域的稳定、递增的改进。 然而，除了少数例外，今天的第一排催化剂具有差的结构完整性、低活性和有限的底物范围。 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种金属成核成功能性的合作单元，每个金属一个。 许多金属，一个配体--第一行过渡金属催化剂设计的“双中心”方法。

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.**