Selective Catalysis with Macrocyclic Nitrogen Ligands

大环氮配体的选择性催化

• 批准号: 2154997
• 负责人: Steven Diver
• 金额: $ 48.11万
• 依托单位: SUNY at Buffalo
• 依托单位国家: 美国
• 项目类别: Standard Grant
• 财政年份: 2022
• 资助国家: 美国
• 起止时间: 2022-09-01 至 2025-08-31
• 项目状态: 未结题
• 来源: https://www.nsf.gov/awardsearch/showAward?AWD_ID=2154997&HistoricalAwards=false
• 关键词: Selective; Catalysis; Macrocyclic; Nitrogen; Ligands

With the support of the Chemical Catalysis Program in the Division of Chemistry, Professor Steven T. Diver of the University at Buffalo is studying the synthesis and use of special macrocyclic ligands to enable metal-based catalysts to perform selective chemical reactions. The combinations of metals and such relatively unexplored macrocyclic ligands will be investigated with the aim of achieving selectivity based upon molecular size. This selectivity principle is a common facet of Nature's catalysts (enzymes), but it represents a challenging frontier for artificial small-molecule catalysts. Success in the endeavors being pursued, which involve earth abundant and low cost metals, will allow for the manufacture of important commodities, such as fine chemicals, pharmaceutical agents, agrochemicals, and other advanced materials of value to the US economy, to be conducted in a more efficient and sustainable manner. The broader impacts of the funded project will extend to the development of a certification program aimed at improving the training of graduate students who are headed towards careers in teaching. In such endeavors, the PI has an excellent record of successfully mentoring a diverse group of mentees. A workshop focused on fostering more effective faculty mentorship is also planned with the expectation of enhancing the performance of teaching and research activities at SUNY Buffalo.The funded project focuses on further development of the concept of size-selective catalysis using complexes of Fe, Co, or Ni, and specially designed macrocyclic ligand families for various cross coupling and hydrofunctionalization reactions. The work builds on previous studies by the Diver research group in which macrocyclic N-heterocyclic carbene ligands were demonstrated for size-selective Ru-catalyzed alkene metathesis. The ability of a catalyst to distinguish between two of the same functional groups within a molecule will allow organic synthesis to be planned and carried out in new ways, potentially obviating (or at least minimizing) the need for extraneous operations involving protecting group and other wasteful synthetic manipulations. The research program is divided across several synergistic aims; in each case, the size selectivity principles previously established will be extended and adapted for catalysts based on earth abundant metals by using new macrocyclic systems that feature bidentate or tridentate nitrogen-containing ligands. For example, macrocyclic and bimacrocyclic phenanthroline ligands will be synthesized and used in Ni- and Co-catalyzed cross coupling and in the Fe-catalyzed hydrosilylation of alkenes. In other work, macrocycles will be utilized for size-selective oxidation to differentiate secondary alcohols within polyol substrates. The transformations being studied are industrially relevant and the findings of this research are expected to highlight efficient and economical alternatives to noble metals for chemical manufacturing.This award reflects NSF's statutory mission and has been deemed worthy of support through evaluation using the Foundation's intellectual merit and broader impacts review criteria.

在化学系化学催化项目的支持下，史蒂文·T·布法罗大学的Diver正在研究特殊大环配体的合成和使用，以使金属基催化剂能够进行选择性化学反应。将研究金属和这种相对未开发的大环配体的组合，目的是基于分子大小实现选择性。这种选择性原理是自然界催化剂（酶）的一个共同方面，但它代表了人工小分子催化剂的一个具有挑战性的前沿。正在追求的努力的成功，涉及地球丰富和低成本的金属，将允许以更有效和可持续的方式制造重要的商品，如精细化学品，药剂，农用化学品和其他对美国经济有价值的先进材料。资助项目的更广泛影响将扩展到认证计划的开发，旨在改善对即将从事教学职业的研究生的培训。在这样的努力中，PI有一个成功地指导不同群体的学员的良好记录。 一个研讨会的重点是促进更有效的教师指导，也计划与提高教学和研究活动的表现在纽约州立大学布法罗的期望。资助的项目侧重于进一步发展的概念，尺寸选择性催化使用配合物的铁，钴，镍，和专门设计的大环配体家族的各种交叉耦合和氢官能化反应。这项工作建立在以前的研究由Diver研究小组，其中大环N-杂环卡宾配体被证明为大小选择性钌催化烯烃复分解。催化剂区分分子内两个相同官能团的能力将允许以新的方式规划和进行有机合成，潜在地消除（或至少最小化）对涉及保护基的无关操作和其他浪费的合成操作的需要。该研究计划分为几个协同目标;在每种情况下，以前建立的尺寸选择性原则将通过使用具有二齿或三齿含氮配体的新的大环体系来扩展和适应基于地球丰富金属的催化剂。例如，大环和双大环菲咯啉配体将被合成并用于Ni和Co催化的交叉偶联和Fe催化的烯烃氢化硅烷化。在其他工作中，大环化合物将用于尺寸选择性氧化，以区分多元醇底物中的仲醇。正在研究的转换是工业相关的，这项研究的结果预计将突出有效和经济的替代贵金属化学制造。这个奖项反映了NSF的法定使命，并已被认为是值得通过使用基金会的智力价值和更广泛的影响审查标准进行评估的支持。