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.

在化学催化计划中，布法罗大学的史蒂文·T·史蒂文·T·史蒂文·T·史蒂文·T·史蒂文·T·史蒂文·T·史蒂文·T·史蒂文·T·史蒂文·T·史蒂文（机 U），正在研究特殊的大环配体的合成和使用，以促进基于金属的催化剂来执行选择性化学反应。将研究金属和这种相对未开发的大环配体的组合，以基于分子大小来达到选择性。这种选择性原理是自然催化剂（酶）的常见方面，但它代表了人造小分子催化剂的具有挑战性的边界。涉及地球丰富和低成本的金属的努力中的成功将允许生产重要的商品，例如精美的化学品，药品，药剂剂，农业化学物质以及其他对美国经济有价值的先进材料，以更有效和可持续的方式进行。该资助项目的更广泛影响将扩展到制定认证计划，旨在改善培训从事教学职业的研究生。在这样的努力中，PI拥有成功指导一群受训者的出色记录。 还计划了一个专注于培养更有效教师指导的研讨会，期望提高SUNY BUFFALO的教学和研究活动的表现。该项目的重点是进一步发展使用FE，CO，CO，NI或NI的尺寸选择性催化的概念。这项工作是基于潜水员研究小组先前的研究，其中大粒细胞碳纤维配体被证明用于大小选择性的RU催化烯烃的烯烃分解。催化剂在分子中区分两个相同官能团的能力将允许以新的方式计划和执行有机合成，从而有可能消除（或至少最小化）对涉及保护组和其他浪费合成操作的外部操作的需求。该研究计划分为几个协同的目标。在每种情况下，先前确定的尺寸选择性原理都将通过使用具有二齿或三国含氮配体的新的大环系统来扩展和适应催化剂。例如，将合成和共同催化的交叉耦合以及烯烃的Fe催化氢硅烷基合成并使用大环和双环酚酚属配体。在其他工作中，将使用大环的大小选择性氧化，以区分多元醇底物内的二次醇。所研究的转换在工业上是相关的，这项研究的发现有望突出化学制造金属的有效且经济的替代方案。该奖项反映了NSF的法定任务，并被认为是值得通过基金会的知识分子优点和更广泛的审查标准通过评估来进行评估的。