Transition metal chemistry ansd catalysis

过渡金属化学与催化

• 批准号: 1311-2008
• 负责人: Morris, Robert
• 金额: $ 7.29万
• 依托单位: University of Toronto
• 依托单位国家: 加拿大
• 项目类别: Discovery Grants Program - Individual
• 财政年份: 2011
• 资助国家: 加拿大
• 起止时间: 2011-01-01 至 2012-12-31
• 项目状态: 已结题
• 来源: https://www.nserc-crsng.gc.ca/ase-oro/Details-Detailles_eng.asp?id=473463
• 关键词: Transition; metal; chemistry; ansd; catalysis

Our long-term research objective is to design and understand the functioning of new catalysts for bulk or fine chemical synthesis with applications in fragrance, flavours and pharmaceutical industries and catalysts for hydrogen storage, production or sensing for applications in the energy field. Over the past five years we have developed a variety of successful homogeneous catalysts and asymmetric catalysts based on ruthenium and osmium with hydride, phosphorus and nitrogen donor ligands. These are active for the selective hydrogenation of polar bonds including ketones for the production of alcohols and the hydrogenation of imines and nitriles for the synthesis of valuable amines. The same versatile catalysts are effective for asymmetric Michael addition reactions for fine chemical synthesis. This year we have discovered very active iron catalysts that are less expensive, less toxic and more environmentally friendly than ruthenium, rhodium or palladium catalysts. The iron catalysts will be a primary focus of the proposed research along with extensions of our ruthenium chemistry and exploratory work with other transition metals. Our successful approach to catalyst discovery involves the synthesis of well-defined complexes within or near to the postulated catalytic cycle and a careful study of their mode of action by measurement of rates and isotope effects, activation energies, and by ab initio calculations. An objective is relating the structure and electronics of the catalytic species with their activity and selectivity. Another objective is to improve the methods of synthesis and the properties of the catalysts to make them useful and easy to reuse. Such catalysts often have metal-hydrogen bonds. The protonic and hydridic reactivity of these compounds will continue to be studied in our lab in order to better understand catalysts and predict new chemical reactions.

我们的长期研究目标是设计和了解用于香料、香精和制药行业的大宗或精细化学合成的新催化剂的功能，以及用于能源领域的储氢、生产或传感的催化剂。在过去的五年中，我们成功地开发了多种基于氢化物，磷和氮给体的钌和锇的均相催化剂和不对称催化剂。它们对包括酮类在内的极性键的选择性氢化有活性，用于生产醇类，对合成有价胺的亚胺和腈的氢化有活性。同样的多功能催化剂在精细化学合成的不对称迈克尔加成反应中是有效的。今年，我们发现了非常活跃的铁催化剂，它们比钌、铑或钯催化剂更便宜、毒性更小、更环保。铁催化剂将是拟议研究的主要重点，同时也将扩展我们的钌化学和其他过渡金属的探索性工作。我们成功发现催化剂的方法包括在假设的催化循环内或附近合成定义明确的配合物，并通过测量速率和同位素效应、活化能和从头计算来仔细研究它们的作用模式。目的是将催化剂的结构和电子学与其活性和选择性联系起来。另一个目标是改进催化剂的合成方法和性能，使其有用并易于重复使用。这种催化剂通常具有金属-氢键。为了更好地理解催化剂和预测新的化学反应，我们将在实验室继续研究这些化合物的质子和水合反应性。