Transition metal chemistry ansd catalysis

我们的长期研究目标是设计和了解用于香料，香料和制药工业的散装或精细化学合成的新型催化剂的功能，以及用于能源领域应用的储氢，生产或传感催化剂。在过去的五年中，我们已经开发了各种成功的均相催化剂和基于钌和锇与氢化物，磷和氮供体配体的不对称催化剂。它们对极性键的选择性氢化具有活性，包括用于生产醇的酮和用于合成有价值的胺的亚胺和腈的氢化。同样的多用途催化剂对于精细化学合成的不对称迈克尔加成反应是有效的。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。铁催化剂将是拟议的研究沿着与我们的钌化学和探索工作与其他过渡金属的扩展的主要焦点。我们成功的方法催化剂的发现涉及到合成的定义明确的配合物内或附近的假设的催化循环和仔细研究他们的行动模式，通过测量速率和同位素效应，活化能，并通过从头计算。一个目标是将催化物种的结构和电子学与它们的活性和选择性相关联。另一个目标是改进合成方法和催化剂的性质，使其有用且易于重复使用。这种催化剂通常具有金属-氢键。这些化合物的质子和质子反应性将在我们的实验室中继续研究，以便更好地了解催化剂并预测新的化学反应。

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.