Harnessing the Unusual Reactivity of Transition Metal Complexes Supported by Multidentate Silyl and Phosphido Ligands

过渡金属催化剂在以高效、选择性和环境友好的方式将丰富的资源转化为附加值产品的新化学工艺的开发中发挥着关键作用。在此背景下，Turculet小组的研究目标是制备反应性过渡金属钳形络合物，这种络合物可以促进涉及大量但顽固不反应的分子(例如碳氢化合物、氨、氮)的选择性化学转化。我们寻求开发高效的新催化反应，将这些“原料”化学物质转化为用于化学合成的有用的功能化构件。这类反应的发展被认为是当前催化领域最大的挑战之一。Turculet基团在合成高活性、非常规的硅基和磷酸盐金属络合物方面做出了开创性的贡献，我们在利用此类络合物断裂碳氢和氨氮-氢键方面取得了重要突破。在这项提议中，我们试图利用这种新的反应性来开发将氨转化为有机胺的新催化工艺。我们还建议合成新的钳形配合物，这些配合物旨在与碳氢化合物或氮(取决于金属中心的同一性)反应，目标是分别打破C-H键和N-N键，从而使它们能够在化学合成中用作合成子。我们的目标是将这种具有挑战性的断键步骤纳入新的催化过程-这是合成化学中的一个长期挑战。这种方法可以在药物、精细化学品和材料的合成中得到广泛应用。Turculet团队的研究吸引了最高水平的研究生和本科生(NSERC、Killam等许多著名奖学金就证明了这一点)，拟议中的计划将继续招聘这些杰出的人才。学生将接受有机和无机合成技术以及催化方面的培训，这将为他们在工业或学术环境中从事不同的职业做好准备。

Transition metal catalysts play a key role in the development of new chemical processes that convert abundant resources into value-added products in an efficient, selective, and environmentally friendly manner. In this context, research in the Turculet group targets the preparation of reactive transition metal pincer complexes that can promote selective chemical transformations involving abundant yet stubbornly unreactive molecules (e.g. hydrocarbons, ammonia, nitrogen). We seek to develop efficient new catalytic reactions that transform such "feedstock" chemicals into useful functionalized building blocks for chemical synthesis. The development of reactions of this type has been deemed one of the greatest current challenges in catalysis. The Turculet group has made pioneering contributions to the synthesis of highly reactive, non-conventional silyl and phosphido pincer metal complexes, and we have made important breakthroughs involving the utilization of such complexes for breaking hydrocarbon C-H and ammonia N-H bonds. In this proposal, we seek to capitalize on this novel reactivity in order to develop new catalytic processes for the transformation of ammonia into organic amines. We also propose the synthesis of new pincer complexes that are designed to react with either hydrocarbons or nitrogen (depending on the identity of the metal center) with the goal of breaking C-H and N-N bonds, respectively, so as to enable their use as synthons in chemical synthesis. We aim to incorporate such challenging bond breaking steps into new catalytic processes - a long-standing challenge in synthetic chemistry. Such methodology could find widespread application in the synthesis of pharmaceuticals, fine chemicals, and materials. Research in the Turculet group has attracted the highest-caliber graduate and undergraduate students (as evidenced by numerous prestigious scholarships, e.g. NSERC, Killam), and the proposed program will continue to recruit such outstanding personnel. Students will be trained in organic and inorganic synthesis techniques, as well as in catalysis, which will prepare them for a diversity of careers in either industrial or academic settings.