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

过渡金属催化剂在将丰富的资源高效、选择性和环保地转化为高附加值产品的新化学工艺的发展中起着关键作用。在这种背景下，Turculet小组的研究目标是制备反应性过渡金属螯合物，这种螯合物可以促进涉及丰富但顽固不反应的分子（如碳氢化合物、氨、氮）的选择性化学转化。我们寻求开发有效的新催化反应，将这些“原料”化学品转化为化学合成的有用功能化构件。这类反应的发展被认为是目前催化领域最大的挑战之一。Turculet团队在合成高活性、非常规的硅基和磷螯合金属配合物方面做出了开创性的贡献，我们在利用这些配合物破坏碳氢化合物碳氢键和氨氮氢键方面取得了重要突破。在本提案中，我们寻求利用这种新的反应性，以开发新的催化过程，将氨转化为有机胺。我们还建议合成新的钳形配合物，旨在与碳氢化合物或氮（取决于金属中心的身份）分别反应，以破坏C-H和N-N键，从而使其在化学合成中作为合成子使用。我们的目标是将这种具有挑战性的键断裂步骤纳入新的催化过程-合成化学中的长期挑战。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小组的研究吸引了最优秀的研究生和本科生（如众多享有声望的奖学金，如NSERC， Killam），拟议的计划将继续招募这些优秀人才。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的各种职业做好准备。

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.