Organotransition Metal Chemistry and Catalysis

有机过渡金属化学与催化

• 批准号: RGPIN-2016-04637
• 负责人: Baird, Michael
• 金额: $ 2.19万
• 依托单位: Queen's University
• 依托单位国家: 加拿大
• 项目类别: Discovery Grants Program - Individual
• 财政年份: 2016
• 资助国家: 加拿大
• 起止时间: 2016-01-01 至 2017-12-31
• 项目状态: 已结题
• 来源: https://www.nserc-crsng.gc.ca/ase-oro/Details-Detailles_eng.asp?id=615202
• 关键词: Organotransition; Metal; Chemistry; Catalysis

Our research program involves investigations of the chemistry of and catalysis by organotransition metal compounds, and is an extension of a very long term program in basic and applied research which goes back over 40 years. My 2015 DG application describes three important, related research Themes which, as they are significantly advanced over the next five years, will greatly contribute to potential industrial applications of metal catalysis in Canada. Theme 1. Elusive intermediates in alkene polymerization catalysis. Prior to our work, researchers had had very little success in detecting several types of short-lived intermediate species in metallocene catalyzed alkene polymerization reactions. We solved this problem using alkenes which can coordinate but cannot, for steric reasons, undergo more than one insertion reaction. As a result, we show that we can use NMR to observe not only unusual alkyl alkene species but also unprecedented types of agostic complexes. This is a proposal to explore complexes of the types [Cp2MMe(alkene)]+ (M = Zr, Hf) for which we have fascinating preliminary results in hand. The results will contribute greatly to our understanding of this very important class of industrial catalysts. Theme 2. Catalysis of cross-coupling reactions by nickel. Nickel has important advantages over the normally used palladium for cross-coupling catalysis because, in addition to its lower cost, nickel works with many more types of substrates than does palladium. This proposal extends our ongoing program on the use of palladium-based catalysts and involves a study of several types of nickel compounds for their catalytic activities. Success will provide opportunities to systematically tailor catalysts by modifying the ligands in order to to effect asymmetric and stereoconvergent cross-coupling reactions. The results, in addition to adding much to basic knowledge of catalytic processes, will be of obvious potential benefit to Canada's pharmaceutical industry. Theme 3. Coordination chemistry of phosphonium indenylides (PHINs). This largely unexplored class of aromatic ligands is of special interest because they bind to transition metals to form planar chiral complexes which are configurationally stable; thus they may well serve as excellent asymmetric catalysts for reactions of prochiral substrates because the catalysts will be rigidly chiral directly at the metal rather than at the periphery of a ligand as is normally the case. This proposal describes research on planar chiral compounds of several metals, chosen because their complexes with other ligands catalyze a very wide range of important catalytic reactions. As is the case with Theme 2, successful results will be of obvious potential benefit to Canada's pharmaceutical industry. Our program will continue, as it has for many years, to train four to eight undergraduate, graduate and postdoctoral researchers per year.

我们的研究计划涉及有机过渡金属化合物的化学和催化作用的调查，是基础和应用研究的长期计划的延伸，可以追溯到40多年前。我的2015年DG申请描述了三个重要的相关研究主题，因为它们在未来五年内将显着推进，将大大有助于加拿大金属催化的潜在工业应用。 主题1.烯烃聚合催化中的挥发性中间体。在我们的工作之前，研究人员在茂金属催化烯烃聚合反应中检测几种类型的短寿命中间体物种方面几乎没有成功。我们解决了这个问题，使用烯烃可以协调，但不能，空间的原因，进行一个以上的插入反应。因此，我们表明，我们可以使用NMR观察不仅不寻常的烷基烯烃物种，但也前所未有的类型agostic配合物。这是一个建议，探索类型的配合物[Cp 2 MMe（烯烃）]+（M = Zr，Hf），我们有迷人的初步结果在手。 这些结果将大大有助于我们对这类非常重要的工业催化剂的理解。 主题2.镍催化交叉偶联反应。镍在交叉偶联催化中比通常使用的钯具有重要的优势，因为除了其较低的成本之外，镍比钯与更多类型的基底一起工作。该提案扩展了我们正在进行的关于使用钯基催化剂的计划，并涉及研究几种类型的镍化合物的催化活性。成功将提供机会，系统地定制催化剂，通过修改的配体，以实现不对称和立体收敛的交叉偶联反应。 结果，除了增加催化过程的基本知识，将是加拿大的制药工业明显的潜在利益。 主题3.磷茚基（PHIN）的配位化学。这类基本上未开发的芳族配体是特别感兴趣的，因为它们与过渡金属结合形成构型稳定的平面手性络合物;因此它们可以很好地用作用于前手性底物反应的优异的不对称催化剂，因为催化剂将直接在金属上而不是在配体的外围具有刚性手性，如通常情况下那样。该提案描述了对几种金属的平面手性化合物的研究，选择这些金属是因为它们与其他配体的络合物催化非常广泛的重要催化反应。与主题2的情况一样，成功的结果将对加拿大的制药业产生明显的潜在利益。 我们的计划将继续，因为它已经多年，每年培养四到八个本科生，研究生和博士后研究人员。