Advances in divalent and trivalent organonickel chemistry: new routes to C-H functionalizations

二价和三价有机镍化学的进展：C-H官能化的新途径

• 批准号: RGPIN-2016-06539
• 负责人: Zargarian, Davit
• 金额: $ 3.35万
• 依托单位: Université de Montréal
• 依托单位国家: 加拿大
• 项目类别: Discovery Grants Program - Individual
• 财政年份: 2020
• 资助国家: 加拿大
• 起止时间: 2020-01-01 至 2021-12-31
• 项目状态: 已结题
• 来源: https://www.nserc-crsng.gc.ca/ase-oro/Details-Detailles_eng.asp?id=709916
• 关键词: Advances; divalent; trivalent; organonickel; chemistry

This application requests funds from NSERC for an innovative scientific research program in organometallic and inorganic chemistry to be carried out in the applicant's laboratory, which is located at the department of chemistry, Université de Montréal. The studies we propose to conduct are primarily curiosity-driven experiments aimed at advancing our fundamental knowledge of the chemical nature and reactivities of complex molecules consisting of a nickel atom bonded to other chemical elements contained within a stabilizing entity called “pincer” ligands. These complex molecules, or complexes for short, adopt discrete structures and geometries dictated by a combination of the pincer ligand's bonding, steric and electronic properties, as well as the nickel atom's valence, i.e., formal degree of ionization. The reciprocal influence of the ligand and the metal centre on each other often gives rise to novel chemical behaviour that a chemist can harness for a various purposes, including for practical applications in fields as diverse as petrochemicals, plastics, pharmaceuticals, and other useful materials. Thus, the program we propose is designed to lead to scientific discoveries, but it also contains elements that can be exploited for commercial and societal gains. The creative ideas for this research program evolved from our laboratory's previous studies, which were also funded by NSERC. The observations we made during these studies allowed us to elaborate synthetic routes to novel organonickel complexes, including a few complexes in which the central nickel atom is in a reactive trivalent state. Careful explorations of the reactivities of these complexes revealed new routes leading to “cross-coupling” protocols, an outcome that holds much promise for developing practical methodologies for making new, useful materials. The proposed work will take our studies in exciting new directions that we anticipate will result in unanticipated discoveries and useful inventions. Since the proposed experiments will be conducted by our students at the B. Sc., M. Sc., and Ph. D. level, our research program will also result in the training of many young scientists. Therefore, the funds we seek will allow us to nurture highly qualified personnel who will go on to valuable careers in scientific research and development. Our previous studies have already trained dozens of young students who occupy many leading scientific-technical positions in universities, colleges, research centers and industry. In this sense, NSERC funds enable novel discoveries and innovations while serving as solid investments in the training of future scientists and technologists.

该申请要求NSERC的资金为有机和无机化学的创新科学研究计划，该计划将在该应用程序的实验室中进行，该计划位于蒙特利尔大学化学系。 我们建议进行的研究主要是好奇心驱动的实验，旨在促进我们对由镍原子组成的复杂分子的化学性质和反应性的基本知识，该镍原子粘合到包含的其他化学元素中，该化学元素包含的稳定实体中，称为“ pincer”配体。这些复杂的分子或简短的复合物采用离散的结构和几何形状，由钳子配体的键合，空间和电子特性以及镍原子的价值（即形式的电离程度）所决定。配体和金属中心彼此之间的相互影响通常会引起新的化学行为，化学家可以利用各种目的来利用，包括在诸如石油化学物质，塑料，药物和其他有用材料的潜水场所中的实际应用。这就是我们提出的计划旨在导致科学发现，但它还包含可以探索商业和社会成就的要素。 该研究计划的创造思想是从我们实验室先前的研究中演变而来的，该研究也由NSERC资助。我们在这些研究中进行的观察结果使我们能够详细阐述与新型Organickel复合物的合成路线，其中包括一些中央镍原子处于反应性三价状态的复合物。仔细探索这些复合物的重复性揭示了导致“交叉耦合”方案的新途径，这一结果具有开发制造新的有用材料的实用方法的很大希望。拟议的工作将使我们的研究以令人兴奋的新方向发展，我们期望这将导致意外的发现和有用的事件。 由于提出的实验将由我们的学生在B.Sc。，M。Sc。和Ph.D. D. Level进行的，我们的研究计划也将导致许多年轻科学家的培训。因此，我们寻求的资金将使我们能够护理高素质的人员，他们将继续从事科学研发领域的宝贵职业。我们以前的研究已经培训了数十名年轻学生，他们在大学，学院，研究中心和工业界占据了许多领先的科学技术职位。从这个意义上讲，NSERC资金可以在培训未来的科学家和技术的培训中为新颖的发现和创新。