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: 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=616373
• 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提供资金，用于在申请人位于蒙特利尔大学化学系的实验室中开展有机金属和无机化学的创新科学研究计划。 我们提议进行的研究主要是好奇心驱动的实验，旨在推进我们对复杂分子的化学性质和反应性的基础知识，复杂分子由镍原子与称为“钳形”配体的稳定实体中包含的其他化学元素键合而成。这些络合物分子或简称络合物采用由钳形配体的键合、空间和电子性质以及镍原子的价态的组合决定的离散结构和几何形状，即，形式电离度。配体和金属中心相互影响，往往会产生新的化学行为，化学家可以利用这些化学行为用于各种目的，包括在石油化工，塑料，制药和其他有用材料等领域的实际应用。因此，我们提出的计划旨在导致科学发现，但它也包含可以用于商业和社会收益的元素。 这项研究计划的创意来自我们实验室以前的研究，这些研究也是由NSERC资助的。我们在这些研究中所做的观察使我们能够详细阐述新型有机镍络合物的合成路线，包括一些中心镍原子处于活性三价状态的络合物。对这些复合物的反应性的仔细探索揭示了导致“交叉偶联”协议的新途径，这一结果为开发用于制造新的有用材料的实用方法带来了很大希望。拟议的工作将把我们的研究带到令人兴奋的新方向，我们预计这将导致意想不到的发现和有用的发明。 由于实验将由我们的学生在B进行。Sc.、M. Sc.、和博士学位我们的研究计划也将培养出许多年轻的科学家。因此，我们寻求的资金将使我们能够培养高素质的人才，他们将在科学研究和发展方面从事有价值的职业。我们以前的研究已经培养了数十名年轻学生，他们在大学，学院，研究中心和行业中占据了许多领先的科学技术职位。从这个意义上说，NSERC基金使新的发现和创新，同时作为坚实的投资，在未来的科学家和技术人员的培训。