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

本申请请求 NSERC 资助一项有机金属和无机化学创新科学研究项目，该项目将在申请人位于蒙特利尔大学化学系的实验室进行。 我们建议进行的研究主要是好奇心驱动的实验，旨在增进我们对复杂分子的化学性质和反应性的基础知识，该复杂分子由与称为“钳形”配体的稳定实体中包含的其他化学元素键合的镍原子组成。这些复杂分子，或简称复合物，采用由钳配体的键合、空间和电子性质以及镍原子的价态（即形式电离度）的组合决定的离散结构和几何形状。配体和金属中心彼此之间的相互影响通常会产生新颖的化学行为，化学家可以将其用于各种目的，包括石化、塑料、制药和其他有用材料等不同领域的实际应用。因此，我们提出的计划旨在带来科学发现，但它也包含可用于商业和社会收益的元素。 这个研究项目的创意源自我们实验室之前的研究，这些研究也得到了国家教育研究委员会的资助。我们在这些研究中进行的观察使我们能够详细阐述新型有机镍配合物的合成路线，包括一些中心镍原子处于反应性三价状态的配合物。对这些配合物反应性的仔细探索揭示了导致“交叉偶联”方案的新途径，这一结果为开发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向令人兴奋的新方向，我们预计将带来意想不到的发现和有用的发明。 由于拟议的实验将由我们的学士、硕士和博士级别的学生进行，因此我们的研究计划也将培训许多年轻科学家。因此，我们寻求的资金将使我们能够培养高素质人才，他们将在科学研究和开发领域从事有价值的职业。我们前期的研究已经培养了数十名青年学生，他们在大学、学院、研究中心和工业界占据了许多领先的科技职位。从这个意义上说，NSERC 基金促进了新的发现和创新，同时也是对未来科学家和技术人员培训的可靠投资。

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.