Stabilization of Unique Chemical Bonding Environments and Exploration of Small Molecule Reactivity

作为我小组正在进行的研究的一部分，在这个提案中，我们将重点关注以下项目，这些项目跨越了我们的专业领域，包括主组和过渡金属合成化学。基于增田研究小组的经验和优势，我建议继续研究并扩大我们在以下领域的知识：半可溶螯合配体：探索小分子反应性和催化作用的金属配合物我们将扩展我们对配位化学的研究，我们的teraryl环戊二烯配体，并探索所得到的金属配合物的反应性。这种配体的半半性是由强结合的阴离子环戊二烯基和弱结合的芳基引起的。我建议继续这个项目，寻找更多令人兴奋的目标，包括利用半可降解的萜烯基的潜在氧化还原特性来帮助稳定低氧化态金属中心。然后，这些物种可以用作低氧化态金属的合成物。将测试这些材料与小分子和催化的进一步反应性。体积庞大的双齿配体已被证明在主基、过渡和f嵌段金属的配位化学中是非常重要的。通常，这些双齿配体由亚胺、胺、磷酰亚胺、羰基、硫羰基、烷氧基和磷氧化物等供体组成。在非对称体系中，可以使用不同的给体来利用给体原子的硬度和柔软度的差异。酰基化合物在有机化学中是很有名的，特别是作为威提格试剂，在配位化学中被用作软的2电子给体。文献中很少有含有芴基的氟化物的例子。我们建议制备多种螯合配体，其中一侧具有典型的给体（N， O， S），另一侧具有柔性的碳基酰/氟酰基-磷烷片段。这种配体排列可以分离出通过硬亚胺和软酰基片段配位的6元金属螯合物，或者通过硬亚胺和芳香氟烯基阴离子的软5元6-p电子部分配位的伪6元螯合物。这两种类型的螯合之间可能存在流动性，这种流动性可以用来影响金属配合物的反应性。2. 十多年来，我一直在探索单线态碳烯和膦基自由基与各种小分子的反应性。这些系统包括反应E-E键、E-H键和扩展p-系统。我建议针对单线态碳烯和膦基自由基与一些外来小分子/官能团的反应，形成具有新的和意想不到的性质的新官能团。

As part of the ongoing research within my group, in this proposal we will be focusing on the following projects that span our areas of specialty including main group and transition metal synthetic chemistry. Building upon the experience and strengths in the Masuda Research Group, I propose to continue research and expand upon our knowledge in the following areas: 1. Hemilabile chelating ligands: metal complexes for exploration of small molecule reactivity and catalysis We will extend our investigation of the coordination chemistry our teraryl cyclopentadienyl ligands and explore the reactivity of the resulting metal complexes. The hemilability of this ligands results from the strongly bound anionic cyclopentadienyl group and the more weakly p-bound aryl group. I propose to continue with this project with more exciting targets including utilizing the potential redox properties of the hemilabile teraryl group to help stabilize low-oxidation state metal centers. These species can then be used as synthons for lower oxidation state metals. These will be tested for further reactivity with small molecules and in catalysis. Sterically bulky, bidentate ligands have proven to be very important in coordination chemistry of main group, transition, and f-block metals. Often, these bidentate ligands consist of donors such as imines, amines, phosphinimines, carbonyls, thiocarbonyls, alkoxides, and phosphine oxides. In the unsymmetrical systems, different donors may be used to exploit differences in the hardness and softness of the donor atoms. Ylides are well known in organic chemistry, particularly as Wittig reagents, and are used as soft, 2-electron donors in the area of coordination chemistry. There are few examples in the literature of ylides that contain the fluorenylidene group. We propose to prepare a variety of chelating ligands, where one side has an typical donor (N, O, S) and the other has the flexible, carbon-based ylide/fluorenylidene-phosphorane fragment. This ligand arrangement will either allow for the isolation of 6-membered metal chelates coordinated via the hard imine and the soft ylide fragment, or pseudo-6-membered chelates coordinated through the hard imine and the soft, 5-membered, 6-p electron portion of the aromatic fluorenyl anion. It is possible that there will be fluxionality between the two types of chelation and this fluxionality can be exploited to affect the reactivity of metal complexes. 2. Reactivity with small molecules with N-Heterocyclic carbenes and phosphinyl radicals For well over a decade, I have explored the reactivity of singlet carbenes and phosphinyl radicals with a wide variety of small molecules. These include systems with reactive E-E bonds, E-H bonds, and extended p-systems. I propose on targeting the reaction of singlet carbenes and phosphinyl radicals with a number of exotic small molecules/functional groups to form new functional groups with new and unexpected properties.