Main Group Cations, Radicals, Metal Complexes and Their Applications

主族阳离子、自由基、金属配合物及其应用

• 批准号: RGPIN-2015-03825
• 负责人: Masuda, Jason
• 金额: $ 2.04万
• 依托单位: Saint Mary's University
• 依托单位国家: 加拿大
• 项目类别: Discovery Grants Program - Individual
• 财政年份: 2018
• 资助国家: 加拿大
• 起止时间: 2018-01-01 至 2019-12-31
• 项目状态: 已结题
• 来源: https://www.nserc-crsng.gc.ca/ase-oro/Details-Detailles_eng.asp?id=659012
• 关键词: Main; Group; Cations; Radicals; Metal

As part of the ongoing research within my research 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:***1. Low-valent and/or low oxidation state heavy Group 13 elements: Cations and radicals stabilized by electron-rich ligands***In the area of Group 13 cations and radicals we aim to develop the appropriate molecular frameworks that are necessary to electronically and sterically stabilize these molecules. A complete understanding of these systems will provide insight to the bonding of Al with other atoms and at the same time, allow us to determine if these molecules can be used as ligands on transition metals. This work is expected to have a high impact in the area involving fundamental reactivity and bonding in these metals.***2. Chelating Cp/aryl based ligands for main group and transition metal complexes ***We aim to prepare a suite of mono anionic ligands similar to known constrained geometry-type of ligands where the metal center is chelated by one cyclopentadienyl (Cp) anionic ring and one, neutral aryl ring, both separated by o-positioning about a backbone aryl ring. Altering the substituents on the (Cp) ring and the aryl ring will tune the electronics and sterics of these molecules, allowing for the studying of the bonding. In the case of some metals, for example iron, the strained Cp-Aryl angle will cause a significant destabilization of the frontier molecular orbitals when compared to ferrocene, Cp2Fe, or [Cp-Fe-Benzene] cations, allowing for unprecedented reactivity to take place.***3. The chemistry of white phosphorus (P4) with hydrogen***Our experience in P4 chemistry has lead us to investigate the fundamental reactivity of P4 with both a proton and a hydrogen atom. To date, there is only evidence of the existence of [P4H]+ in the gas phase. Through judicious selection of a "super acid" and solvent choice we plan on identifying [P4H]+ in solution and isolating it in the solid state. In a similar vein, the reactivity of P4 with a hydrogen atom is proposed to be studied using muonium, a light isotope of hydrogen. ***4. Electron-rich organic and inorganic molecules***Recently we have had success in the preparation of electron rich, highly unsaturated "organic" molecules, many of them highly colored. These systems are stable derivatives of the highly reactive propargyl cation [H2C-CC-H]+ and its related radical. We aim to explore various substitution patterns about a central, highly unsaturated fragment [para-CC-C6H4-CC]. These "inorganic" analogues of our original molecules will be made by substituting the ends of the [para-CC-C6H4-CC] with phosphorus or boron-based molecules. We also propose making a "push-pull" type of system where an e- donating group is attached to one end and an e- withdrawing group is on the other. These substitutions will allow for the tuning of their properties and reactivity.**

作为我的研究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，这些项目跨越我们的专业领域，包括主组和过渡金属合成化学：低价和/或低氧化态重13族元素：由富电子配体稳定的阳离子和自由基***在13族阳离子和自由基领域，我们的目标是开发适当的分子框架，以电子和空间稳定这些分子。对这些系统的全面了解将有助于了解Al与其他原子的键合，同时，使我们能够确定这些分子是否可以用作过渡金属上的配体。这项工作预计将在涉及这些金属的基本反应性和键合的领域产生重大影响。***我们的目标是制备一组类似于已知的约束几何型配体的单阴离子配体，其中金属中心被一个环戊二烯（Cp）阴离子环和一个中性芳基环螯合，两者通过围绕一个主芳基环的o定位分开。改变（Cp）环和芳基环上的取代基将调整这些分子的电子学和立体构型，从而允许研究键合。在某些金属的情况下，例如铁，与二茂铁、Cp2Fe或[cp - fe -苯]阳离子相比，张力的cp -芳基角会导致前沿分子轨道的显著不稳定，从而允许发生前所未有的反应性。白磷（P4）与氢的化学反应***我们在P4化学方面的经验使我们研究了P4与质子和氢原子的基本反应性。到目前为止，只有[P4H]+存在于气相的证据。通过“超强酸”的选择和溶剂的选择，我们计划在溶液中识别[P4H]+并在固态中分离它。同样，P4与氢原子的反应性也被提议用氢的一种轻同位素muonium来研究。* * * 4。富电子的有机和无机分子***最近我们成功地制备了富电子的、高度不饱和的“有机”分子，其中许多是高度着色的。这些体系是高活性丙炔阳离子[H2C-CC-H]+及其相关自由基的稳定衍生物。我们的目标是探索中心高度不饱和片段的各种取代模式[para-CC-C6H4-CC]。这些原始分子的“无机”类似物将通过用磷或硼基分子取代[para-CC-C6H4-CC]的末端而制成。我们也建议做一个“推拉”式的系统，其中一个电子捐赠组连接在一端，一个电子撤回组连接在另一端。这些替换将允许调整它们的性质和反应性