Ylidic Substituents for Electron Rich Organic Materials with Synthetic and Energy Storage Applications

富电子有机材料的Ylidic取代基及其合成和储能应用

• 批准号: RGPIN-2016-04279
• 负责人: Dyker, CAdam
• 金额: $ 2.19万
• 依托单位: University of New Brunswick
• 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=709073
• 关键词: Ylidic; Substituents; Electron; Rich; Organic

Modification of the properties of a compound can be achieved by careful selection of the substituents, the groups attached to the parent structure. Among the multitude of substituents, amino groups, by virtue of their strong pi-donating properties, have been the most heavily used in applications where a more electron rich parent structure is required. We have recently demonstrated that, in contrast to the widespread belief that amino groups are the premier pi-donor substituent, iminophosphorano substituents (R3P=N-) are even stronger in this regard. We exploited this property to prepare the most powerful neutral organic electron donors, which act as homogeneous reducing agents. In complementarity to metal-based reagents, such organic reducing agents hold the promise of allowing for alternate reaction pathways, more mild conditions, and less environmental load. Nevertheless, substrate scope is limited and the reducing strength of many metal reagents greatly surpasses what is possible with the best organic reductants. This proposal will extend our work by developing new iminophospohrano substituents, as well as other substituents (iminosulfurao, and methylenephosphorano) that should be superb pi-donors. Hammett constants for these substituents will be determined, allowing for them to be ranked according to their pi-donor properties. While this information will be of value to chemists of all disciplines, we will utilize the most strongly donating substituents in the development of the most powerful organic reducing agents. This should open the door to the reduction of increasingly challenging substrates using milder conditions. New synthetic processes will thus be developed. As a second aspect of this research program, the strongly reducing organic compounds that we have already prepared, and that we target here, will be investigated as anode materials in organic redox flow batteries. Such redox flow batteries are regarded as promising candidates for large scale energy storage, including the storage of renewable energy for integration with power grids. The investigation of organic materials as active species, rather than metal-based compounds, is a new avenue of research for this technology, but currently there is a lack of low potential materials. Our compounds, coupled with readily available organic cathode materials, will be tested in organic redox flow batteries with the goal of developing systems with increased cell voltages and energy densities.

可以通过仔细选择取代基，附加到母体结构的组来修改化合物的性质。在众多取代基中，氨基群体由于其强大的pi腐蚀特性，已成为需要更丰富电子母体结构的应用中使用的。我们最近证明，与普遍认为氨基群是氨基群是最重要的pi-donor取代基的相反，在这方面，亚米磷酸化取代基（R3P = n-）甚至更强。我们利用了该特性来准备最强大的中性有机电子供体，这些供体是均质减少剂的。在与金属基因试剂的互补性中，这种有机还原剂有望允许替代反应途径，更轻微的条件和较小的环境负荷。然而，底物范围有限，许多金属试剂的降低强度极大地超过了最佳的有机还原剂。 该提议将通过开发新的iminophrano取代基，以及其他应该是极好的pi-donors来扩展我们的工作。将确定这些取代基的Hammett常数，从而使它们根据其pi-donor属性进行排名。尽管这些信息对所有学科的化学家都具有价值，但我们将利用最强大的取代基来开发最强大的有机还原剂。这应该为使用温和条件减少越来越具有挑战性的底物打开大门。因此，将开发新的合成过程。 作为该研究计划的第二个方面，我们已经准备好了有机化的有机化合物，并且我们在这里瞄准了有机氧化还原流量电池中的阳极材料。这种氧化还原流量电池被认为是大规模存储的有前途的候选人，包括将可再生能源与电网集成。对有机材料作为活性物种而不是金属化合物的研究是该技术研究的新途径，但目前缺乏潜在的材料。我们的化合物以及随时可用的有机阴极材料将在有机氧化还原流量电池中进行测试，目的是开发具有增加细胞电压和能量密度的系统。