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: 2019
• 资助国家: 加拿大
• 起止时间: 2019-01-01 至 2020-12-31
• 项目状态: 已结题
• 来源: https://www.nserc-crsng.gc.ca/ase-oro/Details-Detailles_eng.asp?id=683706
• 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.*********

化合物性质的改变可以通过仔细选择取代基，即连接到母体结构上的基团来实现。在众多的取代基中，氨基由于其强的π-供体性质，在需要更富电子的母体结构的应用中使用最多。我们最近已经证明，与普遍认为氨基是首要的π-供体取代基相反，亚氨基磷酰基取代基（R3 P =N-）在这方面甚至更强。我们利用这一特性来制备最强大的中性有机电子供体，其作为均相还原剂。作为金属基试剂的补充，此类有机还原剂有望实现替代反应途径、更温和的条件和更少的环境负荷。然而，底物范围有限，许多金属试剂的还原强度大大超过最好的有机还原剂的可能性。该提议将通过开发新的亚氨基膦酰基取代基以及应该是极好的π-供体的其他取代基（亚氨基磺酰基和亚甲基膦酰基）来扩展我们的工作。将确定这些取代基的哈米特常数，允许根据它们的π-供体性质对它们进行排序。虽然这些信息对所有学科的化学家都有价值，但我们将在开发最强大的有机还原剂时利用最强的捐赠取代基。这将为使用更温和的条件减少日益具有挑战性的底物打开大门。因此，将开发新的合成工艺。* 作为本研究计划的第二个方面，我们已经制备的强还原性有机化合物，以及我们在这里的目标，将作为有机氧化还原液流电池的阳极材料进行研究。这种氧化还原液流电池被认为是大规模储能的有前途的候选者，包括存储可再生能源以与电网集成。将有机材料作为活性物种而不是金属基化合物的研究是该技术的新研究途径，但目前缺乏低潜力材料。我们的化合物，加上现成的有机阴极材料，将在有机氧化还原液流电池中进行测试，目标是开发具有更高电池电压和能量密度的系统。