Tuning the Reactivity of ortho-, meta- and para- Benzyne Analogs and Releated Polyradicals in the Gas Phase

调节邻位、间位和对位苯炔类似物及相关多自由基在气相中的反应性

• 批准号: 1152379
• 负责人: Hilkka Kenttamaa
• 金额: $ 55万
• 依托单位: Purdue University
• 依托单位国家: 美国
• 项目类别: Continuing Grant
• 财政年份: 2012
• 资助国家: 美国
• 起止时间: 2012-07-01 至 2015-06-30
• 项目状态: 已结题
• 来源: https://www.nsf.gov/awardsearch/showAward?AWD_ID=1152379&HistoricalAwards=false
• 关键词: Tuning; Reactivity; ortho; meta; para

Experimental reactivity studies on organic bi- and polyradicals are hindered by the difficulty of generating them cleanly in solution, in addition to their high reactivity and short lifetime. Information on the factors that control the chemical properties of carbon-centered sigma-type biradicals, such as the benzynes and their analogs, is highly desirable since it may allow one to "tune" their reactivity by varying structural details, and hence design bi- and polyradicals with tailored properties. This research program uses the "distonic ion approach" to study the reactivity of gaseous, carbon-centered, sigma-type mono-, bi- and triradicals via their charged analogs by using Fourier-transform ion cyclotron resonance mass spectrometers, a flowing afterglow quadrupole-octapole-quadrupole apparatus, and most recently, a linear quadrupole ion trap. These studies have demonstrated that the electron affinity and singlet-triplet gap of biradicals, as well as dehydrocarbon atom separation for meta-benzyne analogs, are among the reactivity controlling factors that can be used to "tune" the reactivity of some of these species. However, only few different ortho- and meta-benzyne analogs, and most remarkably, no para-benzyne analogs, have been studied thus far. Hence, this research will now be extended to several different and differently substituted ortho- and meta-benzyne analogs. With the means to generate para-benzyne analogs in the gas phase, an examination of their reactions is planned. Finally, the factors that control the reactivity of related tri- and tetraradicals will also be explored.The ability to predict, control and rationalize the outcomes of chemical reactions frequently requires knowledge of key reaction intermediates. Aromatic compounds that carry one (monoradicals) or more unpaired electrons (polyradicals) play an important role, for example, in organic synthesis and the biological activity of organic compounds. This research focuses on improving fundamental understanding of the chemical properties of these reactive intermediates. Ultimately, this research will lead to improved methods to synthesize new organic compounds, including drugs and new materials, as well as more rational design of new drugs. The new experimental methodologies developed here for the characterization of reaction intermediates will have an impact on experimental physical and physical organic chemistry. The broader societal impacts and enhancement of infrastructure include a large number of ethnically diverse, highly qualified science Ph.D. candidates, improved methodology for chemical analysis of organic compounds (including petroleum), and a more solid knowledge base for the design and synthesis of new organic materials and drugs.

除了高反应性和短寿命之外，难以清洁的溶液中，对有机双重自由基和多性自由基的实验反应性研究也阻碍了它们。关于控制以碳为中心的Sigma型Biradicals（例如Benzynes及其类似物）的化学性质的因素的信息是非常可取的，因为它可以使人们可以通过不同的结构细节来“调音”其反应性，因此，双性恋和在政治上都设计了双性恋和量身定制的特性。该研究计划使用“宽敞的离子方法”来研究气体，以碳为中心的，以碳为中心的，sigma型单，双位和三位生的反应性，通过使用傅里叶转基因环形共振仪（一种流动的二氮蛋白酶），近来的二十杆和大多数luup luup saperrup coodraul coodraul prockrat coodraul prockrAup coolant and coodraul prockration and coodraul saperration and coodrant and coodrant and coodrant and procerant and coodrant and procerant和 陷阱。这些研究表明，Biradicals的电子亲和力和单细胞间隙以及元苯甲基类似物的脱氢碳原子分离是可用于“调节”这些物种的反应性的反应性控制因子之一。然而，到目前为止，只有很少的不同的和元苯并类似物，最引人注目的是，尚无para-benzyne类似物。因此，这项研究现在将扩展到几种不同且替代不同的邻苯式和元苯并类似物。有了在气相中产生苯并类似物的手段，计划检查其反应。最后，还将探索控制相关三位形和四方反应性的因素。预测，控制和合理化化学反应结果的能力经常需要了解关键反应中间体的知识。携带一种（单个自由基）或更多未配对电子（多性自由基）的芳香化合物在有机合成和有机化合物的生物学活性中起着重要作用。这项研究重点是提高对这些反应性中间体化学特性的基本理解。最终，这项研究将导致改进的方法来综合新的有机化合物，包括药物和新材料，以及更合理的新药设计。此处开发的用于表征反应中间体的新实验方法将对实验性物理和物理有机化学产生影响。更广泛的社会影响和基础设施的增强包括大量多样化的高素质科学博士学位。候选者，改进的有机化合物化学分析的方法（包括石油），以及设计和合成新有机材料和药物的更坚实的知识库。