Monocoordinated carbon, boron and phosphorus species

单配位碳、硼和磷物种

• 批准号: 1954380
• 负责人: Guy Bertrand
• 金额: $ 51万
• 依托单位: University of California-San Diego
• 依托单位国家: 美国
• 项目类别: Standard Grant
• 财政年份: 2020
• 资助国家: 美国
• 起止时间: 2020-07-01 至 2023-06-30
• 项目状态: 已结题
• 来源: https://www.nsf.gov/awardsearch/showAward?AWD_ID=1954380&HistoricalAwards=false
• 关键词: Monocoordinated; carbon; boron; phosphorus; species

Carbon is the building material upon which the elements of life (DNA, RNA, etc.) are constructed. Carbon generally forms four chemical bonds. In this project funded by the Chemical Synthesis Program of the Chemistry Division, Professor Guy Bertrand of the Chemistry and Biochemistry Department at the University of California – San Diego (UCSD), seeks to prepare compounds that violate the four-bond rule. The isolation of such new carbon species has been impeded by the belief that they are inherently unstable. Professor Bertrand’s laboratory has recently developed new methods to prepare compounds called carbenes, which contain only two bonds to carbon. These methods are extended to carbynes, compounds in which carbon contains only a one bond. The availability of these species leads to better understanding of how chemical reactions of carbon take place, which then permits control of the reactivity of carbon-containing species. Ultimately, this research may help in the advanced manufacturing of chemicals and materials as researchers may develop more selective approaches to synthesis (fewer by-products). The Professor Bertran's laboratory collaborates with the French Le Centre National de la Recherche Scientifique (CNRS). The exchange of undergraduates and graduates between UCSD and CNRS-associated universities enables the students to develop an international perspective on chemical production and workforce development.The idea that monocoordinated carbon species may be isolable followed the discovery of amino substituents that mitigated the intrinsic tendency of carbenes to undergo dimerization and other reactions. Building on this idea, monocoordinated aminocarbanions (R2NC), aminocarbynes (R2NC), aminocarbocations (R2NC+), which feature six, five and four valence electrons, respectively, are prepared. Due to the importance of low coordinate main group compounds, aminophosphinidenes (R2NP) and aminoborylenes (R2NB), which are isoelectronic with the monocoordinated aminocarbanions and aminocarbocations, respectively, are synthesized. Some of the targeted species are non-isolable. Nonetheless, the pursuit of these high risk, high reward leads to new methodologies for in situ generated analogues. The fact that carbenes can simultaneously form two sigma bonds and monocoordinated compounds may form three opens a new model of chemical reactivity.This award reflects NSF's statutory mission and has been deemed worthy of support through evaluation using the Foundation's intellectual merit and broader impacts review criteria.

碳是生命元素（DNA，RNA等）的建筑材料。是建造的。碳通常形成四个化学键。在这个由化学系化学合成项目资助的项目中，加州大学圣地亚哥分校（UCSD）化学和生物化学系的Guy Bertrand教授试图制备违反四键规则的化合物。这种新的碳物种的分离一直受到人们认为它们本质上不稳定的阻碍。贝特朗教授的实验室最近开发出了制备卡宾化合物的新方法，这种化合物只含有两个碳键。这些方法被扩展到碳炔，其中碳只包含一个键的化合物。这些物种的可用性导致更好地理解碳的化学反应如何发生，然后允许控制含碳物种的反应性。 最终，这项研究可能有助于化学品和材料的先进制造，因为研究人员可能会开发出更具选择性的合成方法（更少的副产品）。 Bertran教授的实验室与法国国家科学研究中心（CNRS）合作。 UCSD和CNRS合作大学之间的本科生和研究生交流使学生能够对化学生产和劳动力发展形成国际视野。单配位碳物种可能是可分离的想法是在发现氨基取代基之后发现的，这些氨基取代基减轻了卡宾进行二聚化和其他反应的内在趋势。在此基础上，分别合成了具有6个、5个和4个价电子的单配位氨基碳负离子（R2NC）、氨基碳炔（R2NC）和氨基碳正离子（R2NC+）。由于低配位主族化合物的重要性，合成了分别与单配位氨基碳负离子和氨基碳正离子等电子的氨基膦（R2NP）和氨基硼（R2NB）。一些目标物种是不可分离的。尽管如此，追求这些高风险，高回报导致新的方法原位生成的类似物。卡宾可以同时形成两个σ键，单配位化合物可以形成三个σ键，这一事实开启了化学反应性的新模式。该奖项反映了NSF的法定使命，并通过使用基金会的知识价值和更广泛的影响审查标准进行评估，被认为值得支持。

项目成果

Stable Singlet Carbenes as Organic Superbases

作为有机超碱的稳定单线态卡宾

• DOI: 10.1002/anie.202111588
• 发表时间: 2021
• 期刊: Angewandte Chemie International Edition
• 作者: Vermersch, François;Yazdani, Sima;Junor, Glen P.;Grotjahn, Douglas B.;Jazzar, Rodolphe;Bertrand, Guy
• 通讯作者: Bertrand, Guy

An air-stable radical with a redox-chameleonic amide

具有氧化还原变色酰胺的空气稳定自由基

• DOI: 10.1039/d2cc05404c
• 发表时间: 2023
• 期刊: Chemical Communications
• 影响因子: 4.9
• 作者: Peltier, Jesse L.;Serrato, Melinda R.;Thery, Valentin;Pecaut, Jacques;Tomás-Mendivil, Eder;Bertrand, Guy;Jazzar, Rodolphe;Martin, David
• 通讯作者: Martin, David

Cyclic (amino)(barrelene)carbenes: an original family of CAACs through a novel synthetic pathway

环状（氨基）（桶烯）卡宾：通过新颖的合成途径形成的 CAAC 原始家族

• DOI: 10.1039/d2cc02565e
• 发表时间: 2022
• 期刊: Chemical Communications
• 影响因子: 4.9
• 作者: Serrato, Melinda R.;Melaimi, Mohand;Bertrand, Guy
• 通讯作者: Bertrand, Guy

An Air-Stable “Masked” Bis(imino)carbene: A Carbon-Based Dual Ambiphile

空气稳定的“掩蔽”双（亚氨基）卡宾：碳基双亲两性化合物

• DOI: 10.1021/jacs.2c12847
• 发表时间: 2023
• 期刊: Journal of the American Chemical Society
• 影响因子: 15
• 作者: Loh, Ying Kai;Melaimi, Mohand;Munz, Dominik;Bertrand, Guy
• 通讯作者: Bertrand, Guy