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.

碳是建造生命元素（DNA，RNA等）的建筑材料。碳通常形成四种化学键。在化学部化学合成计划资助的该项目中，加利福尼亚大学圣地亚哥分校（UCSD）的化学和生物化学系的盖伊·贝特兰德教授旨在准备违反四个基准规则的化合物。这种新碳物种的隔离受到了这样一种信念，即它们本质上是不稳定的。伯特兰教授的实验室最近开发了新的方法来制备称为碳纤维的化合物，该化合物仅包含两种碳。这些方法扩展到Carbynes，其中碳仅包含一个键的化合物。这些物种的可用性可以更好地理解碳的化学反应如何发生，从而可以控制含碳物种的反应性。最终，这项研究可能有助于化学和材料的高级制造，因为研究人员可能会开发出更多选择性的合成方法（副产品较少）。 Bertran教授的实验室与法国Le Center National de La Recherche Scientifique（CNRS）合作。 UCSD和与CNRS相关大学之间的本科生和毕业生的交流使学生能够开发出关于化学生产和劳动力发展的国际观点。在发现氨基亚物种可能会发现氨基材料的情况下，可以分离出碳含量的碳种类，从而减轻了Carbones的固有趋势，从而使carbone敏感既不及格化，从而使carbone ysimentions nistions cocbones nostions coctions coctions coctions nationge de Recionsions和其他杂物化。在这个想法的基础上，分别以六个，五和四价电子为基础，单核协调的氨基氨基裂（R2NC），Aminocarbynes（R2NC），Aminocarbocations（R2NC+）。由于低坐标主要组化合物的重要性，氨基磷酸烯（R2NP）和氨基居烯（R2NB）分别构成了等质激素，分别是单核协调的amokabaranions和aminoakarbocations。一些靶向物种是非分离的。尽管如此，追求这些高风险，高奖励为原位产生的类似物带来了新的方法。碳纤维可以轻松地形成两种sigma债券和单核化合物的事实可能会形成三种化学反应性的新模型。该奖项反映了NSF的法定任务，并通过使用该基金会的智力优点和更广泛的影响来诚实地认为，通过评估诚实地支持了审查标准。

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