Highly Electron-Deficient Carbon, Boron and Silicon Compounds

高度缺电子的碳、硼和硅化合物

• 批准号: 2246948
• 负责人: Guy Bertrand
• 金额: $ 55万
• 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: 2023
• 资助国家: 美国
• 起止时间: 2023-07-01 至 2026-06-30
• 项目状态: 未结题
• 来源: https://www.nsf.gov/awardsearch/showAward?AWD_ID=2246948&HistoricalAwards=false
• 关键词: Highly; Electron; Deficient; Carbon; Boron

With support from the Chemical Synthesis Program of the Chemistry Division, Professor Guy Bertrand of the Department of Chemistry and Biochemistry at the University of California – San Diego, is studying highly electron-deficient carbon, boron and silicon compounds. Usually atoms such as carbon, boron, and silicon contain a full octet, i.e. are surrounded by eight electrons when they form compounds with other atoms. This project seeks to isolate species that only possess 4 or 5 surrounding electrons. The isolation such compounds has been impeded by the belief that they are inherently unstable. However, by attaching groups that are specially designed to stabilize electron deficiencies stable compounds with these very low electron counts will be prepared. The availability of these stable versions provides a better understanding of chemical reaction mechanisms and opens the way for new applications. As an example, carbon compounds with six-valence electrons have become powerful tools in chemistry and have found medicinal and material science applications. This project will prepare carbon, silicon and boron with as few as four valence electrons. Although the work is fundamental in nature, the resulting species will certainly find a plethora of applications and benefit society at large. The laboratory of the PI is a joint venture between UCSD and the French CNRS. It serves to promote the exchange of undergraduates and graduates between UCSD and European Universities. The recent isolation of a monsubstituted carbene, namely an aminocarbene (R2NCH), demonstrates that an amino substituent can tame the intrinsic instability of a six-electron species. Therefore, the Bertrand team believes that using this principle compounds featuring a main-group element with only five- and even four-valence electrons can be isolated. Monocoordinated carbon compounds, namely amino carbynes (R2NC:●) and amino carbocations (R2NC:+), as well as the isoelectronic borylene radical anions (R2NB:●-) and borylenes (R2NB:) will be prepared. Apart from monocoordinate systems, dicoordinate carbon radical cations (R2C+●) and carbodications (R2C++), which also feature only five and four valence-electrons around the carbon atom and are the one and two electron oxidized forms of a carbene, respectively, are also being targeted. Once these electron-deficient species are in hand, their synthetic utility will be explored. As an illustration, carbodications R2C++ could find applications as strong Lewis acids, including in frustrated Lewis pair chemistry. This project which is at the nexus of physical, organic, inorganic and organometallic chemistry is well suited to the education of chemists at all levels.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.

在化学部化学综合计划的支持下，加利福尼亚大学化学和生物化学系的盖伊·贝特兰教授 - 圣地亚哥大学正在研究高度电子缺陷的碳，硼和硅化合物。通常，诸如碳，硼和硅等原子包含一个完整的八位位，即，当它们与其他原子形成化合物时，它们被八个电子包围。该项目试图隔离物种，仅包含4或5个周围电子。这种化合物的隔离受到了这样一种信念，即它们本质上是不稳定的。但是，通过连接经过专门设计的组，可以制备这些非常低的电子计数的稳定化合物稳定化合物。这些稳定版本的可用性为化学反应机制提供了更好的理解，并为新应用打开了道路。例如，具有六价电子的碳化合物已成为化学中有力的工具，并发现了医学和材料科学应用。该项目将准备碳，硅和硼，其中只有四个价电子。尽管这项工作本质上是基本的，但所产生的物种肯定会发现大量的应用和福利社会。 PI的实验室是UCSD和法国CNR之间的合资企业。它有助于促进UCSD和欧洲大学之间的本科生和毕业生的交流。最近分离的莫纳抗碳烯，即氨基酸（R2NCH），表明氨基取代可以驯服六电子物种的内在不稳定。因此，Bertrand团队认为，使用该原理化合物具有一个只有五个甚至四价电子的主组元素。单核协调的碳化合物，即氨基Carbynes（R2NC：●）和氨基碳酸化合物（R2NC：+），以及等纤维型borylene自由基阴离子（R2NB：● - ）和Borylenes和Borylenes（R2NB）（R2NB :)将准备好。除了单位坐标系统外，在碳原子周围仅具有五个和四个价值电子的碳自由基阳离子（R2C+●）和碳染色（R2C ++）（R2C ++），分别是碳原子周围的五个和四个价值电子，分别是碳烯的一种和两种电子氧化物形式。一旦这些电子缺陷物种掌握在手头，将探索它们的合成效用。作为例证，CarboDications R2C ++可以找到用作强刘易斯酸的应用，包括在沮丧的刘易斯对化学中。该项目与物理，有机，无机和有机化学的联系非常适合各个级别的化学家教育。该奖项反映了NSF的法定任务，并通过基金会的智力优点和更广泛的影响来评估NSF的法定任务。

项目成果

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

A crystalline doubly oxidized carbene

结晶双氧化卡宾

• DOI: 10.1038/s41586-023-06539-x
• 发表时间: 2023
• 期刊: Nature
• 影响因子: 64.8
• 作者: Loh, Ying Kai;Melaimi, Mohand;Gembicky, Milan;Munz, Dominik;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