Monocoordinated carbon, boron and phosphorus species

单配位碳、硼和磷物种

基本信息

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

项目摘要

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.

碳是构成生命元素（DNA、RNA 等）的建筑材料，该项目由化学系的化学合成项目、化学系的 Guy Bertrand 教授资助。加州大学圣地亚哥分校 (UCSD) 生物化学系试图制备违反四键规则的化合物，但 Bertrand 教授的实验室认为它们本质上不稳定，因而阻碍了这种新碳物种的分离。最近开发了一种新方法来制备仅包含两个碳键的化合物，这些方法扩展到碳烯，即碳仅包含一个键的化合物。这些物质的可用性有助于更好地了解碳烯的化学反应。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（更少的副产物）。与法国实验室合作国家科学研究中心 (CNRS) 加州大学圣地亚哥分校和 CNRS 附属大学之间的本科生和研究生交流使学生能够培养化学生产和劳动力发展的国际视野。单配位碳物种可能是可分离的这一想法遵循了以下观点：发现氨基取代基可以减轻卡宾发生二聚化和其他反应的内在趋势，基于这一想法，单配位氨基碳负离子（R2NC）、氨基碳炔。由于低主配位化合物的重要性，制备了分别具有六价电子、五价电子和四价电子的氨基碳正离子(R2NC)、氨基碳正离子(R2NC+)、与单配位等电子的氨基膦亚膦(R2NP)和氨基硼烯(R2NB)。然而，一些目标物种是不可分离的，但追求这些高。风险、高回报导致了原位生成类似物的新方法。卡宾可以同时形成两个西格玛键，单配位化合物可以形成三个西格玛键，这一事实开启了化学反应的新模式。该奖项反映了 NSF 的法定使命，并被认为是值得的。通过使用基金会的智力优势和更广泛的影响审查标准进行评估来提供支持。

项目成果

期刊论文数量（5）

专著数量（0）

科研奖励数量（0）

会议论文数量（0）

专利数量（0）

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
影响因子：
0
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