Stable synthetic equivalents of the monophosphorus anion (P-): a clean substitute for PCl3

一磷阴离子 (P-) 的稳定合成等价物：PCl3 的清洁替代品

• 批准号: 1661518
• 负责人: Guy Bertrand
• 金额: $ 49.5万
• 依托单位: University of California-San Diego
• 依托单位国家: 美国
• 项目类别: Continuing Grant
• 财政年份: 2017
• 资助国家: 美国
• 起止时间: 2017-07-01 至 2020-06-30
• 项目状态: 已结题
• 来源: https://www.nsf.gov/awardsearch/showAward?AWD_ID=1661518&HistoricalAwards=false
• 关键词: Stable; synthetic; equivalents; monophosphorus; anion

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, will prepare environmentally benign building blocks for the synthesis of phosphorus derivatives. Phosphorus is vital not only for food production but also for other agricultural commodities such as ethanol, biofuels, and any biorenewable chemicals. Phosphorus availability is a looming crisis even more severe than dwindling supplies of fossil fuels, simply because no alternative for this element exists. The ultimate goal of this project is to induce a shift in current phosphorus research, and hopefully industry, toward more sustainable practices. The aim is to circumvent traditional phosphorus starting materials, such as PCl3, whose transformation into the desired chemicals produces an enormous amount of waste as well as being extremely energy-inefficient. 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.PCl3 features a phosphorus center, which can be viewed as a P3+ synthetic equivalent. The aim of this project is to develop stable sustainable "P¯" building blocks, including PN2¯ and P3¯, phosphorus-containing analogues of the azide anion (N3¯). Through reaction with electrophiles (E+), these building blocks will lead to highly reactive phosphinidenes (E-P), including their room temperature stable version. This monocoordinated phosphorus species, isoelectronic with carbenes, will readily be transformed into a broad range of phosphorus compounds, including artificial allotropes of phosphorus. The "P¯" synthetic equivalents will also be used for the preparation of RNP2 and RP3, which are di- and tri-phosphorus analogues of azido derivatives, as well as R2C=P2 which are diphosphorus analogues of diazo derivatives. These compounds will not only act as 1,3-dipoles allowing for the preparation of a variety of phosphorus heterocycles, but will also be generators of the highly reactive dinuclear P2, which will be chemically trapped. The broader impacts of this work include potential societal benefits, and since this project is at the interface between physical, organic, inorganic and organometallic chemistry, it is well suited to the education of chemists at all levels. This project will contribute to the education of four Graduate Students, three of whom are minorities, and the first of their family to earn an undergraduate degree.

在这个由化学系化学合成计划资助的项目中，加州大学圣地亚哥分校化学和生物化学系的盖伊·贝特朗教授将为合成磷衍生物准备环境友好的积木。磷不仅对粮食生产至关重要，而且对乙醇、生物燃料和任何生物可再生化学品等其他农产品也是至关重要的。磷的可获得性是一场迫在眉睫的危机，甚至比化石燃料供应减少更严重，原因很简单，因为这种元素别无选择。该项目的最终目标是促使当前的磷研究--希望是工业--转向更可持续的实践。其目的是绕过传统的磷原料，如PCl3，这些原料转化为所需的化学品会产生大量浪费，而且能源效率极低。PI的实验室是加州大学圣地亚哥分校和法国CNRS的合资企业。它旨在促进加州大学圣迭戈分校和欧洲大学之间的本科生和毕业生的交流。PCl3的特点是一个磷中心，可以被视为P3+的合成等价物。该项目的目的是开发稳定、可持续的“P”积木，包括叠氮阴离子(N3)的含磷类似物PN2和P3。通过与亲电体(E+)的反应，这些构件将产生高活性的膦(E-P)，包括它们的室温稳定版本。这种与卡宾等电子的单配位磷物种很容易转化为广泛的磷化合物，包括人造磷的同素异形体。“P”合成的等价物还将用于制备RNP2和RP3，它们是叠氮衍生物的二磷和三磷类似物，以及R2C=P2，它们是重氮衍生物的二磷类似物。这些化合物不仅将作为1，3-偶极，允许制备各种磷杂环，而且还将成为高活性双核P2的生成器，该P2将被化学捕获。这项工作的更广泛影响包括潜在的社会效益，由于该项目处于物理化学、有机化学、无机化学和有机金属化学的交界处，因此非常适合各级化学家的教育。该项目将有助于四名研究生的教育，其中三名是少数民族，也是他们家庭中第一个获得本科学位的人。

项目成果

Transition-Metal-like Behavior of Main Group Elements: Ligand Exchange at a Phosphinidene

• DOI: 10.1021/jacs.6b11496
• 发表时间: 2016-12-14
• 期刊: JOURNAL OF THE AMERICAN CHEMICAL SOCIETY
• 影响因子: 15
• 作者: Hansmann, Max M.;Bertrand, Guy
• 通讯作者: Bertrand, Guy

The serendipitous discovery of a readily available redox-bistable molecule derived from cyclic(alkyl)(amino)carbenes

偶然发现一种易于获得的源自环状（烷基）（氨基）卡宾的氧化还原双稳态分子

• DOI: 10.1039/c8qo00447a
• 发表时间: 2018
• 期刊: Organic Chemistry Frontiers
• 影响因子: 5.4
• 作者: Mahoney, Janell K.;Regnier, Vianney;Romero, Erik A.;Molton, Florian;Royal, Guy;Jazzar, Rodolphe;Martin, David;Bertrand, Guy
• 通讯作者: Bertrand, Guy

Organic Mixed Valence Compounds Derived from Cyclic (Alkyl)(amino)carbenes

• DOI: 10.1021/jacs.7b11184
• 发表时间: 2018-02-14
• 期刊: JOURNAL OF THE AMERICAN CHEMICAL SOCIETY
• 影响因子: 15
• 作者: Hansmann, Max M.;Melaimi, Mohand;Bertrand, Guy
• 通讯作者: Bertrand, Guy

The Advantages of Cyclic Over Acyclic Carbenes To Access Isolable Capto-Dative C-Centered Radicals

• DOI: 10.1002/chem.201700144
• 发表时间: 2017-05-02
• 期刊: CHEMISTRY-A EUROPEAN JOURNAL
• 影响因子: 4.3
• 作者: Mahoney, Janell K.;Jazzar, Rodolphe;Bertrand, Guy
• 通讯作者: Bertrand, Guy

A crystalline monosubstituted carbene

结晶单取代卡宾

• DOI: 10.1038/s41557-018-0153-1
• 发表时间: 2018
• 期刊: Nature Chemistry
• 影响因子: 21.8
• 作者: Nakano, Ryo;Jazzar, Rodolphe;Bertrand, Guy
• 通讯作者: Bertrand, Guy