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

基本信息

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

项目摘要

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项目资助的项目中，加州大学圣地亚哥分校化学与生物化学系的 Guy Bertrand 教授将制备对磷衍生物合成至关重要的环境友好型构件。对于粮食生产以及乙醇、生物燃料和任何生物可再生化学品等其他农产品来说，磷的供应是一场迫在眉睫的危机，甚至比供应的减少更为严重。化石燃料，因为该元素不存在替代品，该项目的最终目标是促使当前的磷研究以及工业界转向更可持续的实践，其目的是规避传统的磷起始材料，例如三氯化磷。其转化为所需的化学品会产生大量废物，而且能源效率极低。 PI 的实验室是 UCSD 和法国 CNRS 的合资企业，旨在促进 UCSD 之间的本科生和研究生交流。和欧洲Universities.PCl3 具有一个磷中心，可被视为 P3+ 合成等价物。该项目的目的是开发稳定可持续的“P´”结构单元，包括 PN2´ 和 P3´，叠氮化物阴离子的含磷类似物。 (N3´)。通过与亲电子试剂 (E+) 反应，这些结构单元将产生高反应性的膦亚胺 (E-P)，包括其室温稳定版本。与卡宾等电子的单配位磷物质很容易转化为多种磷化合物，包括磷的人工同素异形体，“P´”合成等效物也将用于制备 RNP2 和 RP3，它们是二元和 RP3。叠氮衍生物的三磷类似物，以及重氮衍生物的二磷类似物 R2C=P2 这些化合物不仅充当。 1,3-偶极子允许制备各种磷杂环，但也将成为高反应性双核 P2 的发生器，该双核 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，因为该项目是该项目位于物理、有机、无机和有机金属化学的交叉点，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，也是他们的第一个。家庭获得本科学位。

项目成果

期刊论文数量（17）

专著数量（0）

科研奖励数量（0）

会议论文数量（0）

专利数量（0）

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

Borylenes: An Emerging Class of Compounds

DOI：
10.1002/anie.201705153
发表时间：
2017-08-21
期刊：
ANGEWANDTE CHEMIE-INTERNATIONAL EDITION
影响因子：
16.6
作者：
Soleilhavoup, Michele;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