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

在这个由化学部化学合成计划资助的项目中，加州大学圣地亚哥分校化学与生物化学系的Guy Bertrand教授将为合成磷衍生物准备对环境无害的构建模块。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至关重要。磷的可用性是一个迫在眉睫的危机，甚至比化石燃料供应减少更严重，原因很简单，因为这种元素没有替代品。这个项目的最终目标是促使目前的磷研究转向更可持续的做法，希望工业也是如此。其目的是绕过传统的磷起始材料，如PCl3，将其转化为所需的化学物质会产生大量的废物，而且能源效率极低。PI实验室是加州大学圣地亚哥分校和法国国家科学研究中心的合资企业。它旨在促进加州大学圣地亚哥分校与欧洲大学之间的本科生和研究生交流。PCl3具有磷中心，可视为P3+的合成等价物。该项目的目的是开发稳定可持续的“P¯”构建块，包括PN2¯和P3¯，氮化阴离子（N3¯）的含磷类似物。通过与亲电试剂（E+）的反应，这些构建块将生成高活性的磷脂（E- p），包括室温稳定的版本。这种单配位的磷与碳烯等电子，很容易转化为各种各样的磷化合物，包括磷的人工同素异形体。“P¯”合成等价物也将用于制备叠氮衍生物的二磷和三磷类似物RNP2和RP3，以及重氮衍生物的二磷类似物R2C=P2。这些化合物不仅可以作为1,3偶极子，用于制备各种磷杂环，而且还可以产生高活性的双核P2，它将被化学捕获。这项工作的广泛影响包括潜在的社会效益，并且由于该项目处于物理，有机，无机和有机金属化学之间的界面，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，他们是家庭中第一个获得本科学位的人。

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.