US-France Cooperative Research: Generation, Structural Characterization, and Chemistry of New Free Phosphinidenes and Phosphinidene-Metal Complexes

该奖项将支持华盛顿大学的Peter P. Gaspar博士和法国Palaiseau的Phosphere Chimie and des Metaux de Transition实验室的Francois Mathey博士之间的合作研究。该项目的目的是制备和研究一种不寻常的、寿命短的化学物质，一种叫做膦烯的含磷分子。相信这些分子将具有极其不寻常的性质，对膦烯的研究将进一步加深对化学反应基本原理的理解，并导致新分子的合成，包括一些生物化学的兴趣。作为从头计算在有机金属化学中应用的基准，需要将膦酸酯及其金属配合物的实际结构和详细反应路径与理论预测的结构和机理进行比较。研究人员计划进行一系列的实验，包括合成一种立体受阻的膦-金属配合物，其热化学或光化学分解应形成一个足够长寿命的膦-金属配合物，以便进行直接的光谱观察。该项目将受益于两位研究者的互补实验专业知识。Mathey博士和他的同事在金属-膦配合物的合成方面有相当丰富的经验，包括酞和它们的脱金属。加斯帕博士的实验室已经完善了主基团氢化物的金刚烷化，以及硅烷等相关三元环的光化学和热分解。这个项目应该提供机会，开发新的路线，以有趣和有用的反应中间体，迄今为止还没有详细的研究。膦烯类化合物在有机磷化合物的合成和通过电子结构的细微变化来增加对反应途径的控制的机理研究方面都有很大的前景。这项研究的结果可能会澄清如何修改有机化学的思想，以处理元素周期表第一行以下的成键和断键现象。

This award will support collaborative research between Dr. Peter P. Gaspar, Washington University and Dr. Francois Mathey, Laboratoire de Chimie du Phosphere et des Metaux de Transition, Palaiseau, France. The objective of the project is the preparation and study of an unusual, short-lived chemical species, a phosphorus-containing molecule called phosphinidene. It is believed that these molecules will have extremely unusual properties and that the study of phosphini- denes will further the understanding of fundamental principles of chemical reactivity, as well as lead to the synthesis of new kinds of molecules, including some biochemical interest. As a benchmark for the applications of ab initio calculations in organometallic chemistry, there is a need to compare the actual structures and detailed reaction paths of phosphinidenes and their metal complexes with theoretically predicted structures and mechanisms. The investigators plan to carry out a series of experiments to include the synthesis of a sterically hindered phophirane-metal complex, whose thermal or photochemical decomposition should form a phosphinidene- metal complex sufficiently long-lived for direct spectroscopic observation. This project will benefit from the complementary experimental expertise of the two investigators. Dr. Mathey and his colleagues have considerable experience in the synthesis of metal-phosphine complexes, including phophiranes and their demetallation. Dr. Gaspar's laboratory has perfected the adamantylation of main group hydrides and the photochemical as well as thermal decomposition of related three-membered rings such as siliranes. This project should provide the opportunity to develop new routes to interesting and useful reactive intermediates that have thus far eluded detailed study. Phosphinidenes hold great promise both for the synthesis of organophosphorus compounds and for the mechanistic studies aimed at increasing control of reaction pathways by subtle changes in electronic structures. Results of this research may clarify how the ideas of organic chemistry must be modified to deal with bond-making and bond-breaking phenomena below the first row of the periodic table.