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的实验室的Francois Mathee博士之间的合作研究。该项目的目标是准备和研究一种不寻常的、短暂的化学物种，一种名为亚膦的含磷分子。人们认为，这些分子将具有极其特殊的性质，对亚膦类化合物的研究将加深对化学反应基本原理的理解，并导致合成新类型的分子，包括一些生化兴趣。作为从头计算在金属有机化学中应用的基准，有必要比较具有理论预测的结构和机理的膦及其金属络合物的实际结构和详细的反应路径。研究人员计划进行一系列实验，包括合成空间受阻的膦-金属络合物，其热或光化学分解应形成足以进行直接光谱观察的亚膦-金属络合物。该项目将受益于两位研究人员互补的实验专业知识。马西博士和他的同事们在合成金属-膦络合物方面拥有丰富的经验，包括邻菲咯烷及其脱金属。加斯帕博士的实验室已经完善了主族氢化物的烷基化，以及相关三元环(如硅烷)的光化学和热分解。这个项目应该提供机会，开发新的路线，以获得有趣和有用的活性中间体，这些中间体到目前为止还没有得到详细的研究。膦系化合物在有机磷化合物的合成和旨在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希望。这项研究的结果可能会阐明有机化学的思想必须如何修改，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.