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

美法合作研究：新型游离膦亚胺和膦亚胺-金属配合物的生成、结构表征和化学

• 批准号: 8914578
• 负责人: Peter Gaspar
• 金额: $ 0.78万
• 依托单位: Washington University
• 依托单位国家: 美国
• 项目类别: Standard Grant
• 财政年份: 1990
• 资助国家: 美国
• 起止时间: 1990-03-15 至 1993-12-31
• 项目状态: 已结题
• 来源: https://www.nsf.gov/awardsearch/showAward?AWD_ID=8914578&HistoricalAwards=false
• 关键词: US; France; Cooperative; Research; Generation

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.

该奖项将支持博士之间的合作研究。 彼得·加斯帕，华盛顿大学和弗朗索瓦博士 Mathey，Phosphere化学和金属化学公司 过渡，帕莱索，法国。 该项目的目标 是准备和研究一个不寻常的，短暂的 化学物种，一种含磷分子， 次膦。 据信，这些分子将具有 这是一种非常不寻常的性质， 丹尼斯将进一步了解基本原则， 化学反应性，以及导致合成 新型分子，包括一些生物化学的兴趣。 作为从头计算应用的基准 在有机金属化学中，有必要比较 膦酰亚胺的实际结构和详细反应路径 和它们的金属配合物， 结构和机制。 调查人员计划进行 进行了一系列的实验，包括合成一种 空间位阻膦-金属配合物，其热稳定性 或光化学分解应该形成亚膦基， 金属络合物的寿命足够长， 观察. 该项目将受益于互补的 两名研究人员的实验经验。 马希博士 他和他的同事在这方面有着丰富的经验， 金属-膦络合物，包括磷杂菲的合成 和他们的种族灭绝 加斯帕博士的实验室 完善了主体基团的金刚烷化， 光化学以及热分解有关 三元环如硅烷。 这个项目应该 提供开发新路线的机会， 和有用的活性中间体， 详细研究。 膦酰亚胺具有很大的希望， 有机磷化合物的合成， 旨在加强反应控制的机理研究 电子结构的细微变化。 结果 这项研究可能会澄清有机的想法是如何 化学必须被修改以处理键的形成， 第一行以下的周期性断裂现象 表.