Synthesis and Reactivity of Phosphatetrahedranes and Related Species: New Phosphaorganic Building Blocks

磷酸四面体及相关物种的合成和反应性：新的磷有机结构单元

• 批准号: 451444676
• 负责人: Professor Dr. Robert Wolf
• 金额: --
• 依托单位: Institut für Anorganische Chemie
• 依托单位国家: 德国
• 项目类别: Research Grants
• 资助国家: 德国
• 项目状态: 未结题
• 来源: https://gepris.dfg.de/gepris/projekt/451444676?language=en
• 关键词: Synthesis; Reactivity; Phosphatetrahedranes; Related; Species

Tetrahedranes are highly strained and reactive organic molecules comprised of four carbon at-oms in a tetrahedral arrangement. They have been of considerable interest due to their scarcity and increased reactivity resulting from high bond strain. Due to the difficulty of isolating such species the tetrahedrane family is limited, and neutral heteroatomic tetrahedranes were almost unknown until very recently. The synthesis of di-tert-butyldiphosphatetrahedrane, (tBuCP)2, re-ported by our group in late 2019, and the report of tri-tert-butylphosphatetrahedrane, (tBuC)3P by C. C. Cummins and co-workers in March 2020 have opened exciting opportunities in this previ-ously dormant research field. This project will systematically study the chemistry of the phosphatetrahedranes to understand their synthesis, chemical properties and reactivity. This will open a path toward their utilization as versatile building blocks for phosphaorganic and phosphaorgan-ometallic compounds. The investigations will focus on the isolation of a wider variety of phosphatetrahedranes, followed by the study of their interaction toward fundamental reagents such as electrophiles, nucleophiles and reducing agents, and their coordination chemistry with transition metals. The project particularly focusses on the chemistry of diphosphatetrahedranes, but the synthesis of related mono- and triphosphatetrahedranes is likewise investigated. In particular, we intend to compare the behavior of the new family of phosphatetrahedranes with that of the most relevant inorganic tetrahedrane known to date, white phosphorus (P4). It is anticipated that the fundamental investigations proposed in this project will deliver a profound understanding of the chemistry of phosphatetrahedranes. In addition, this will lay the ground for the discovery of further unusual organophosphorus compounds.

四面体烷是由四面体排列的四个碳原子组成的高度应变和反应性的有机分子。由于它们的稀缺性和高键应变导致的反应性增加，它们受到了相当大的关注。由于分离这些物种的困难，四面体烷家族是有限的，中性杂原子四面体烷几乎是未知的，直到最近。本课题组于2019年下半年报道了二叔丁基二磷杂四面体（tBuCP）2的合成，C. C. 2020年3月，康明斯及其同事在这个以前处于休眠状态的研究领域开辟了令人兴奋的机会。本项目将系统地研究磷杂四面体的化学，以了解其合成，化学性质和反应性。这将开辟一条道路，他们的利用作为多功能的建筑砌块的磷有机和磷有机化合物。调查将集中在更广泛的各种磷杂四面体的分离，其次是他们对基本试剂，如亲电试剂，亲核试剂和还原剂的相互作用的研究，及其与过渡金属的配位化学。该项目特别侧重于双磷杂四面体的化学，但相关的单磷杂四面体和三磷杂四面体的合成也同样进行了研究。特别是，我们打算比较的行为的新家庭的磷四面体与最相关的无机四面体已知的日期，白色磷（P4）。预计在这个项目中提出的基础研究将提供一个深刻的理解磷四面体的化学。此外，这将为发现更多不寻常的有机磷化合物奠定基础。