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

四面体是由四面体排列的四个碳原子组成的高度应变和活性有机分子。由于它们的稀缺性和由于高键应变而增加的反应性，它们引起了相当大的兴趣。由于分离这些物种的困难，四面体家族是有限的，中性杂原子四面体几乎是未知的，直到最近。我们小组在2019年底报道的二叔丁基二磷酸四面体烷（tBuCP）2的合成，以及C. C. Cummins及其同事在2020年3月报道的三叔丁基磷酸四面体烷（tBuC）3P的合成，为这个之前休眠的研究领域开辟了令人兴奋的机会。本项目将系统研究磷酸四面体烷的化学性质，了解其合成、化学性质和反应性。这将为它们作为磷有机化合物和磷有机金属化合物的通用构建块开辟一条道路。研究将集中于分离更多种类的磷酸四面体，随后研究它们与基本试剂（如亲电试剂、亲核试剂和还原剂）的相互作用，以及它们与过渡金属的配位化学。该项目特别侧重于二磷酸四面体烷的化学反应，但也研究了相关的单磷酸和三磷酸四面体烷的合成。特别是，我们打算比较新的磷酸盐四面体烷家族与迄今为止已知的最相关的无机四面体，白磷的行为（P4）。预计本项目提出的基础研究将对磷酸四面体的化学性质提供深刻的理解。此外，这将为发现更多不寻常的有机磷化合物奠定基础。

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.