Isolation of an elusive phosphatetrahedrane

摘要

This exploratory synthesis investigation was undertaken to determine the viability of replacing a single carbon vertex with another p-block element in a highly strained tetrahedrane molecule. Phosphorus was selected for this purpose because the stable molecular form of elemental phosphorus is tetrahedral. Our synthetic strategy was to generate an unsaturated phosphorus center bonded to a substituted cyclopropenyl group, a situation that could lead to closure to provide the desired phosphatetrahedrane framework. This was accomplished by dehydrofluorination of the in situ generated fluorophosphine H(F)P(C supt/sup Bu)sub3/sub. Tri- tert -butyl phosphatetrahedrane, P(C supt/sup Bu)sub3/sub, was then isolated in 19% yield as a low-melting, volatile, colorless solid and characterized spectroscopically and by a single-crystal x-ray diffraction study, confirming the tetrahedral nature of the molecule’s PCsub3/sub core. The molecule exhibits unexpected thermal stability.