Isolation of an elusive phosphatetrahedrane

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 tetrah...

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Bibliographic Details
Main Authors: Riu, Martin-Louis Y., Jones, Rebecca L., Transue, Wesley, Müller, Peter, Cummins, Christopher C
Other Authors: Massachusetts Institute of Technology. Department of Chemistry
Format: Article
Language:English
Published: American Association for the Advancement of Science (AAAS) 2020
Online Access:https://hdl.handle.net/1721.1/127739
Description
Summary: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(CtBu)3. Tri-tert-butyl phosphatetrahedrane, P(CtBu)3, 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 PC3 core. The molecule exhibits unexpected thermal stability. Copyright ©2020 The Authors, some rights reserved.