The paper, Isolation of an elusive phosphatetrahedrane, was published online on March 25, 2020.
A paper authored by Martin-Louis Y. Riu, Rebecca L. Jones, Wesley J. Transue, Peter Müller and Christopher C. Cummins was published in Science Advances on March 25, 2020.
Isolation of an elusive phosphatetrahedrane
Martin-Louis Y. Riu, Rebecca L. Jones, Wesley J. Transue, Peter Müller and Christopher C. Cummins
Department of Chemistry, Massachusetts Institute of Technology, Cambridge MA, USA.
Science Advances 25 Mar 2020:
Vol. 6, no. 13, eaaz3168
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.
Research in the Cummins group is focused on developing new methods of inorganic synthesis to address a variety of interesting questions.