A Molecular Precursor to Phosphaethyne and Its Application in Synthesis of the Aromatic 1,2,3,4-Phosphatriazolate Anion
Author(s)Martin-Drumel, Marie-Aline; Hou, Gao-Lei; Wang, Xue-Bin; McCarthy, Michael C.; Transue, Wesley; Velian, Alexandra; Nava, Matthew Jordan; Womack, Caroline C.; Jiang, Jun; Field, Robert W; Cummins, Christopher C.; ... Show more Show less
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Dibenzo-7-phosphanorbornadiene Ph[subscript 3]PC(H)PA (1, A = C[subscript 14]H[subscript 10], anthracene) is reported here as a molecular precursor to phosphaethyne (HC≡P), produced together with anthracene and triphenylphosphine. HCP generated by thermolysis of 1 has been observed by molecular beam mass spectrometry, laser-induced fluorescence, microwave spectroscopy, and nuclear magnetic resonance (NMR) spectroscopy. In toluene, fragmentation of 1 has been found to proceed with activation parameters of ΔH[superscript ⧧] = 25.5 kcal/mol and ΔS[superscript ⧧] = −2.43 eu and is accompanied by formation of an orange insoluble precipitate. Results from computational studies of the mechanism of HCP generation are in good agreement with experimental data. This high-temperature method of HCP generation has pointed to new reaction chemistry with azide anion to produce the 1,2,3,4-phosphatriazolate anion, HCPN3–, for which structural data have been obtained in a single-crystal X-ray diffraction study. Negative-ion photoelectron spectroscopy has shown the adiabatic detachment energy for this anion to be 3.555(10) eV. The aromaticity of HCPN[subscript 3]– has been assessed using nucleus-independent chemical shift, quantum theory of atoms in molecules, and natural bond orbital methods.
DepartmentMassachusetts Institute of Technology. Department of Chemistry
Journal of the American Chemical Society
American Chemical Society (ACS)
Transue, Wesley J., Alexandra Velian, Matthew Nava, Marie-Aline Martin-Drumel, Caroline C. Womack, Jun Jiang, Gao-Lei Hou, et al. “A Molecular Precursor to Phosphaethyne and Its Application in Synthesis of the Aromatic 1,2,3,4-Phosphatriazolate Anion.” Journal of the American Chemical Society 138, no. 21 (June 2016): 6731–6734.
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