A Molecular Precursor to Phosphaethyne and Its Application in Synthesis of the Aromatic 1,2,3,4-Phosphatriazolate Anion
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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
Date Issued
May 2016
Journal
Journal of the American Chemical Society
Publisher
American Chemical Society (ACS)
Citation
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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Author's final manuscript
Abstract
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.
MIT Department
Massachusetts Institute of Technology. Department of Chemistry
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DOI of Published Version
https://doi.org/10.1021/jacs.6b03910
