A Molecular Precursor to Phosphaethyne and Its Application in Synthesis of the Aromatic 1,2,3,4-Phosphatriazolate Anion
Abstract
Dibenzo-7-phosphanorbornadiene Ph3PC(H)PA (1, A = C14H10, 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‡ = 25.5 kcal/mol and ΔS‡ = –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 HCPN3– has been assessed using nucleus-independent chemical shift, quantum theory of atoms in molecules, and natural bond orbital methods.
- Authors:
-
- Department of Chemistry, Massachusetts Institute of Technology, Cambridge, Massachusetts 02139, United States
- Harvard−Smithsonian Center for Astrophysics, Cambridge, Massachusetts 02138, United States
- Physical Sciences Division, Pacific Northwest National Laboratory, Richland, Washington 99352, United States
- Publication Date:
- Research Org.:
- Pacific Northwest National Laboratory (PNNL), Richland, WA (United States). Environmental Molecular Sciences Laboratory (EMSL); Massachusetts Inst. of Technology (MIT), Cambridge, MA (United States)
- Sponsoring Org.:
- USDOE Office of Science (SC), Basic Energy Sciences (BES). Chemical Sciences, Geosciences & Biosciences Division; National Science Foundation (NSF); USDOE
- Contributing Org.:
- Smithsonian Astrophysical Observatory
- OSTI Identifier:
- 1253822
- Alternate Identifier(s):
- OSTI ID: 1326146; OSTI ID: 1597418; OSTI ID: 1733337; OSTI ID: 1831798
- Report Number(s):
- PNNL-SA-117573
Journal ID: ISSN 0002-7863
- Grant/Contract Number:
- FG02-87ER13671; CHE-1362118; AC05-76RL01830
- Resource Type:
- Published Article
- Journal Name:
- Journal of the American Chemical Society
- Additional Journal Information:
- Journal Name: Journal of the American Chemical Society Journal Volume: 138 Journal Issue: 21; Journal ID: ISSN 0002-7863
- Publisher:
- American Chemical Society (ACS)
- Country of Publication:
- United States
- Language:
- English
- Subject:
- 37 INORGANIC, ORGANIC, PHYSICAL, AND ANALYTICAL CHEMISTRY; Azides; Anions; Precursors; Aromatic compounds; Nuclear magnetic resonance spectroscopy
Citation Formats
Transue, Wesley J., Velian, Alexandra, Nava, Matthew, Martin-Drumel, Marie-Aline, Womack, Caroline C., Jiang, Jun, Hou, Gao-Lei, Wang, Xue-Bin, McCarthy, Michael C., Field, Robert W., and Cummins, Christopher C. A Molecular Precursor to Phosphaethyne and Its Application in Synthesis of the Aromatic 1,2,3,4-Phosphatriazolate Anion. United States: N. p., 2016.
Web. doi:10.1021/jacs.6b03910.
Transue, Wesley J., Velian, Alexandra, Nava, Matthew, Martin-Drumel, Marie-Aline, Womack, Caroline C., Jiang, Jun, Hou, Gao-Lei, Wang, Xue-Bin, McCarthy, Michael C., Field, Robert W., & Cummins, Christopher C. A Molecular Precursor to Phosphaethyne and Its Application in Synthesis of the Aromatic 1,2,3,4-Phosphatriazolate Anion. United States. https://doi.org/10.1021/jacs.6b03910
Transue, Wesley J., Velian, Alexandra, Nava, Matthew, Martin-Drumel, Marie-Aline, Womack, Caroline C., Jiang, Jun, Hou, Gao-Lei, Wang, Xue-Bin, McCarthy, Michael C., Field, Robert W., and Cummins, Christopher C. Tue .
"A Molecular Precursor to Phosphaethyne and Its Application in Synthesis of the Aromatic 1,2,3,4-Phosphatriazolate Anion". United States. https://doi.org/10.1021/jacs.6b03910.
@article{osti_1253822,
title = {A Molecular Precursor to Phosphaethyne and Its Application in Synthesis of the Aromatic 1,2,3,4-Phosphatriazolate Anion},
author = {Transue, Wesley J. and Velian, Alexandra and Nava, Matthew and Martin-Drumel, Marie-Aline and Womack, Caroline C. and Jiang, Jun and Hou, Gao-Lei and Wang, Xue-Bin and McCarthy, Michael C. and Field, Robert W. and Cummins, Christopher C.},
abstractNote = {Dibenzo-7-phosphanorbornadiene Ph3PC(H)PA (1, A = C14H10, 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‡ = 25.5 kcal/mol and ΔS‡ = –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 HCPN3– has been assessed using nucleus-independent chemical shift, quantum theory of atoms in molecules, and natural bond orbital methods.},
doi = {10.1021/jacs.6b03910},
journal = {Journal of the American Chemical Society},
number = 21,
volume = 138,
place = {United States},
year = {Tue May 17 00:00:00 EDT 2016},
month = {Tue May 17 00:00:00 EDT 2016}
}
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