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Title: A Molecular Precursor to Phosphaethyne and Its Application in Synthesis of the Aromatic 1,2,3,4-Phosphatriazolate Anion

Journal Article · · Journal of the American Chemical Society
DOI:https://doi.org/10.1021/jacs.6b03910· OSTI ID:1253822
 [1];  [1];  [1];  [2];  [1];  [1];  [3];  [3];  [2];  [1];  [1]
  1. Department of Chemistry, Massachusetts Institute of Technology, Cambridge, Massachusetts 02139, United States
  2. Harvard−Smithsonian Center for Astrophysics, Cambridge, Massachusetts 02138, United States
  3. Physical Sciences Division, Pacific Northwest National Laboratory, Richland, Washington 99352, United States
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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.

Research Organization:
Pacific Northwest National Laboratory (PNNL), Richland, WA (United States). Environmental Molecular Sciences Laboratory (EMSL); Massachusetts Inst. of Technology (MIT), Cambridge, MA (United States)
Sponsoring Organization:
USDOE Office of Science (SC), Basic Energy Sciences (BES). Chemical Sciences, Geosciences & Biosciences Division; National Science Foundation (NSF); USDOE
Contributing Organization:
Smithsonian Astrophysical Observatory
Grant/Contract Number:
FG02-87ER13671; CHE-1362118; AC05-76RL01830
OSTI ID:
1253822
Alternate ID(s):
OSTI ID: 1326146; OSTI ID: 1597418; OSTI ID: 1733337; OSTI ID: 1831798
Report Number(s):
PNNL-SA-117573
Journal Information:
Journal of the American Chemical Society, Journal Name: Journal of the American Chemical Society Vol. 138 Journal Issue: 21; ISSN 0002-7863
Publisher:
American Chemical Society (ACS)Copyright Statement
Country of Publication:
United States
Language:
English
Citation Metrics:
Cited by: 32 works
Citation information provided by
Web of Science

References (45)

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Related Subjects

37 INORGANIC, ORGANIC, PHYSICAL, AND ANALYTICAL CHEMISTRY
Azides
Anions
Precursors
Aromatic compounds
Nuclear magnetic resonance spectroscopy