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Title: Oxidative Hydrophenylation of Ethylene Using a Cationic Ru(II) Catalyst: Styrene Production with Ethylene as the Oxidant

Abstract

The complex [(MeOTTM)Ru(P(OCH 2) 3CEt)(NCMe)Ph][BAr' 4] (MeOTMM = 4,4',4"-(methoxymethanetriyl)-tris(1-benzyl-1H-1,2,3-triazole), BAr' 4 = tetrakis[3,5-bis(trifluoromethyl)phenyl]borate) is used to catalyze the hydrophenylation of ethylene to produce styrene and ethylbenzene. The selectivity of styrene versus ethylbenzene varies as a function of ethylene pressure, and replacing the MeOTTM ligand with tris(1-phenyl-1H-1,2,3-triazol-4-yl)methanol reduces the selectivity toward styrene. For styrene production ethylene serves as the oxidant to produce ethane, as determined by both 1H NMR spectroscopy and GC-MS. The Ru(III/II) potentials of [(MeOTTM)Ru[P(OCH 2) 3CEt](NCMe)Ph][BAr' 4] (0.86 V) and [(HC(pz 5) 3)Ru[P(OCH 2) 3CEt](NCMe)Ph][BAr' 4] (0.82 V) (HC(pz 5) 3 = tris(5-methyl-pyrazolyl)methane) are nearly identical. Since catalytic conversion of ethylene and benzene by [(HC(pz 5) 3)Ru[P(OCH 2) 3CEt](NCMe)Ph][BAr' 4] is known to selectively produce ethylbenzene, the formation of styrene using [(MeOTTM)Ru[P(OCH 2) 3CEt](NCMe)Ph][BAr' 4] is attributed to the substituents on the triazole rings of the MeOTTM ligand.

Authors:
 [1];  [2];  [3];  [4];  [1]
  1. Univ. of Virginia, Charlottesville, VA (United States). Dept. of Chemistry
  2. Stephen F. Austin State Univ., Nacogdoches, TX (United States). Dept. of Chemistry & Biochemistry
  3. Univ. of Virginia, Charlottesville, VA (United States). Dept. of Chemistry; Wuhan Textile University, Wuhan, Hubei (China). School of Materials Science and Engineering
  4. Univ. of North Texas, Denton, TX (United States). Dept. of Chemistry, Center for Advanced Scientific Computing and Modeling (CASCaM)
Publication Date:
Research Org.:
Univ. of Virginia, Charlottesville, VA (United States)
Sponsoring Org.:
USDOE Office of Science (SC), Basic Energy Sciences (BES) (SC-22)
OSTI Identifier:
1596958
Alternate Identifier(s):
OSTI ID: 1434551
Grant/Contract Number:  
[SC0000776; FG02-03ER15387]
Resource Type:
Accepted Manuscript
Journal Name:
Israel Journal of Chemistry
Additional Journal Information:
[ Journal Volume: 57; Journal Issue: 10-11]; Journal ID: ISSN 0021-2148
Publisher:
Wiley
Country of Publication:
United States
Language:
English
Subject:
37 INORGANIC, ORGANIC, PHYSICAL, AND ANALYTICAL CHEMISTRY

Citation Formats

Jia, Xiaofan, Gary, J. Brannon, Gu, Shaojin, Cundari, Thomas R., and Gunnoe, T. Brent. Oxidative Hydrophenylation of Ethylene Using a Cationic Ru(II) Catalyst: Styrene Production with Ethylene as the Oxidant. United States: N. p., 2017. Web. doi:10.1002/ijch.201700099.
Jia, Xiaofan, Gary, J. Brannon, Gu, Shaojin, Cundari, Thomas R., & Gunnoe, T. Brent. Oxidative Hydrophenylation of Ethylene Using a Cationic Ru(II) Catalyst: Styrene Production with Ethylene as the Oxidant. United States. doi:10.1002/ijch.201700099.
Jia, Xiaofan, Gary, J. Brannon, Gu, Shaojin, Cundari, Thomas R., and Gunnoe, T. Brent. Wed . "Oxidative Hydrophenylation of Ethylene Using a Cationic Ru(II) Catalyst: Styrene Production with Ethylene as the Oxidant". United States. doi:10.1002/ijch.201700099. https://www.osti.gov/servlets/purl/1596958.
@article{osti_1596958,
title = {Oxidative Hydrophenylation of Ethylene Using a Cationic Ru(II) Catalyst: Styrene Production with Ethylene as the Oxidant},
author = {Jia, Xiaofan and Gary, J. Brannon and Gu, Shaojin and Cundari, Thomas R. and Gunnoe, T. Brent},
abstractNote = {The complex [(MeOTTM)Ru(P(OCH2)3CEt)(NCMe)Ph][BAr'4] (MeOTMM = 4,4',4"-(methoxymethanetriyl)-tris(1-benzyl-1H-1,2,3-triazole), BAr'4 = tetrakis[3,5-bis(trifluoromethyl)phenyl]borate) is used to catalyze the hydrophenylation of ethylene to produce styrene and ethylbenzene. The selectivity of styrene versus ethylbenzene varies as a function of ethylene pressure, and replacing the MeOTTM ligand with tris(1-phenyl-1H-1,2,3-triazol-4-yl)methanol reduces the selectivity toward styrene. For styrene production ethylene serves as the oxidant to produce ethane, as determined by both 1H NMR spectroscopy and GC-MS. The Ru(III/II) potentials of [(MeOTTM)Ru[P(OCH2)3CEt](NCMe)Ph][BAr'4] (0.86 V) and [(HC(pz5)3)Ru[P(OCH2)3CEt](NCMe)Ph][BAr'4] (0.82 V) (HC(pz5)3 = tris(5-methyl-pyrazolyl)methane) are nearly identical. Since catalytic conversion of ethylene and benzene by [(HC(pz5)3)Ru[P(OCH2)3CEt](NCMe)Ph][BAr'4] is known to selectively produce ethylbenzene, the formation of styrene using [(MeOTTM)Ru[P(OCH2)3CEt](NCMe)Ph][BAr'4] is attributed to the substituents on the triazole rings of the MeOTTM ligand.},
doi = {10.1002/ijch.201700099},
journal = {Israel Journal of Chemistry},
number = [10-11],
volume = [57],
place = {United States},
year = {2017},
month = {11}
}

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