Electron-Deficient Ru(II) Complexes as Catalyst Precursors for Ethylene Hydrophenylation
Abstract
Ruthenium(II) complexes with the general formula TpRu(L)(NCMe)Ph (Tp = hydrido(trispyrazolyl)borate, L = CO, PMe3, P(OCH2)3CEt, P(pyr)3, P(OCH2)2(O)CCH3) have previously been shown to catalyze arene alkylation via Ru-mediated arene C–H activation including the conversion of benzene and ethylene to ethylbenzene. Previous studies have suggested that the catalytic performance of these TpRu(II) catalysts increases with reduced electron-density at the Ru center. Herein, three new structurally related Ru(II) complexes are synthesized, characterized, and studied for possible catalytic benzene ethylation. TpRu(NO)Ph2 exhibited low stability due to the facile elimination of biphenyl. The Ru(II) complex (TpBr3)Ru(NCMe)(P(OCH2)3CEt)Ph (TpBr3 = hydridotris(3,4,5-tribromopyrazol-1-yl)borate) showed no catalytic activity for the conversion of benzene and ethylene to ethylbenzene, likely due to the steric bulk introduced by the bromine substituents. (Ttz)Ru(NCMe)(P(OCH2)3CEt)Ph (Ttz = hydridotris(1,2,4-triazol-1-yl)borate) catalyzed approximately 150 turnover numbers (TONs) of ethylbenzene at 120 °C in the presence of Lewis acid additives. Here, we compare the activity and features of catalysis using (Ttz)Ru(NCMe)(P(OCH2)3CEt)Ph to previously reported catalysis based on TpRu(L)(NCMe)Ph catalyst precursors.
- Publication Date:
- Research Org.:
- Univ. of Virginia, Charlottesville, VA (United States)
- Sponsoring Org.:
- USDOE Office of Science (SC), Basic Energy Sciences (BES). Chemical Sciences, Geosciences & Biosciences Division (CSGB)
- OSTI Identifier:
- 1981149
- Grant/Contract Number:
- SC0000776
- Resource Type:
- Accepted Manuscript
- Journal Name:
- Inorganics
- Additional Journal Information:
- Journal Volume: 10; Journal Issue: 6; Journal ID: ISSN 2304-6740
- Publisher:
- MDPI
- Country of Publication:
- United States
- Language:
- English
- Subject:
- 37 INORGANIC, ORGANIC, PHYSICAL, AND ANALYTICAL CHEMISTRY; olefin hydroarylation; ruthenium; catalysis; ethylbenzene; C–H activation
Citation Formats
Jia, Xiaofan, Tian, Songyuan, Shivokevich, Philip J., Harman, W. Dean, Dickie, Diane A., and Gunnoe, T. Brent. Electron-Deficient Ru(II) Complexes as Catalyst Precursors for Ethylene Hydrophenylation. United States: N. p., 2022.
Web. doi:10.3390/inorganics10060076.
Jia, Xiaofan, Tian, Songyuan, Shivokevich, Philip J., Harman, W. Dean, Dickie, Diane A., & Gunnoe, T. Brent. Electron-Deficient Ru(II) Complexes as Catalyst Precursors for Ethylene Hydrophenylation. United States. https://doi.org/10.3390/inorganics10060076
Jia, Xiaofan, Tian, Songyuan, Shivokevich, Philip J., Harman, W. Dean, Dickie, Diane A., and Gunnoe, T. Brent. Tue .
"Electron-Deficient Ru(II) Complexes as Catalyst Precursors for Ethylene Hydrophenylation". United States. https://doi.org/10.3390/inorganics10060076. https://www.osti.gov/servlets/purl/1981149.
@article{osti_1981149,
title = {Electron-Deficient Ru(II) Complexes as Catalyst Precursors for Ethylene Hydrophenylation},
author = {Jia, Xiaofan and Tian, Songyuan and Shivokevich, Philip J. and Harman, W. Dean and Dickie, Diane A. and Gunnoe, T. Brent},
abstractNote = {Ruthenium(II) complexes with the general formula TpRu(L)(NCMe)Ph (Tp = hydrido(trispyrazolyl)borate, L = CO, PMe3, P(OCH2)3CEt, P(pyr)3, P(OCH2)2(O)CCH3) have previously been shown to catalyze arene alkylation via Ru-mediated arene C–H activation including the conversion of benzene and ethylene to ethylbenzene. Previous studies have suggested that the catalytic performance of these TpRu(II) catalysts increases with reduced electron-density at the Ru center. Herein, three new structurally related Ru(II) complexes are synthesized, characterized, and studied for possible catalytic benzene ethylation. TpRu(NO)Ph2 exhibited low stability due to the facile elimination of biphenyl. The Ru(II) complex (TpBr3)Ru(NCMe)(P(OCH2)3CEt)Ph (TpBr3 = hydridotris(3,4,5-tribromopyrazol-1-yl)borate) showed no catalytic activity for the conversion of benzene and ethylene to ethylbenzene, likely due to the steric bulk introduced by the bromine substituents. (Ttz)Ru(NCMe)(P(OCH2)3CEt)Ph (Ttz = hydridotris(1,2,4-triazol-1-yl)borate) catalyzed approximately 150 turnover numbers (TONs) of ethylbenzene at 120 °C in the presence of Lewis acid additives. Here, we compare the activity and features of catalysis using (Ttz)Ru(NCMe)(P(OCH2)3CEt)Ph to previously reported catalysis based on TpRu(L)(NCMe)Ph catalyst precursors.},
doi = {10.3390/inorganics10060076},
journal = {Inorganics},
number = 6,
volume = 10,
place = {United States},
year = {Tue May 31 00:00:00 EDT 2022},
month = {Tue May 31 00:00:00 EDT 2022}
}
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