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Hydrophenylation of ethylene using a cationic Ru( ii ) catalyst: comparison to a neutral Ru( ii ) catalyst

Journal Article · · Chemical Science
DOI:https://doi.org/10.1039/C4SC01665C· OSTI ID:1607834
 [1];  [2];  [2];  [3];  [2];  [4]
  1. Univ. of Virginia, Charlottesville, VA (United States); University of Virginia
  2. Univ. of Virginia, Charlottesville, VA (United States)
  3. Univ. of North Texas, Denton, TX (United States)
  4. Univ. of Richmond, VA (United States)
+ Show Author Affiliations
Charge neutral Ru(II) complexes of the type TpRu(L)(NCMe)Ph [Tp = hydridotris(pyrazolyl)borate; L = CO, PMe3, P(OCH2)3CEt] have been previously reported to catalyze the hydrophenylation of ethylene (Organometallics 2012, 31, 6851-6860). Yet, catalyst longevity for the TpRu(L)(NCMe)Ph complexes is inhibited by competitive ethylene C–H activation. For example, ethylene C–H activation limits catalysis using TpRu(P(OCH2)3CEt)(NCMe)Ph to a maximum of 20 turnover numbers for conversion of benzene and ethylene to ethylbenzene. In contrast, reaction of the cationic Ru(II) complex [(HC(pz5)3)Ru(P(OCH2)3CEt)(NCMe)Ph][BAr'4] [HC(pz5)3 = tris(5-methyl-pyrazolyl)methane; BAr'4 = tetrakis[3,5-bis(trifluoromethyl)phenyl]borate] (0.025 mol% relative to benzene) in benzene with C2H4 (15 psi) at 90 °C gives 565 turnover numbers of ethylbenzene after 131 hours. The production of 565 turnovers of ethylbenzene corresponds to an approximate one-pass 95% yield with ethylene is the limiting reagent and is a 28-fold improvement compared to the charge neutral catalyst TpRu(P(OCH2)3CEt)(NCMe)Ph. Under identical conditions, the activity of [(HC(pz5)3)Ru(P(OCH2)3CEt)(NCMe)Ph][BAr'4] is only 1.3 times less than TpRu(P(OCH2)3CEt)(NCMe)Ph, but the increased stability of the cationic Ru(II) catalyst allows reactivity at much higher temperatures (up to 175 °C) and significantly enhanced rates.
Research Organization:
Univ. of North Texas, Denton, TX (United States); Univ. of Virginia, Charlottesville, VA (United States)
Sponsoring Organization:
National Science Foundation (NSF); USDOE Office of Science (SC), Basic Energy Sciences (BES) (SC-22)
Grant/Contract Number:
FG02-03ER15387; SC0000776
OSTI ID:
1607834
Journal Information:
Chemical Science, Journal Name: Chemical Science Journal Issue: 11 Vol. 5; ISSN 2041-6520; ISSN CSHCBM
Publisher:
Royal Society of ChemistryCopyright Statement
Country of Publication:
United States
Language:
English

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Jenseits von Friedel und Crafts: immanente Alkylierung von C‐H‐Bindungen in Arenen journal April 2019
Beyond Friedel and Crafts: Innate Alkylation of C−H Bonds in Arenes journal June 2019
Nickel-catalysed anti-Markovnikov hydroarylation of unactivated alkenes with unactivated arenes facilitated by non-covalent interactions journal February 2020
Investigations of the generality of quaternary ammonium salts as alkylating agents in direct C–H alkylation reactions: solid alternatives for gaseous olefins journal January 2019
Investigations of the generality of quaternary ammonium salts as alkylating agents in direct C-H alkylation reactions: solid alternatives for gaseous olefins text January 2019

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