Mechanistic Studies of Ethylene Hydrophenylation Catalyzed by Bipyridyl Pt(II) Complexes

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This article discusses mechanistic studies of ethylene hydrophenylation catalyzed by bipyridyl Pt(II) complexes.

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22 p.

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McKeown, Bradley A.; Gonzalez, Hector Emanuel; Friedfeld, Max R.; Gunnoe, T. Brent; Cundari, Thomas R., 1964- & Sabat, Michal November 8, 2011.

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This article discusses mechanistic studies of ethylene hydrophenylation catalyzed by bipyridyl Pt(II) complexes.

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22 p.

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Reprinted with permission from the Journal of the American Chemical Society. Copyright 2011 American Chemical Society.

Abstract: Cationic platinum (II) complexes [(ᵗbpy)Pt(Ph)-(L)]⁺[ᵗbpy=4,4'-di-tert-butyl-2,2'-bipyridyl; L = THF, NC₅F₅, or NCMe] catalyze the hydrophenylation of ethylene to generate ethylbenzene and isomers of diethylbenzene. Using ethylene as the limiting reagent, an 89% yield of alkylarene products is achieved after 4 h at 120 ˚C. Catalyst efficiency for ethylene hydrophenylation is diminished only slightly under aerobic conditions. Mechanistic studies support a reaction pathway that involves ethylene coordination to Pt(II), insertion of ethylene into the Pt-phenyl bond, and subsequent metal-mediated benzene C-H activation. Studies of stoichiometric benzene (C₆H₆ or C₆D₆) C-H/C-D activation by [(ᵗbpy)Pt(Ph-dn)-(THF)]⁺ (n = 0 or 5) indicate a kʜ/kᴅ = 1.4(1), while comparative rates of ethylene hydrophenylation using C₆H₆ and C₆D₆ reveal kʜ/kᴅ = 1.8(4) for the overall catalytic reaction. DFT calculations suggest that the transition state for benzene C-H activation is the highest energy species along the catalytic cycle. In CD₂Cl₂, [(ᵗbpy)Pt(Ph)(THF)][BAr'₄] [Ar' = 3,5-bis(trifluoromethyl)phenyl] reacts with ethylene to generate [(ᵗbpy)Pt(CH₂CH₂Ph)(ɳ²-C₂H₄)][BAr'₄] with kobs = 1.05(4) x 10⁻³ s⁻¹ (23 ˚C, [C₂H₄] = 0.10(1) M). In the catalytic hydrophenylation of ethylene, substantial amounts of diethylbenzenes are produced, and experimental studies suggest that the selectivity for the monoalkylated arene is diminished due to a second aromatic C-H activation competing with ethylbenzene dissociation.

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  • Journal of the American Chemical Society, 2011, Washington DC: American Chemical Society, pp. 19131-19152

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  • Publication Title: Journal of the American Chemical Society
  • Volume: 133
  • Issue: 47
  • Page Start: 19131
  • Page End: 19152
  • Peer Reviewed: Yes

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  • November 8, 2011

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  • Oct. 9, 2012, 10:02 a.m.

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  • July 22, 2013, 2:08 p.m.

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McKeown, Bradley A.; Gonzalez, Hector Emanuel; Friedfeld, Max R.; Gunnoe, T. Brent; Cundari, Thomas R., 1964- & Sabat, Michal. Mechanistic Studies of Ethylene Hydrophenylation Catalyzed by Bipyridyl Pt(II) Complexes, article, November 8, 2011; [Washington, DC]. (digital.library.unt.edu/ark:/67531/metadc107788/: accessed July 21, 2017), University of North Texas Libraries, Digital Library, digital.library.unt.edu; crediting UNT College of Arts and Sciences.