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

作者：McKeown Bradley A; Gonzalez Hector Emanuel; Friedfeld Max R; Gunnoe T Brent^*; Cundari Thomas R; Sabat Michal

来源：Journal of the American Chemical Society, 2011, 133(47): 19131-19152.

DOI：10.1021/ja206064v

Cationic platinum(II) complexes [((t)bpy)Pt(Ph)-(L)](+) [(t)bpy =4,4'-di-tert-butyl-2,2'-bipyridyl; L = THF, NC(5)F(5), or NCMe] catalyze the hydrophenylation of ethylene to generate ethylbenzene and isomers of diethylbenzene. Using ethylene as the limiting reagent, an 89% yield of alkyl arene 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 (C(6)H(6) or C(6)D(6)) C H/C-D activation by Opy)Pt(Ph-d)(THF)](+) (n = 0 or 5) indicate a k(H)/k(D) = 1.4(1), while comparative rates of ethylene hydrophenylation using C(6)H(6) and C(6)D(6) reveal k(H)/k(D) = 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 CD(2)Cl(2), [((t)bpy)Pt(Ph)(THF)][BAr'(4)] [Ar = 3,5-bis(trifluoromethyl)phenyl] reacts with ethylene to generate [((t)bpy)Pt(CH(2)CH(2)Ph)(eta(2)-C(2)-H(4))][BAr'(4)] with k(obs) = 1.05(4) x 10(-3) s(-1) (23 degrees C, [C(2)H(4)] = 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.

• 出版日期2011-11-30