Carboxylic Solvents and O-Donor Ligand Effects on CH Activation by Pt(II)

• Published in: Journal of the American Chemical Society Vol. 128; no. 23; pp. 7404 - 7405
• Main Authors: Ziatdinov, Vadim R, Oxgaard, Jonas, Mironov, Oleg A, Young, Kenneth J. H, Goddard, William A, Periana, Roy A
• Format: Journal Article
• Language: English
• Published: Washington, DC American Chemical Society 14.06.2006
• Subjects: Chemistry; Exact sciences and technology; Kinetics and mechanisms; Organic chemistry; Reactivity and mechanisms; Platinum Complexes; Catalytic reaction; Hydrocarbon; Isotope exchange; Organic ligand; Theoretical study; Activation parameter; Transition metal Complexes; Complex catalyst; Experimental study; Benzene; Transition state; Reaction mechanism; Density functional method; Chloro complex; Catalyst activity
• ISSN: 0002-7863; 1520-5126
• DOI: 10.1021/ja060973k

We report on the design of more efficient C−H activation catalysts based on DFT calculations. The first examples of well-defined, N,O-donor ligated platinum complexes that are competent for fast C−H activation are detailed. These complexes exhibit thermal and protic stability and are efficient catalysts for H/D exchange reactions with benzene. The C−H activation is shown to benefit from design elements that (A) reduce the barrier for substrate coordination and (B) retain a low barrier for CH cleavage via a novel six-membered transition state involving the carboxylate group of the solvent.