E. D. Smurnyi, I. P. Gloriozov, and Yu. A. Ustynyuk
Faculty of Chemistry, Moscow State University, Vorob’evy gory, Moscow, 119899 Russia
E-mail: smurniy@nmr.chem.msu.su
Received January 14, 2003
Abstract—The oxidative addition of methane and fluoromethane to nickel, palladium, and platinum atoms and
to their diphosphine and ethylenediphosphine complexes was studied using a unique approach by the density
functional theory with the PBE functional and the TZ2p basis set taking into account relativistic corrections (the
SBK effective core potential). The complete reaction paths were determined, and the saddle points were iden-
tified by calculating the Hessians. The reactions under consideration (except the dissociation of the C–H bond
with the participation of atomic platinum, which was a barrierless reaction) involved the stage of formation of
donor–acceptor prereaction complexes. The electrophilic and nucleophilic reaction phases were discovered.
The barriers to reactions were found to decrease, and the heats of reactions to increase along the series of metals
Pd, Ni, Pt, and along the series of complexes M(PH3)2, M(PH2CH2CH2PH2). Fluoromethane was more active
than methane. The conclusion was drawn that the oxidative addition of fluoromethane at the C–H bond was a
kinetically controlled reaction, and the addition at the C–F bond was more favorable under thermodynamically
controlled conditions.
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