jp0657383_si_001.pdf (610.42 kB)
Theoretical Survey of the Gas-Phase Reactions of Allylamine with Co+
journal contribution
posted on 2007-07-19, 00:00 authored by Yan Ma, Wenyue Guo, Lianming Zhao, Songqing Hu, Jun Zhang, Qingtao Fu, Xiangfeng ChenDensity functional theory calculations have been carried out to survey the gas-phase reactions of allylamine
with Co+. The geometries and bonding characteristics of all the stationary points involved in the reactions
have been investigated at the B3LYP/6-311++G(d,p) level. Final energies are obtained by means of the
B3LYP/6-311+G(2df,2pd) single-point calculations. The performance of these theoretical methods is valuated
with respect to the available thermochemical data. Co+ strongly binds allylamine by forming a chelated structure
in which the metal cation binds concomitantly to the two functional groups of the neutral molecule. Various
mechanisms leading to the loss of NH3, NH2, C2H2, and H2 are analyzed in terms of the topology of the
potential energy surface. The most favorable mechanism corresponds to the loss of NH3, through a process
of C−N activation followed by a concerted β-H shift. The accompanying NH2 elimination is also discussed.
The loss of C2H2 is also favorable, through C−C activation and stepwise β-H shift, giving Co+(NH2CH3) and
Co+H(NH2CH2) as the product ions. Various possible channels for the loss of H2 are considered. The most
favorable mechanism of the H2 loss corresponds to a pathway through which the metal acts as a carrier,
connecting a hydrogen atom from the methylidyne group of allylamine with a hydrogen atom of the terminal
methylene group. The product ion of this pathway has a tricoordinated structure in which Co+ binds to the
terminal two Cs and N atoms of the NH2CH2CCH moiety.