Theoretical Survey of the Gas-Phase Reactions of Allylamine with Co⁺

Abstract

Density 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 beta-H shift. The accompanying NH2 elimination is also discussed. The loss of C2H2 is also favorable, through C-C activation and stepwise beta-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.

Theoretical survey of the reaction between osmium and acetaldehyde

“…To better understand the fundamental aspects of this reaction, several studies have been reported on the investigation of the relevant mechanism [7][8][9][10][11][12][13][14][15][16][17][18][19][20]. As one of the sim ple carbonyl containing organic molecules, acetalde hyde is used in many practical application fields such as organic synthesis, catalysis, etc.…”

“…Since catalytic hydrogenation of carbon monoxide as well as C-H activation of aldehydes is usually promoted by metal bearing catalysts, it is interesting and instructive to explore the reactions of gas phase transition metal cations and atoms with aldehyde, which may lead to a better understanding of fundamental aspects of ele mentary transition metal reactions initiated by C-H insertion. Earlier studies have focused mainly on the reactions between acetaldehyde and first row transi tion metal cations such as Co + , Fe + , Cr + , Ti + , and Ni + et al [6][7][8][9][10][11].…”

Co+-Assisted Decomposition of h6-Acetone and d6-Acetone: Acquisition of Reaction Rate Constants and Dynamics of the Dissociative Mechanism

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Mechanistic Insight into the Gas-Phase Reactions of Methylamine with Ground State Co+(3F) and Ni+(2D)

“…28,30,40 Starting with initial N-H activation, species 6 could be formed via M + insertion into one of the N-H bonds of complex 1. This probability involves TS 1-6 , which lies only 0.5 and 0.1 kcal/mol above 6 in the Co + /MA and Ni + /MA reactions, as shown in Figure 4.…”

“…In light of the successful use of the density functional theory (DFT) in predicting molecular geometries and energies of small-sized organometallics, − in this paper we perform a DFT investigation on the reactions of MA with low-spin ground state Co + ( 3 F) and Ni + ( 2 D). The structures and energies for all the reactants, intermediates, and products involved are discussed in detail.…”