Theoretical investigation of the reactivity in the C–F bond activation of CH3F by La+ in the gas phase

Wang, Yongcheng; Liu, Zeyu; Geng, Zhi‐Yuan; Yang, Xiao-Yan; Gao, Liguo; Chen, Xiaoxia

doi:10.1016/j.theochem.2006.03.005

Cited by 18 publications

(11 citation statements)

References 25 publications

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“…In accord with this study, this is the lowest-energy pathway through which the elimination species can be attained from the ground state of the reactants. The energy profile in Figure 4 for this triplet channel is in good agreement with the two-step elimination mechanism recently proposed by Li et al [9] for this reaction. (Based on DFT calculations and the IRC scheme, followed by CCSD(T) single-point calculations on the detected stationary points, these authors found two possible paths emerging from the ground state of the reactants which correlate with the asymptote CH 2 As + + HF.)…”

supporting

confidence: 89%

“…[9] In that study two pathways are discussed that evolve from the ground state of the reactants that can lead to the observed elimination products CH 2 As + + HF. The description obtained for this reaction herein is in agreement with the two-step elimination mechanism proposed by these authors.…”

Section: Introductionmentioning

confidence: 99%

“…In addition to the results reported in ref. [9], we discuss herein those reaction channels emerging from the first excited state of the reactants. To our best knowledge, theoretical results for any of the remaining interactions investigated herein have not been reported.…”

Section: Introductionmentioning

confidence: 99%

“…The calculated barrier herein (8.4 kcal mol À1 ) is lower than the energy reported in ref. [9] for this transition state by nearly 8 kcal mol À1 (for the remaining stationary points the energy difference falls into the interval 1-5 kcal mol…”

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confidence: 96%

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Theoretical Study of the Reactions M⁺+CH₃F (M=Ge, As, Se, Sb)

Méndez

Colmenares

2010

ChemPhysChem

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CASSCF-MRMP2 calculations have been carried out to analyze the reactions of the methyl fluoride molecule with the atomic ions Ge(+), As(+), Se(+) and Sb(+). For these interactions, potential energy curves for the low-lying electronic states were calculated for different approaching modes of the fragments. Particularly, those channels leading to C-H and C--F oxidative addition products, H(2)FC-M-H(+) and H(3)C-M-F(+), respectively were explored, as well as the paths which evolve to the abstraction (M-F(+)+CH(3)) and the elimination (CH(2)M(+)+HF) asymptotes. For the reaction Ge(+)+CH(3)F the only favorable channel leads to fluorine abstraction by the ion. As(+) and Sb(+) can react with CH(3)F along pathways yielding stable addition products. However, a viable path joining the oxidative addition product H(3)C-M-F(+) with the elimination asymptote CH(2)M(+)+HF was found for the reaction of the fluorocarbon compound with As(+). No favorable channels were detected for the interaction of fluoromethane with Se(+). The results discussed herein allow rationalizing some of the experimental data found for these interactions through gas-phase mass spectrometry.

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supporting

confidence: 89%

Section: Introductionmentioning

confidence: 99%

Section: Introductionmentioning

confidence: 99%

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confidence: 96%

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Theoretical Study of the Reactions M⁺+CH₃F (M=Ge, As, Se, Sb)

Méndez

Colmenares

2010

ChemPhysChem

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“…This conclusion warned us about the reliability of some theoretical results on the M + +CH 3 F reactions employing these types of functionals. 1,[13][14][15] Indeed, the tendency of the DFT͑B3LYP͒ methodology to underestimate reaction barriers is well documented, 16 and ͑b͒ although the theoretical exploration of the potential energy surface ͑PES͒ and the analysis in terms of the valence bond theory strongly suggest that an harpoon-like mechanism operates, there is no a single correlation between IE͑M + ͒ and reactiv-ity, which indicates that the mechanism through which metal-mediated activation of carbon-halide bonds is not fully understood yet. Bearing in mind that Zhao et al 17 recently reported rate coefficients from inductively coupled plasma/selected-ion flow tube experiments for the reactions of methyl fluoride with a number of atomic cations involving fourth-, fifth-, and sixth-period atomic cations ͑including Ca + ͒, we planned a systematic theoretical research combining the characterization of the PESs for the M + +CH 3 X ͑X =H,F,Cl͒ reactions, followed by kinetics calculations allowing us to compute rate constants to be compared with the experimental data available.…”

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confidence: 99%

Gas-phase reaction between calcium monocation and fluoromethane: Analysis of the potential energy hypersurface and kinetics calculations

Varela‐Álvarez

Rayón

Barrientos

et al. 2009

The Journal of Chemical Physics

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A quantum reaction dynamics study of the translational, vibrational, and rotational motion effects on the HD + H3+ reaction J. Chem. Phys. 135, 114307 (2011) First-principles simulation of molecular dissociation-recombination equilibrium J. Chem. Phys. 135, 104310 (2011) Direct simulation of electron transfer using ring polymer molecular dynamics: Comparison with semiclassical instanton theory and exact quantum methods J. Chem. Phys. 135, 074106 (2011) Charge-transfer-induced suppression of galvanic replacement and synthesis of (Au@Ag)@Au double shell nanoparticles for highly uniform, robust and sensitive bioprobes Appl. Phys. Lett. 99, 073107 (2011) Additional information on J. Chem. Phys. The gas-phase reaction between calcium monocation and fluoromethane: Ca + +CH 3 F → CaF + +CH 3 was theoretically analyzed. The potential energy hypersurface was explored by using density functional theory methodology with different functionals and Pople's, Dunning's, Ahlrichs', and Stuttgart-Dresden basis sets. Kinetics calculations ͑energy and total angular momentum resolved microcanonical variational/conventional theory͒ were accomplished. The theoretically predicted range for the global kinetic rate constant values at 295 K ͑7.2ϫ 10 −11 -5.9 ϫ 10 −10 cm 3 molecule −1 s −1 ͒ agrees reasonably well with the experimental value at the same temperature ͓͑2.6Ϯ 0.8͒ ϫ 10 −10 cm 3 molecule −1 s −1 ͔. Explicit consideration of a two transition state model, where the formation of a weakly bounded prereactive complex is preceded by an outer transition state ͑entrance channel͒ and followed by an inner transition state connecting with a second intermediate that finally leads to products, is mandatory. Experimental observations on the correlation, or lack of correlation, between reaction rate constants and second ionization energies of the metal might well be rationalized in terms of this two transition state model.

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