A Theoretical Study of the Reaction Paths for Cobalt Cation + Propane

Fedorov, Dmitri G.; Gordon, Mark S.

doi:10.1021/jp9932766

Cited by 13 publications

(9 citation statements)

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“…Note that the BDEs of the nonclassical complexes are close to those of Co + complexes with small alkanes, such as ethane and propane. [42][43][44][45][46][47][48]…”

Section: Molecular Reactants and Encountermentioning

confidence: 99%

Gas-Phase Reactions of Co⁺ with Ethylamine: A Theoretical Approach to the Reaction Mechanisms of Transition Metal Ions with Primary Amines

Guo

Yang

et al. 2008

J. Phys. Chem. A

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We report herein a comprehensive study of gas-phase reactions of Co(+) with ethylamine using density functional theory. Geometries and energies for all the stationary points involved in the reactions are investigated at the B3LYP/6-311++G(2df,2pd) level. Six different "classical" N and "nonclassical" ethyl-H attached isomers are found for the Co(+)-ethylamine complexes. The classical complexes are much more stable than the nonclassical ones, which have the complexation energies close to Co(+) complexes with small alkanes. Extensive conversions could occur readily between these encounter complexes. All conceivable reaction pathways from each encounter complex to the experimentally observed products are carefully surveyed, and the most likely reaction mechanisms are derived. Activation of the C(alpha)-H bond of ethylamine by Co(+) through both the classical and nonclassical complexes leads to not only the H2 loss but also the hydride abstraction. The loss of ethylene arises from Co(+) insertion into the polar C-N bond in the classical complexes as well as from C(beta)-H activation through the nonclassical methyl-H attached complex of Co(+)- gauche-ethylamine. CH4 only forms via C-C activation from the nonclassical complex with the metal bound to two Hs from the different carbons. Initial N-H insertion is unlikely to be important. It is the reactions of the nonclassical complexes that closely parallel with the Co(+) + alkane reactions. The theoretical work sheds new light on the title reactions and can serve as a theoretical approach to the reaction mechanisms of transition metal ions with primary amines.

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“…Note that the BDEs of the nonclassical complexes are close to those of Co + complexes with small alkanes, such as ethane and propane. [42][43][44][45][46][47][48]…”

Section: Molecular Reactants and Encountermentioning

confidence: 99%

Gas-Phase Reactions of Co⁺ with Ethylamine: A Theoretical Approach to the Reaction Mechanisms of Transition Metal Ions with Primary Amines

Guo

Yang

et al. 2008

J. Phys. Chem. A

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“…Of the first-row transition metal series, for the activation of propane, the early members (Sc + [ 6 ], Ti + [ 7 ], and V + [ 8 ]) exhibit efficiency for the dehydrogenation of propane. Co + cation favors H 2 over CH 4 [ 9 , 10 ], whereas Fe + and Ni + cations favor CH 4 over H 2 [ 9 , 11 ]. Cr + cation does not show any efficiency for the activation of propane [ 12 ].…”

Section: Introductionmentioning

confidence: 99%

Activation of Propane C-H and C-C Bonds by Gas-Phase Pt Atom: A Theoretical Study

Yang

et al. 2012

IJMS

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The reaction mechanism of the gas-phase Pt atom with C3H8 has been systematically investigated on the singlet and triplet potential energy surfaces at CCSD(T)//BPW91/6-311++G(d, p), Lanl2dz level. Pt atom prefers the attack of primary over secondary C-H bonds in propane. For the Pt + C3H8 reaction, the major and minor reaction channels lead to PtC3H6 + H2 and PtCH2 + C2H6, respectively, whereas the possibility to form products PtC2H4 + CH4 is so small that it can be neglected. The minimal energy reaction pathway for the formation of PtC3H6 + H2, involving one spin inversion, prefers to start at the triplet state and afterward proceed along the singlet state. The optimal C-C bond cleavages are assigned to C-H bond activation as the first step, followed by cleavage of a C-C bond. The C-H insertion intermediates are kinetically favored over the C-C insertion intermediates. From C-C to C-H oxidative insertion, the lowering of activation barrier is mainly caused by the more stabilizing transition state interaction ΔE≠int, which is the actual interaction energy between the deformed reactants in the transition state.

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“…29 In particular, B3LYP consistently finds that the lowest-energy pathways to elimination products involve concerted passage over rate-limiting multicenter transition states ͑MCTS͒, rather than initial CC or CH bond insertion and stepwise rearrangement as previously supposed. 10,15,16,19,26,28 In earlier work, we combined pulsed, crossed-beam methods and pulsed, time-of-flight mass spectrometry ͑TOF-MS͒ to study M ϩ ϩalkane reactions for which reactant electronic state and collision energy were carefully controlled. 16,19,20,26,28 Preparation of M ϩ by resonant twophoton ionization ͑R2PI͒ using ns dye lasers allowed us to monitor the evolution of long-lived M͑alkane) ϩ complexes to H 2 or CH 4 elimination products in real time with sub-s time resolution.…”

Section: Introductionmentioning

confidence: 99%

Velocity map imaging of ion-molecule reaction products: Co+(3F4)+isobutane

Reichert

Thurau

Weisshaar

2002

The Journal of Chemical Physics

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The velocity map imaging technique is applied to mass-selected CoC3H6++CH4 and CoC4H8++H2 elimination products from the Co+(3F4)+isobutane reaction studied under crossed-beam conditions at 0.21 eV collision energy. For both reactions we obtain the joint scattering probability distribution P(E,Θ), where E and Θ are the product translational energy and scattering angle. The fraction of available energy deposited into product translation is 0.4 for H2, compared with 0.1 for CH4. For the CH4 product, the angular distribution is forward-backwards symmetric and sharply peaked at Θ=0 and 180°. P(E,Θ) is not separable into the product of an energy and an angular function; rather, the angular distribution peaks more sharply at higher translational energy. Evidently, incipient CoC3H6++CH4 products equilibrate in the Co+(C3H6)(CH4) exit-channel well, from which they decay statistically. The product translational energy distribution P(E) is consistent with orbiting-transition state phase-space theory with no exit-channel barrier. In addition, the energy-integrated angular distribution T(Θ) is consistent with the predictions of the early statistical complex decay model of Miller and Herschbach for fragmentation from a transition state that is a prolate top. In sharp contrast, P(E) for the CoC4H8++H2 products exhibits a substantial hot, nonstatistical tail towards high energy. Perhaps the H2 channel has a late potential energy barrier some 0.5 eV above products, but we view this explanation as highly unlikely. Instead, we suggest that the potential energy from an earlier multicenter transition state is funneled efficiently, and highly nonstatistically, into product translation. This surprising conclusion may apply to H2 products for the entire family of reactions of the late-3D series transition metal cations Fe+, Co+, and Ni+ with alkanes.

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A Theoretical Study of the Reaction Paths for Cobalt Cation + Propane

Cited by 13 publications

References 13 publications

Gas-Phase Reactions of Co⁺ with Ethylamine: A Theoretical Approach to the Reaction Mechanisms of Transition Metal Ions with Primary Amines

Gas-Phase Reactions of Co⁺ with Ethylamine: A Theoretical Approach to the Reaction Mechanisms of Transition Metal Ions with Primary Amines

Activation of Propane C-H and C-C Bonds by Gas-Phase Pt Atom: A Theoretical Study

Velocity map imaging of ion-molecule reaction products: Co+(3F4)+isobutane

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A Theoretical Study of the Reaction Paths for Cobalt Cation + Propane

Cited by 13 publications

References 13 publications

Gas-Phase Reactions of Co+ with Ethylamine: A Theoretical Approach to the Reaction Mechanisms of Transition Metal Ions with Primary Amines

Gas-Phase Reactions of Co+ with Ethylamine: A Theoretical Approach to the Reaction Mechanisms of Transition Metal Ions with Primary Amines

Activation of Propane C-H and C-C Bonds by Gas-Phase Pt Atom: A Theoretical Study

Velocity map imaging of ion-molecule reaction products: Co+(3F4)+isobutane

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Gas-Phase Reactions of Co⁺ with Ethylamine: A Theoretical Approach to the Reaction Mechanisms of Transition Metal Ions with Primary Amines

Gas-Phase Reactions of Co⁺ with Ethylamine: A Theoretical Approach to the Reaction Mechanisms of Transition Metal Ions with Primary Amines