Theoretical investigation of C–H activation in Mg+–CH3X (X=H, NH2 and CHO)

Guo, Wenyue; Yuan, Tao; Chen, Xiangfeng; Zhao, Lianming; Lu, Xiaoqing; Wu, Shujuan

doi:10.1016/j.theochem.2006.02.011

Cited by 18 publications

(6 citation statements)

References 43 publications

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“…4 conversation indeed involves a CT process between CH 2 NH 2 and CuH + . It is interesting to note that such a process has been extensively found in Mg + -amine reactions [16][17][18], which may be driven by the ionization potential difference between iminium radical and magnesium hydride. For the Cu + + methylamine system, a similar situation is expected if the ionization potentials of CuH ($9.5 eV) [36] and CH 2 NH 2 ($6.3 eV) [18,37] are considered.…”

Section: Resultsmentioning

confidence: 94%

“…Recently, we have theoretically investigated the hydride abstraction mechanism of Mg + -amine complexes [16][17][18]. Our results suggest the reaction involves indeed a ''classical'' N attached complex rather than a ''nonclassical'' form (such as methyl-or CH 2 -attachment) and shares a common reaction mechanism -C a -H activation, H migration, charge-transfer (CT), and decomposition.…”

Section: Introductionmentioning

confidence: 91%

“…Our results suggest the reaction involves indeed a ''classical'' N attached complex rather than a ''nonclassical'' form (such as methyl-or CH 2 -attachment) and shares a common reaction mechanism -C a -H activation, H migration, charge-transfer (CT), and decomposition. The driving force for this process is dictated by the special stability of iminium cations, which arises from the lower ionization potentials of their precursors relative to that of their partner, metal hydrides (MgH) [16][17][18]. In spite of these investigations, the hydride abstraction by transition metal ions is still worthy of theoretical consideration, since different electronic configurations of the metal ions could result in significantly different structures and energetics of species involved, which are of particular importance in understanding a reaction mechanism and in modeling dynamic parameters for a reaction using statistical theory as well.…”

Section: Introductionmentioning

confidence: 99%

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Hydride abstraction of methylamine with Cu+(1S) in the gas phase: A density functional theory study

Guo

Zhao

et al. 2007

Journal of Organometallic Chemistry

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Section: Resultsmentioning

confidence: 94%

Section: Introductionmentioning

confidence: 91%

Section: Introductionmentioning

confidence: 99%

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Hydride abstraction of methylamine with Cu+(1S) in the gas phase: A density functional theory study

Guo

Zhao

et al. 2007

Journal of Organometallic Chemistry

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“…Loss of MnH + has two isomeric neutral products, i.e., acetyl radical CH 3 CO and vinyloxy radical CH 2 CHO. Both radicals are important intermediates in combustion and photochemical smog cycles and have been widely investigated in the gas-phase oxidation of unsaturated hydrocarbons. − PESs together with schematic structures involved in the septet and quintet pathways for the MnH + formation are shown in Figure .…”

Section: Resultsmentioning

confidence: 99%

Theoretical Investigation of the Reaction of Mn⁺ with Ethylene Oxide

Guo

Zhao

et al. 2011

J. Phys. Chem. A

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The potential energy surfaces of Mn(+) reaction with ethylene oxide in both the septet and quintet states are investigated at the B3LYP/DZVP level of theory. The reaction paths leading to the products of MnO(+), MnO, MnCH(2)(+), MnCH(3), and MnH(+) are described in detail. Two types of encounter complexes of Mn(+) with ethylene oxide are formed because of attachments of the metal at different sites of ethylene oxide, i.e., the O atom and the CC bond. Mn(+) would insert into a C-O bond or the C-C bond of ethylene oxide to form two different intermediates prior to forming various products. MnO(+)/MnO and MnH(+) are formed in the C-O activation mechanism, while both C-O and C-C activations account for the MnCH(2)(+)/MnCH(3) formation. Products MnO(+), MnCH(2)(+), and MnH(+) could be formed adiabatically on the quintet surface, while formation of MnO and MnCH(3) is endothermic on the PESs with both spins. In agreement with the experimental observations, the excited state a(5)D is calculated to be more reactive than the ground state a(7)S. This theoretical work sheds new light on the experimental observations and provides fundamental understanding of the reaction mechanism of ethylene oxide with transition metal cations.

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“…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.…”

Section: Introductionmentioning

confidence: 99%

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

Wei

Guo

et al. 2010

J. Phys. Chem. A

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The gas-phase reaction mechanisms of methylamine (MA) with the ground-state Co(+)((3)F) and Ni(+)((2)D) are theoretically investigated using density functional theory at both the B3LYP/6-311++G(d,p) and B3LYP/6-311++G(3df,2p) levels. The reactions for hydride abstraction and dehydrogenation are analyzed in terms of the topology of potential energy surfaces (PESs). Co(+) and Ni(+) perform similar roles along the isomerization processes to the final products. Hydride abstraction takes place via the key species of metal cation-methyl-H intermediate, followed by a charge transfer process before the direct dissociation of CH(2)NH(2)(+)···MH (M = Co, Ni). The enthalpies of reaction, stability of metal cation-methyl-H species, and competition between different channels account for the sequence of the hydride abstraction products: CoH < NiH < CuH. The most competitive dehydrogenation route occurs through a stepwise reaction, consisting of initial C-H activation, amino-H shift, and direct dissociation of the precursor CH(2)NHM(+)···H(2). This theoretical work sheds new light on the experimental observations and provides fundamental understanding of the reaction mechanisms of amine prototype with late first-row transition metal cations.

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Theoretical investigation of C–H activation in Mg+–CH3X (X=H, NH2 and CHO)

Cited by 18 publications

References 43 publications

Hydride abstraction of methylamine with Cu+(1S) in the gas phase: A density functional theory study

Hydride abstraction of methylamine with Cu+(1S) in the gas phase: A density functional theory study

Theoretical Investigation of the Reaction of Mn⁺ with Ethylene Oxide

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

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Theoretical investigation of C–H activation in Mg+–CH3X (X=H, NH2 and CHO)

Cited by 18 publications

References 43 publications

Hydride abstraction of methylamine with Cu+(1S) in the gas phase: A density functional theory study

Hydride abstraction of methylamine with Cu+(1S) in the gas phase: A density functional theory study

Theoretical Investigation of the Reaction of Mn+ with Ethylene Oxide

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

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Product

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Theoretical Investigation of the Reaction of Mn⁺ with Ethylene Oxide

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