Erratum to “Reactions of M+ and MO+ (M=V, Nb, Ta) with methanol” [J. Mol. Struct.: THEOCHEM 683 (2004) 141–146]

Cao, Yingnan; Zhao, Xiang; Xin, Bin; Xiong, Shaoxiang; Tang, Zichao

doi:10.1016/j.theochem.2004.12.027

Cited by 27 publications

(53 citation statements)

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“…An analogous situation has also been found in the reaction of M + (M ) Sc, Ti, and Cr) with NH 3 and H 2 O [14][15][16][17]19 as well as in the V + , Nb + , or Ta + reaction with methanol. 9 If the spin inversion is not considered, then initial C-O activation is energetically the most favorable because of the lowest energy barrier involved. Along this coordinate, CH 3 elimination affording TiOH + ( 4 P 1 ) from the C-O insertion minimum ( 4 2) is expected to be very favored because it involves a simple bond insertion-reductive elimination pathway as well as the single-state reactivity (SSR) paradigm, which explains the SIDT-LV experimental finding that TiOH + accounts for over 50% of the overall products.…”

Section: Reaction Mechanismsmentioning

confidence: 99%

“…5 The Fourier transform ICR (FT-ICR) study showed that reaction of M + (M ) V, Nb, and Ta) with CH 3 OH accounts for the dominant products of MO + and MOH + , accompanied by fewer NbOCH 2 + and VOCH 3 + . 9 Although experimental works are very extensive, it still remains open to address the mechanistic details of the reaction of transition-metal ions with primary alcohols. A complete characterization of the actual reaction mechanism as well as the relevant intermediates needs a close collaboration between experiment and theory.…”

Section: Introductionmentioning

confidence: 99%

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Theoretical Survey of the Potential Energy Surface of Ti⁺ + Methanol Reaction

et al. 2009

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The gas-phase reaction of Ti(+) ((4)F and (2)F) with methanol is investigated using density functional theory. Geometries and energies of the reactants, intermediates, and products involved are calculated. The approach of Ti(+) toward methanol could form either a "classical" O- or a "nonclassical" eta(3)-methyl H-attached complex. The reaction products observed in the experiment (Guo, Kerns, Castleman J. Phys. Chem. 1992, 96, 4879) are produced via the classical association rather than the nonclassical complex. All possible pathways starting with C-O, C-H, and O-H activation are searched. Methane and methyl loss products (TiO(+) and TiOH(+)) are produced via the C-O activation; the O-H activation accounts for the H(2) and H elimination (producing TiOCH(2)(+) and TiOCH(3)(+)); and the C-H activation is unlikely to be important. Through the bond insertion (H shift) reductive elimination mechanism, the products of a closed-shell molecule (H(2) or methane) elimination could take place on both the quartet and doublet PESs owing to a spin inversion occurring in the course of initial bond insertion, whereas only the quartet products are produced adiabatically via the simple bond insertion-reductive elimination mechanism for the loss of a radical-type species (H or CH(3)). The computational results are in concert with the available experimental information and add new insight into the details of the individual elementary steps.

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Section: Reaction Mechanismsmentioning

confidence: 99%

Section: Introductionmentioning

confidence: 99%

Theoretical Survey of the Potential Energy Surface of Ti⁺ + Methanol Reaction

et al. 2009

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“…All calculations were conducted using the Gaussian09 [19] program. Optimized structures were obtained at the M06-2X [10] level of theory using basis sets of 6-31G(d) [20] [C, H, N, Si], LanL2DZ [21] [Sc], and SDD [22] [Lu].…”

Section: Methodsmentioning

confidence: 99%

Photoreactions of Sc₃N@I_h‐C₈₀ and Lu₃N@I_h‐C₈₀ with disilirane: Isolation and characterization of labile 1,2‐adducts

Kako

Ozeki

Kanzawa

et al. 2018

Heteroatom Chemistry

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The photolysis of Sc3N@Ih‐C80 with disilirane (1,2‐disilacyclopropane) afforded the corresponding 1,2‐ and 1,4‐adducts. The relatively unstable 1,2‐product was characterized using spectroscopic and electrochemical analyses, and theoretical calculations. The relative energies of the optimized structures are consistent with the experimentally observed isomerization of the 1,2‐adduct to the 1,4‐adduct. The electron‐donating effects of the silyl groups in these products were confirmed by comparing the redox potentials of the related Sc3N@Ih‐C80 derivatives. The relative stabilities and electronic properties of the 1,2‐ and 1,4‐adducts of Lu3N@Ih‐C80 show similar aspects to those obtained for the corresponding Sc3N@Ih‐C80 derivatives.

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“…[14][15][16][17][18][19][20][21][22][23][24][25][26][27][28] In particular, studies of the reactivity of the vanadium oxide cluster ions with alcohols is driven by the industrial applications of heterogeneous vanadium oxide catalysts in the oxidation of methanol, and the likely intermediacy of vanadium alkoxide species in other oxidation reactions mediated by vanadium oxides. [25][26][27][28][29][30][31][32] Heavier niobium and tantalum gas-phase clusters have also been examined, [25,26,29,[33][34][35][36][37] again in the context of the catalytic application of niobium and tantalum oxide surfaces. [38,39] The majority of these gas-phase studies have been supported by theoretical calculations.…”

Section: H T U N G T R E N N U N G (H 2 -Ochr)]mentioning

confidence: 99%

“…[38,39] The majority of these gas-phase studies have been supported by theoretical calculations. [26,27,31,32,[40][41][42] We recently described the gas-phase catalytic oxidation of methanol to formaldehyde with the mononuclear metavanadate anion [VO 3 ]…”

Section: H T U N G T R E N N U N G (H 2 -Ochr)]mentioning

confidence: 99%

Gas‐Phase Reactivity of Metavanadate [VO₃]⁻ towards Methanol and Ethanol: Experiment and Theory

Waters¹,

Wedd²,

O’Hair³

2007

Chemistry A European J

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The gas-phase reactivity of the metavanadate anion [VO3]- towards methanol and ethanol was examined by a combination of ion-molecule reaction and isotope labelling experiments in a quadrupole ion-trap mass spectrometer. The experimental data were interpreted with the aid of density functional theory calculations. [VO3]- dehydrated methanol to eliminate water and form [VO2(eta2-OCH2)]-, which features an [eta2-C,O-OCH2]2- ligand formed by formal removal of two protons from methanol and which is isoelectronic with peroxide. [VO3]- reacted with ethanol in an analogous manner to form [VO2(eta2-OCHCH3)]-, as well as by loss of ethene to form [VO2(OH)2]-. The calculations predicted that important intermediates in these reactions were the hydroxo alkoxo anions [VO2(OH)(OCH2R)]- (R: H, CH3). These were predicted to undergo intramolecular hydrogen-atom transfer to form [VO(OH)2(eta1-OCHR)]- followed by eta1-O-->eta2-C,O rearrangements to form [VO(OH)2(eta2-OCHR)]-. The latter reacted further to eliminate water and generate the product [VO2(eta2-OCHR)]-. This major product observed for [VO3]- is markedly different from that observed previously for [NbO3]- containing the heavier Group 5 congener niobium. In that case, the major product of the reaction was an ion of stoichiometry [Nb, O3, H2]- arising from the formal dehydrogenation of methanol to formaldehyde. The origin of this difference was examined theoretically and attributed to the intermediate alkoxo anion [NbO2(OH)(OCH3)]- preferring hydride transfer to form [HNbO2(OH)]- with loss of formaldehyde. This contrasts with the hydrogen-atom-transfer pathway observed for [VO2(OH)(OCH3)]-.

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Erratum to “Reactions of M+ and MO+ (M=V, Nb, Ta) with methanol” [J. Mol. Struct.: THEOCHEM 683 (2004) 141–146]

Cited by 27 publications

References 0 publications

Theoretical Survey of the Potential Energy Surface of Ti⁺ + Methanol Reaction

Theoretical Survey of the Potential Energy Surface of Ti⁺ + Methanol Reaction

Photoreactions of Sc₃N@I_h‐C₈₀ and Lu₃N@I_h‐C₈₀ with disilirane: Isolation and characterization of labile 1,2‐adducts

Gas‐Phase Reactivity of Metavanadate [VO₃]⁻ towards Methanol and Ethanol: Experiment and Theory

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Erratum to “Reactions of M+ and MO+ (M=V, Nb, Ta) with methanol” [J. Mol. Struct.: THEOCHEM 683 (2004) 141–146]

Cited by 27 publications

References 0 publications

Theoretical Survey of the Potential Energy Surface of Ti+ + Methanol Reaction

Theoretical Survey of the Potential Energy Surface of Ti+ + Methanol Reaction

Photoreactions of Sc3N@Ih‐C80 and Lu3N@Ih‐C80 with disilirane: Isolation and characterization of labile 1,2‐adducts

Gas‐Phase Reactivity of Metavanadate [VO3]− towards Methanol and Ethanol: Experiment and Theory

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Theoretical Survey of the Potential Energy Surface of Ti⁺ + Methanol Reaction

Theoretical Survey of the Potential Energy Surface of Ti⁺ + Methanol Reaction

Photoreactions of Sc₃N@I_h‐C₈₀ and Lu₃N@I_h‐C₈₀ with disilirane: Isolation and characterization of labile 1,2‐adducts

Gas‐Phase Reactivity of Metavanadate [VO₃]⁻ towards Methanol and Ethanol: Experiment and Theory