A DFT study on the mechanism of the gas phase reaction of ground-state Y (4d15s2,2D) with 2-butyne

Li, Tao Hong; Wang, Chuanming; Yu, Shuanbao; Liu, Xiang Yi; Fu, Hui; Xie, Xiao Guang

doi:10.1016/j.theochem.2009.08.025

Cited by 7 publications

(5 citation statements)

References 28 publications

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“…Theoretical calculations identified similar mechanisms for these reactions 12, 16, 18, and the calculated potential energy surfaces (PESs) rationalized the observed different reactivity of these metals. Recent experiments 15, 17 and our calculations 19–21 on the reactions of Y and Zr with propylene, propyne, and 2‐butyne confirmed that CC bond of some hydrocarbons can also be broken by the early metal atoms.…”

Section: Introductionsupporting

confidence: 66%

“…gap of Pd atom was calculated to be 74.0 and 74.9 kJ/mol at B3LYP/BS1 and CCSD(T)/BS2, respectively, slightly underestimating the experimental value of (91.5 kJ/mol) 33. Although Andrews and coworker's experiment does not provide the information of the reaction energies 22, our previous studies 19–21 indicate that the present theoretical levels can provide satisfactory accuracy and can at least qualitatively describe the PESs of the reactions. Considering that the CCSD(T) method can generally provide more reliable energies than B3LYP, the energies described below, unless otherwise indicated, refer to those obtained at CCSD(T)/BS2 level of theory.…”

Section: Resultsmentioning

confidence: 58%

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CH bond activation of ethylene by bare neutral palladium and platinum atoms: a theoretical investigation

Wang

Xie

2011

J of Physical Organic Chem

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The reactions of bare neutral palladium (Pd) and platinum (Pt) atoms with ethylene on both singlet and triplet surfaces were investigated at B3LYP and CCSD (T) levels of theory. The calculated potential energy profiles clearly show that Pt has higher reactivity than Pd toward ethylene. For both Pd and Pt, the reactions on singlet surfaces are energetically more favorable than those on triplet surfaces. However, notable barriers lie on the singlet and triplet surfaces for Pd +ethylene. This result rationalizes the experimental observation that Pd mainly forms π‐complex with ethylene. But under high‐energy condition, the reaction can proceed to yield dehydrogenation products, Pd‐CCH. and Pd (HCCH). For Pt, triplet‐singlet surface crossing was suggested to occur in the region where Pt forms π‐complex with ethylene to lead the reactions to the energetically more favorable singlet surfaces. For both the two metals, π‐complex and CH bond insertion species are the reaction intermediates and the H.‐elimination products are the final products. Copyright © 2010 John Wiley & Sons, Ltd.

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Section: Introductionsupporting

confidence: 66%

Section: Resultsmentioning

confidence: 58%

CH bond activation of ethylene by bare neutral palladium and platinum atoms: a theoretical investigation

Wang

Xie

2011

J of Physical Organic Chem

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“…We consider the concerted H 2 elimination because previous studies have shown that stepwise dehydrogenation paths are less favorable for the metal atom-mediated dehydrogenation of small alkenes and alkynes. 26,28,[30][31][32][63][64][65][66][67][68][69]…”

Section: Formation Of the Two Isomers Of La(c 4 H 6 )mentioning

confidence: 99%

Lanthanum-mediated dehydrogenation of butenes: Spectroscopy and formation of La(C4H6) isomers

Cao

Hewage

Yang

2018

The Journal of Chemical Physics

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La atom reactions with 1-butene, 2-butene, and isobutene are carried out in a laser-vaporization molecular beam source. The three reactions yield the same La-hydrocarbon products from the dehydrogenation and carbon-carbon bond cleavage and coupling of the butenes. The dehydrogenated species La(CH) is the major product, which is characterized with mass-analyzed threshold ionization (MATI) spectroscopy and quantum chemical computations. The MATI spectrum of La(CH) produced from the La+1-butene reaction exhibits two band systems, whereas the MATI spectra produced from the La+2-butene and isobutene reactions display only a single band system. Each of these spectra shows a strong origin band and several vibrational progressions. The two band systems from the spectrum of the 1-butene reaction are assigned to the ionization of two isomers: La[C(CH)] (Iso A) and La(CHCHCHCH) (Iso B), and the single band system from the spectra of the 2-butene and isobutene reactions is attributed to Iso B and Iso A, respectively. The ground electronic states are A (C) for Iso A and A' (C) for Iso B. The ionization of the doublet state of each isomer removes a La 6s-based electron and leads to the A ion of Iso A and the A' ion of Iso B. The formation of both isomers consists of La addition to the C=C double bond, La insertion into two C(sp)-H bonds, and H elimination. In addition to these steps, the formation of Iso A from the La+1-butene reaction may involve the isomerization of 1-butene to isobutene prior to the C-H bond activation, whereas the formation of Iso B from the La+trans-2-butene reaction may include the trans- to cis-butene isomerization after the C-H bond activation.

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“…42 To investigate reaction mechanisms, Li et al and Ma et al reported density functional theory (DFT) calculations on Y and Nb reactions with 2-butyne. 43,44 The calculated potential energy profiles suggested that two possible isomers of MC 4 H 4 (M = Y and Nb) were M(HCCCCH 3 ) and M(H 2 CCCCH 2 ) formed preferably by concerted H 2 eliminations.…”

Section: Introductionmentioning

confidence: 98%

Lanthanum-mediated dehydrogenation of 1- and 2-butynes: Spectroscopy and formation of La(C4H4) isomers

Cao

Hewage

Yang

2017

The Journal of Chemical Physics

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La atom reactions with 1-butyne and 2-butyne are carried out in a laser-vaporization molecular beam source. Both reactions yield the same La-hydrocarbon products from the dehydrogenation and carbon-carbon bond cleavage and coupling of the butynes. The dehydrogenated species La(CH) is characterized with mass-analyzed threshold ionization (MATI) spectroscopy and quantum chemical computations. The MATI spectra of La(CH) produced from the two reactions exhibit two identical transitions, each consisting of a strong origin band and several vibrational intervals. The two transitions are assigned to the ionization of two isomers: La(η-CHCCCH) (Iso A) and La(η-CHCHCCH) (Iso B). The ground electronic states are A (C) for Iso A and A (C) for Iso B. The ionization of the doublet state of each isomer removes a La 6s-based electron and results in a A ion of Iso A and a A ion of Iso B. The formation of Iso A from 2-butyne and Iso B from 1-butyne involves the addition of La to the C≡C triple bond, the activation of two C(sp)-H bonds, and concerted elimination of a H molecule. The formation of Iso A from 1-butyne and Iso B from 2-butyne involves the isomerization of the two butynes to 1,2-butadiene in addition to the concerted H elimination.

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A DFT study on the mechanism of the gas phase reaction of ground-state Y (4d15s2,2D) with 2-butyne

Cited by 7 publications

References 28 publications

CH bond activation of ethylene by bare neutral palladium and platinum atoms: a theoretical investigation

CH bond activation of ethylene by bare neutral palladium and platinum atoms: a theoretical investigation

Lanthanum-mediated dehydrogenation of butenes: Spectroscopy and formation of La(C4H6) isomers

Lanthanum-mediated dehydrogenation of 1- and 2-butynes: Spectroscopy and formation of La(C4H4) isomers

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