Assignments of the Infrared and Raman Spectra of the OS2(.mu.2-CHCH3) Group of [(.mu.2-CHCH3)Os2(CO)8] and of its d1 and d4 Isotopologs as Models for the Spectra of Such Ethylidene Groups on Metal Surfaces

Anson, Christopher E.; Sheppard, N.; Powell, D.B.; Norton, Jack R.; Fischer, Wolfgang; Keiter, Richard L.; Johnson, Brian F. G.; Lewis, J. D.; Bhattacharrya, Ashok K.

doi:10.1021/ja00086a039

Cited by 27 publications

(16 citation statements)

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“…In the case of ethylidene moieties, osmium cluster work by Anson et al has shown that the CH 3 asymmetric stretch comes at 2950 cm-~ and is the strongest feature in the CH stretch region for this species [23]. Further, in the case of K promoted Pt(lll), where ethylidene has been identified as the stable intermediate in ethylene decomposition to ethylidyne, a peak in the CH stretch portion of the HREELS spectrum was seen at 2955 cm ~ [10].…”

Section: Discussionmentioning

confidence: 90%

The conversion of di-σ bonded ethylene to ethylidyne on Pt(111) monitored with sum frequency generation: evidence for an ethylidene (or ethyl) intermediate

Cremer¹,

Stanners²,

et al. 1995

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Section: Discussionmentioning

confidence: 90%

The conversion of di-σ bonded ethylene to ethylidyne on Pt(111) monitored with sum frequency generation: evidence for an ethylidene (or ethyl) intermediate

Cremer¹,

Stanners²,

et al. 1995

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“…The 2960 cm -1 feature in Figure b is characteristic of an ν as (CH 3 ). , Other possibilities such as vinyl can be ruled out on the basis of previous work with the corresponding iodide …”

Section: Resultsmentioning

confidence: 99%

Temperature-Dependent Rearrangements and Reactions of Acetylene Adsorbed on Pt(111) Monitored in the Range 125−381 K by Sum Frequency Generation

Cremer

Shen

et al. 1997

J. Phys. Chem. B

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The thermally induced rearrangements and reactions of acetylene on the (111) crystal face of platinum were observed by monitoring the vibrational spectra of surface adsorbates in the CH stretch range with infrared−visible sum frequency generation. It was found that adsorption of acetylene at 125 K led directly to the formation of an adsorbed vinylidene species (η2-μ3-CCH2). Upon annealing, a variety of different species were formed that included ethylidene (MCHCH3), di-σ-bonded ethylene (M−CH2CH2−M), μ-vinylidene (MCCH2), and ethylidyne (M⋮CCH3). The presence of species with C2H4 and C2H3 stoichiometry was strong evidence that a disproportionation reaction must occur. Above 381 K ethylidyne was the only observable species on the surface.

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“…The incompatibility of the remaining species, ethylidene CH−CH 3 , with the spectra in Figure is the most difficult case to demonstrate because of ethylidene's structural similarity with C−CH 3 . In fact, an early study 4 erroneously assigned the spectrum of C−CH 3 adsorbed on Pt(111) to CH−CH 3 . , More recently, ethylidene has been reported to be the decomposition product of C 2 H 4 on a potassium-covered Pt(111) surface, and the spectra of organometallic complexes containing a CH−CH 3 moiety have been studied . The frequency of the C−C stretching mode in these systems has been reported at 900 and 989 cm -1 , respectively, considerably lower than the frequency found for the species associated with the spectra shown in Figures , , , and 7.…”

Section: Discussionmentioning

confidence: 97%

Synthesis and Spectroscopic Identification of Ethylidyne Adsorbed on Ni(111)

et al. 1998

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The interaction of ethylene adsorbed on Ni(111) with gas-phase H atoms has been investigated. The major adsorbed reaction product is identified by high-resolution electron energy loss spectroscopy to be ethylidyne (C−CH3). This study is the first direct spectroscopic observation of a C−CH3 species adsorbed on Ni in an ultrahigh-vacuum environment. Spectra of four isotopomers, C−CH3, 13C−13CH3, C−CD3, and 13C−13CD3, are reported, and a complete and consistent vibrational assignment of their fundamental modes is presented. Based on this assignment, a force field is derived from the measured vibrational frequencies using a normal-modes analysis and is found to be in good agreement with that deduced from IR spectra of an ethylidyne species in an organometallic complex. Inspection of the eigenvectors of the normal-mode displacements reveals that substantial mixing of harmonic bond motions is the origin of the unusual upshift in frequency of the C−C stretching mode upon deuteration. A quantitative determination of the relative dynamic bond dipole moments demonstrates that the changes in intensity and dipole activity of the C−C stretching and symmetric CH3 deformation modes upon deuteration, phenomena common to all C−CD3 spectra, also arise from extensive mixing of bond motions. A detailed analysis of the spectra strongly suggests a C 3 v or C 3 local environment for ethylidyne and a 3-fold hollow adsorption site.

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Assignments of the Infrared and Raman Spectra of the OS2(.mu.2-CHCH3) Group of [(.mu.2-CHCH3)Os2(CO)8] and of its d1 and d4 Isotopologs as Models for the Spectra of Such Ethylidene Groups on Metal Surfaces

Cited by 27 publications

References 0 publications

The conversion of di-σ bonded ethylene to ethylidyne on Pt(111) monitored with sum frequency generation: evidence for an ethylidene (or ethyl) intermediate

The conversion of di-σ bonded ethylene to ethylidyne on Pt(111) monitored with sum frequency generation: evidence for an ethylidene (or ethyl) intermediate

Temperature-Dependent Rearrangements and Reactions of Acetylene Adsorbed on Pt(111) Monitored in the Range 125−381 K by Sum Frequency Generation

Synthesis and Spectroscopic Identification of Ethylidyne Adsorbed on Ni(111)

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