Reactions of Trifluoromethyl Iodide on Ni(100)

Myli, K. B.; Grassian, Vicki H.

doi:10.1021/j100005a021

Cited by 24 publications

(11 citation statements)

References 4 publications

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“…The Chemistry of CF 3 I. There has been a great deal of interest in understanding the reactions of fluorinated alkyl fragments on metal surfaces. − Again, because the C−I bond scission is facile, the fluorinated alkyl iodides are excellent precursors for investigating the basic chemistry of fluorinated alkyl groups. Their chemistry can be compared to the well-studied reactions of alkyl halides on metals to give insight into the effects of fluorination on reactivity.…”

Section: Results and Interpretationmentioning

confidence: 99%

Surface Reactions of CH₃I and CF₃I with Coadsorbed CH₂I₂ on Ag(111) as Mechanistic Probes for Carbon−Carbon Bond Formation via Methylene Insertion

Hsu

Chiang

1999

J. Am. Chem. Soc.

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The insertion of methylene into metal−alkyl bonds has been studied on an Ag(111) surface under ultrahigh-vacuum conditions. Methyl (CH3) and methylene (CH2) groups are generated on Ag(111) by thermal scission of the C−I bonds in adsorbed methyl iodide (CH3I) and methylene iodide (CH2I2) below 200 K. When studying the bimolecular interaction of coadsorbed CH3 and CH2 moieties, propane and butane are detected in the temperature-programmed reaction (TPR) experiments, suggesting that CH2 inserts into the Ag−CH3 bond to produce metal-bound ethyl (CH2CH3) groups, followed by facile self-/cross-coupling of existing alkyl groups on the surface. In a separate approach, CF3 is used instead of CH3 as the target for CH2 insertion. TPR studies of the coadsorbed CF3 and CD2 show that CD2 also inserts into the Ag−CF3 bond to form a new C−C bond; however, a different chain termination step (β-fluoride elimination) is observed to produce 1,1-difluoroethylene-d 2 (CF2CD2) in the gas phase. Two sequential methylene insertions are also implicated, as evidenced by the production of 1,1,1-trifluoropropyl iodide-2,3-d 4 (CF3CD2CD2I) as a result of the recombination of CF3CD2CD2 groups with surface iodine. The relative rates of methylene insertion, alkyl coupling, and β-elimination involved in the reaction mechanisms are systematically compared. The effect of coadsorbed iodine on the reaction pathways is assessed. The methylene insertion rate is found to be more facile on silver than on copper surfaces.

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Section: Results and Interpretationmentioning

confidence: 99%

Surface Reactions of CH₃I and CF₃I with Coadsorbed CH₂I₂ on Ag(111) as Mechanistic Probes for Carbon−Carbon Bond Formation via Methylene Insertion

Hsu

Chiang

1999

J. Am. Chem. Soc.

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“…D. Reflectance Absorption Infrared Spectroscopy. A Mattson 6021 Galaxy FTIR spectrometer equipped with external beam capabilities and a narrowband mercury-cadmium-telluride (MCT) detector was used for reflectance infrared measurements at the University of Iowa . The lower limit of the spectral range was limited to ∼750 cm -1 by the MCT detector.…”

Section: Methodsmentioning

confidence: 99%

HBr Uptake on Ice: Uptake Coefficient, H₂O/HBr Hydrate Formation, and H₂O Desorption Kinetics

Hudson¹,

Foster²,

Tolbert³

et al. 2001

J. Phys. Chem. A

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HBr uptake on thin ice films was examined using laser-induced thermal desorption (LITD), temperatureprogrammed desorption (TPD) and Fourier transform infrared (FTIR) spectroscopy techniques. LITD was used to determine the uptake coefficient in situ during low HBr exposures as a function of HBr pressure and ice film temperature. The HBr uptake coefficient on ice was γ ) 0.61 ( 0.06 at 140 K and γ ) 0.24 ( 0.05 at 100 K at low HBr coverages for HBr pressures ranging from 3 × 10 -8 to 1.4 × 10 -7 Torr. TPD and FTIR were used to examine HBr uptake on ice at higher HBr exposures. TPD studies observed that thin ice films exposed to HBr at 140 K saturated with HBr after large exposures and formed an HBr hydrate with an H 2 O:HBr ratio of ∼3.6:1. FTIR measurements monitored the development of the H 3 O + bending vibration versus HBr exposure on ice. Saturation of the integrated absorbance for this H 3 O + bending vibration was observed after large HBr exposures. The uptake of HBr on ice also had a profound effect on H 2 O desorption from ice. H 2 O desorbed at higher temperatures in the presence of HBr. The zero-order kinetics for H 2 O desorption from pure ice were E d ) 13.4 kcal mol -1 and ν 0 ) 1.9 × 10 32 cm -2 s -1 . The zero-order kinetics for H 2 O desorption from the HBr hydrate formed after saturation HBr exposures were E d ) 10.6 kcal mol -1 and ν 0 ) 6.3 × 10 27 cm -2 s -1 .

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“…We are interested in such problems regarding controlled C−F activation of small fluorocarbons bound to metal surfaces. The chemistry of trifluoromethyl groups adsorbed on metal single-crystal surfaces was explored by the reactions of trifluoromethyl iodide (CF 3 I) with Ni, − Ru, , Pt , , and Ag …”

mentioning

confidence: 99%

Selective and Facile C−F Bond Activation of Trifluoromethyl Groups on Cu(111)

Hou

Chiang

1999

J. Am. Chem. Soc.

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Reactions of Trifluoromethyl Iodide on Ni(100)

Cited by 24 publications

References 4 publications

Surface Reactions of CH₃I and CF₃I with Coadsorbed CH₂I₂ on Ag(111) as Mechanistic Probes for Carbon−Carbon Bond Formation via Methylene Insertion

Surface Reactions of CH₃I and CF₃I with Coadsorbed CH₂I₂ on Ag(111) as Mechanistic Probes for Carbon−Carbon Bond Formation via Methylene Insertion

HBr Uptake on Ice: Uptake Coefficient, H₂O/HBr Hydrate Formation, and H₂O Desorption Kinetics

Selective and Facile C−F Bond Activation of Trifluoromethyl Groups on Cu(111)

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Reactions of Trifluoromethyl Iodide on Ni(100)

Cited by 24 publications

References 4 publications

Surface Reactions of CH3I and CF3I with Coadsorbed CH2I2 on Ag(111) as Mechanistic Probes for Carbon−Carbon Bond Formation via Methylene Insertion

Surface Reactions of CH3I and CF3I with Coadsorbed CH2I2 on Ag(111) as Mechanistic Probes for Carbon−Carbon Bond Formation via Methylene Insertion

HBr Uptake on Ice: Uptake Coefficient, H2O/HBr Hydrate Formation, and H2O Desorption Kinetics

Selective and Facile C−F Bond Activation of Trifluoromethyl Groups on Cu(111)

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Surface Reactions of CH₃I and CF₃I with Coadsorbed CH₂I₂ on Ag(111) as Mechanistic Probes for Carbon−Carbon Bond Formation via Methylene Insertion

Surface Reactions of CH₃I and CF₃I with Coadsorbed CH₂I₂ on Ag(111) as Mechanistic Probes for Carbon−Carbon Bond Formation via Methylene Insertion

HBr Uptake on Ice: Uptake Coefficient, H₂O/HBr Hydrate Formation, and H₂O Desorption Kinetics