Optimized structures and proton affinities of fluorinated dimethyl ethers: an ab initio study

Orgel, Victoria B.; Ball, David W.; Zehe, Michael J.

doi:10.1016/s0166-1280(96)04923-8

Cited by 10 publications

(14 citation statements)

References 16 publications

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“…However this is not the most meaningful geometrical effect introduced by protonation. As it has been previously reported, we have also found that some of the polyfluorinated compounds experience a substantial relative reorientation of the CH n F 3 - n groups upon protonation. The extent of this reorientation is measured by the w F - C1 ···C2−F parameter (Table ).…”

Section: Resultssupporting

confidence: 88%

“…Ab initio molecular structures have been reported on neutral CH 3 OCF 3 , (CH 2 F) 2 O, (CHF 2 ) 2 O, , (CF 3 ) 2 O, − and (CH 3 ) 2 O 7,8 and protonated (CH 2 F) 2 OH + , (CHF 2 ) 2 OH + , (CF 3 ) 2 OH + , , and (CH 3 ) 2 OH. , The aim of the present paper is 3-fold: (i) to perform a study of the structure and proton affinities of the whole series of fluorinated dimethyl ethers, since the available work deals only with part of this series; (ii) to systematically examine the effects of stepwise fluorination on the atomic and bond properties of fluorinated dimethyl ethers; (iii) as the systems under consideration present a different number of C−O−C−F anomeric units, this work also deals with the interpretation of the anomeric effect in the light of the AIM theory.…”

Section: Introductionmentioning

confidence: 99%

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Topological Analysis of Fluorinated Dimethyl Ethers and Their Protonated Forms

Vila

Mosquera

2000

J. Phys. Chem. A

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Changes induced by stepwise substitution of hydrogen for fluorine in neutral and protonated dimethyl ethers are analyzed in the light of the Atoms in Molecules (AIM) theory. AIM atomic and bond properties were computed by using B3LYP/6-31++G(d,p)//B3LYP/6-31G(d,p) wave functions. The effects brought about by fluorine substitution on the atomic and bond properties of the C-O-C chain were analyzed. Fluorine substitution was found to strengthen the C-H bonds. The computed proton affinities were related to the charge and energy of the proton. Reorientation of the CF n H 3-n groups upon protonation was explained in terms of the balance between anomeric and steric interactions. This interpretation and lacking of F-H bond paths allow the rejection of the previously proposed hydrogen bonding O-H‚‚‚F linkages in these systems. The fluorine substitution destabilizes C atoms in neutral and protonated forms, whereas the O is stabilized in the neutral molecule and destabilized in the cation.

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Section: Resultssupporting

confidence: 88%

Section: Introductionmentioning

confidence: 99%

Topological Analysis of Fluorinated Dimethyl Ethers and Their Protonated Forms

Vila

Mosquera

2000

J. Phys. Chem. A

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“…As a final point of comparison, a recent study has calculated the proton affinities (PA) of dimethyl ether (CH 3 OCH 3 ) and perfluorodimethyl ether (CF 3 OCF 3 ) . These calculations reveal structures in which the proton is shown to interact with the oxygen atom of the ether.…”

Section: Discussionmentioning

confidence: 99%

Bonding of Ethers and Alcohols to a-CN_x Films

Paserba¹,

Shukla²,

Gellman³

et al. 1999

Langmuir

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The surface chemistry of fluorinated ethers and fluorinated alcohols adsorbed on amorphous nitrogenated carbon (a-CN x ) have been studied as models for the interaction of perfluoropolyalkyl ether (PFPE) lubricants with the surfaces of magnetic data storage media. Temperature-programmed desorption experiments conducted in ultrahigh vacuum using small fluorinated ethers and fluorinated alcohols have measured their desorption energies and have provided insight into the nature of bonding between PFPEs and a-CN x films. Preliminary results indicate that ether linkages interact with a-CN x films through electron donation from the oxygen lone pair electrons. In contrast, alcohol end groups show evidence of hydrogen bonding with a-CN x films. The models derived from this study can aid in the future development of both lubricants and protective overcoats to ensure that the magnetic hard disks display optimal wear resistance and performance.

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“…4 Moreover, computational evidence suggested that the proton affinity of the oxygen atom of perfluoro(diethyl ether) exceeds the proton affinity of methane only slighly. 5, 6 Interestingly, the proton affinity of the fluorine atoms of this ether was assessed to be 6–13% lower than for the oxygen. Unfortunately, attempts to confirm these results by mass spectrometry were not successful due to the prominent formation of HF.…”

Section: Introductionmentioning

confidence: 99%

Cation-coordinating properties of perfluoro-15-crown-5

Lai¹,

Reardon²,

Boswell³

et al. 2010

Journal of Fluorine Chemistry

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The coordinative properties of perfluoro-15-crown-5 with monocations were investigated using 19F NMR spectroscopy and ion-selective electrodes with perfluoro-15-crown-5 as the matrix of their sensor membranes and the fluorophilic tetrakis[3,5-bis(perfluorohexyl)phenyl]borate as ion exchanger site. The results show that perfluoro-15-crown-5 interacts weakly but significantly with Na+ and K+. Assuming 1:1 stoichiometry, the formal complexation constants were determined to be 5.5 and 1.7 M−1, respectively. This weak binding is consistent with the strong electron withdrawing nature of the many fluorine atoms in the perfluorocrown ether. While perfluorinated crown ethers have been known to form host–guest complexes with the anions O2− and F− in the gas phase, this is the first study that quantitatively confirms cation binding to a perfluorocrown ether.

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Optimized structures and proton affinities of fluorinated dimethyl ethers: an ab initio study

Cited by 10 publications

References 16 publications

Topological Analysis of Fluorinated Dimethyl Ethers and Their Protonated Forms

Topological Analysis of Fluorinated Dimethyl Ethers and Their Protonated Forms

Bonding of Ethers and Alcohols to a-CN_x Films

Cation-coordinating properties of perfluoro-15-crown-5

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Optimized structures and proton affinities of fluorinated dimethyl ethers: an ab initio study

Cited by 10 publications

References 16 publications

Topological Analysis of Fluorinated Dimethyl Ethers and Their Protonated Forms

Topological Analysis of Fluorinated Dimethyl Ethers and Their Protonated Forms

Bonding of Ethers and Alcohols to a-CNx Films

Cation-coordinating properties of perfluoro-15-crown-5

Contact Info

Product

Resources

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Bonding of Ethers and Alcohols to a-CN_x Films