The seeming lack of CF…HO intramolecular hydrogen bonds in linear aliphatic fluoroalcohols in solution

R. A. Cormanich; R. Rittner; M. P. Freitas; M. Buehl

doi:10.1039/c4cp02463j

The seeming lack of CF^…HO intramolecular hydrogen bonds in linear aliphatic fluoroalcohols in solution

R. A. Cormanich, R. Rittner, M. P. Freitas^*, M. Buehl

^*Corresponding author for this work

Research output: Contribution to journal › Article › peer-review

Abstract

No CF^…HO intramolecular hydrogen bonds (IHBs) in 2-fluoroethanol, 3-fluoropropanol and 4-fluorobutanol can be detected experimentally in solution by NMR and infrared spectroscopies. According to ab initio (MP2/aug-cc-pVDZ) and DFT calculations (B3LYP), a CF^…HO IHB has no influence on the conformational behavior of 2-fluoroethanol, while it stabilises the global minima of 3-fluoropropanol and 4-fluorobutanol for the isolated molecules. Entropy and bulk solvation effects, even in nonpolar media, such as CCl₄, cyclohexane and dichloromethane, are indicated to diminish the population of these global minima, apparently below the detection limit.

Original language	English
Pages (from-to)	19212-19217
Number of pages	6
Journal	Physical Chemistry Chemical Physics
Volume	16
Issue number	36
Early online date	24 Jul 2014
DOIs	https://doi.org/10.1039/c4cp02463j
Publication status	Published - 28 Sept 2014

Keywords

Phase electron-diffraction
Spin coupling-constants
Conformational-analysis
AB-initio
Fluorine
Acceptor

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10.1039/c4cp02463j

Buehl_2014_PCCP_TheSeeming_AM
© Royal Society of Chemistry 2014. This work is made available online in accordance with the publisher’s policies. This is the author created, accepted version manuscript following peer review and may differ slightly from the final published version. The final published version of this work is available at http://dx.doi.org/10.1039/C4CP02463J
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title = "The seeming lack of CF…HO intramolecular hydrogen bonds in linear aliphatic fluoroalcohols in solution",

abstract = "No CF…HO intramolecular hydrogen bonds (IHBs) in 2-fluoroethanol, 3-fluoropropanol and 4-fluorobutanol can be detected experimentally in solution by NMR and infrared spectroscopies. According to ab initio (MP2/aug-cc-pVDZ) and DFT calculations (B3LYP), a CF…HO IHB has no influence on the conformational behavior of 2-fluoroethanol, while it stabilises the global minima of 3-fluoropropanol and 4-fluorobutanol for the isolated molecules. Entropy and bulk solvation effects, even in nonpolar media, such as CCl4, cyclohexane and dichloromethane, are indicated to diminish the population of these global minima, apparently below the detection limit.",

keywords = "Phase electron-diffraction, Spin coupling-constants, Conformational-analysis, AB-initio, Fluorine, Acceptor",

author = "Cormanich, {R. A.} and R. Rittner and Freitas, {M. P.} and M. Buehl",

note = "The authors acknowledge a Grant #2012/03933-5, S{\~a}o Paulo Research Foundation (FAPESP) for providing financial support for this research (scholarship to RAC #2011/01170-1, FAPESP). FAPEMIG (Minas Gerais Research Foundation) is also acknowledged, such as CNPq for fellowships (to RR and MPF) and a studentship (to RAC). ",

year = "2014",

month = sep,

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doi = "10.1039/c4cp02463j",

language = "English",

volume = "16",

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publisher = "ROYAL SOC CHEMISTRY",

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T1 - The seeming lack of CF…HO intramolecular hydrogen bonds in linear aliphatic fluoroalcohols in solution

AU - Cormanich, R. A.

AU - Rittner, R.

AU - Freitas, M. P.

AU - Buehl, M.

N1 - The authors acknowledge a Grant #2012/03933-5, São Paulo Research Foundation (FAPESP) for providing financial support for this research (scholarship to RAC #2011/01170-1, FAPESP). FAPEMIG (Minas Gerais Research Foundation) is also acknowledged, such as CNPq for fellowships (to RR and MPF) and a studentship (to RAC).

PY - 2014/9/28

Y1 - 2014/9/28

N2 - No CF…HO intramolecular hydrogen bonds (IHBs) in 2-fluoroethanol, 3-fluoropropanol and 4-fluorobutanol can be detected experimentally in solution by NMR and infrared spectroscopies. According to ab initio (MP2/aug-cc-pVDZ) and DFT calculations (B3LYP), a CF…HO IHB has no influence on the conformational behavior of 2-fluoroethanol, while it stabilises the global minima of 3-fluoropropanol and 4-fluorobutanol for the isolated molecules. Entropy and bulk solvation effects, even in nonpolar media, such as CCl4, cyclohexane and dichloromethane, are indicated to diminish the population of these global minima, apparently below the detection limit.

AB - No CF…HO intramolecular hydrogen bonds (IHBs) in 2-fluoroethanol, 3-fluoropropanol and 4-fluorobutanol can be detected experimentally in solution by NMR and infrared spectroscopies. According to ab initio (MP2/aug-cc-pVDZ) and DFT calculations (B3LYP), a CF…HO IHB has no influence on the conformational behavior of 2-fluoroethanol, while it stabilises the global minima of 3-fluoropropanol and 4-fluorobutanol for the isolated molecules. Entropy and bulk solvation effects, even in nonpolar media, such as CCl4, cyclohexane and dichloromethane, are indicated to diminish the population of these global minima, apparently below the detection limit.

KW - Phase electron-diffraction

KW - Spin coupling-constants

KW - Conformational-analysis

KW - AB-initio

KW - Fluorine

KW - Acceptor

UR - http://www.rsc.org/suppdata/cp/c4/c4cp02463j/c4cp02463j1.pdf

U2 - 10.1039/c4cp02463j

DO - 10.1039/c4cp02463j

M3 - Article

SN - 1463-9076

VL - 16

SP - 19212

EP - 19217

JO - Physical Chemistry Chemical Physics

JF - Physical Chemistry Chemical Physics

IS - 36

ER -

The seeming lack of CF^…HO intramolecular hydrogen bonds in linear aliphatic fluoroalcohols in solution

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Keywords

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