Inter‐ and intramolecular CF···co interactions on aliphatic and cyclohexane carbonyl derivatives

Cormanich, Rodrigo A.; Rittner, Roberto; O’Hagan, David; Bühl, Michæl

doi:10.1002/jcc.23918

Cited by 18 publications

(15 citation statements)

References 44 publications

(61 reference statements)

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“…A similar protonation enhancing effect was also reported for the –CH 3 group [32]. In addition to sp 3 -hybridized carbon being involved in carbon bonding, the sp 2 -hybridized carbon in C=C and C=O bonds also acts as a Lewis acid [33,34,35,36,37,38,39,40,41]. Moreover, the sp 3 -hybridized carbon forms a weaker carbon bond than does the sp 2 -hybridized carbon in most cases.…”

Section: Introductionsupporting

confidence: 53%

“…Owing to the greater electronegativity and lower polarization, carbon atoms seldom engages in tetrel bonding, wherein it is also called a carbon bond if the carbon atom acts as a Lewis acid. Even so, carbon bonding has been observed in different systems [27,28,29,30,31,32,33,34,35,36,37,38,39,40,41,42,43]. A weak Ar···C interaction was firstly detected in an Ar···propargyl alcohol complex by microwave spectroscopy and ab initio calculations [27].…”

Section: Introductionmentioning

confidence: 99%

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Tetrel Bond between 6-OTX3-Fulvene and NH3: Substituents and Aromaticity

et al. 2018

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Carbon bonding is a weak interaction, particularly when a neutral molecule acts as an electron donor. Thus, there is an interesting question of how to enhance carbon bonding. In this paper, we found that the –OCH3 group at the exocyclic carbon of fulvene can form a moderate carbon bond with NH3 with an interaction energy of about −10 kJ/mol. The –OSiH3 group engages in a stronger tetrel bond than does the –OGeH3 group, while a reverse result is found for both –OSiF3 and –OGeF3 groups. The abnormal order in the former is mainly due to the stronger orbital interaction in the –OSiH3 complex, which has a larger deformation energy. The cyano groups adjoined to the fulvene ring not only cause a change in the interaction type, from vdW interactions in the unsubstituted system of –OCF3 to carbon bonding, but also greatly strengthen tetrel bonding. The formation of tetrel bonding has an enhancing effect on the aromaticity of the fulvene ring.

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Section: Introductionsupporting

confidence: 53%

Section: Introductionmentioning

confidence: 99%

Tetrel Bond between 6-OTX3-Fulvene and NH3: Substituents and Aromaticity

et al. 2018

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“…However, while a good deal of information has accumulated in recent years concerning certain aspects of the halogen and related bonds, there is less information available concerning their spectra. The data that has appeared [36,53,54,55,56,57,58,59,60,61,62] has been informative, but does not consider these systems in a systematic manner. As such, currently, there is no thorough account of the manner in which each sort of interaction modulates the spectra, nor a solid understanding of the contributing factors.…”

Section: Introductionmentioning

confidence: 99%

Effects of Halogen, Chalcogen, Pnicogen, and Tetrel Bonds on IR and NMR Spectra

Scheiner

2019

Molecules

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Complexes were formed pairing FX, FHY, FH2Z, and FH3T (X = Cl, Br, I; Y = S, Se, Te; Z = P, As, Sb; T = Si, Ge, Sn) with NH3 in order to form an A⋯N noncovalent bond, where A refers to the central atom. Geometries, energetics, atomic charges, and spectroscopic characteristics of these complexes were evaluated via DFT calculations. In all cases, the A–F bond, which is located opposite the base and is responsible for the σ-hole on the A atom, elongates and its stretching frequency undergoes a shift to the red. This shift varies from 42 to 175 cm−1 and is largest for the halogen bonds, followed by chalcogen, tetrel, and then pnicogen. The shift also decreases as the central A atom is enlarged. The NMR chemical shielding of the A atom is increased while that of the F and electron donor N atom are lowered. Unlike the IR frequency shifts, it is the third-row A atoms that undergo the largest change in NMR shielding. The change in shielding of A is highly variable, ranging from negligible for FSnH3 all the way up to 1675 ppm for FBr, while those of the F atom lie in the 55–422 ppm range. Although smaller in magnitude, the changes in the N shielding are still easily detectable, between 7 and 27 ppm.

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“…Despite the recent amassing of fundamental information about these noncovalent bonds, their effects upon the IR and NMR spectra have attracted far less attention. The data that have appeared [37,44,45,46,47,48,49,50,51,52,53,54] are informative to be sure, but they do not consider these systems in a systematic manner. As such, a thorough understanding is not available of the manner in which each type of interaction modulates the spectra, or of the processes by which they might do so.…”

Section: Introductionmentioning

confidence: 99%

Theoretical Studies of IR and NMR Spectral Changes Induced by Sigma-Hole Hydrogen, Halogen, Chalcogen, Pnicogen, and Tetrel Bonds in a Model Protein Environment

et al. 2019

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Various types of σ-hole bond complexes were formed with FX, HFY, H2FZ, and H3FT (X = Cl, Br, I; Y = S, Se, Te; Z = P, As, Sb; T = Si, Ge, Sn) as Lewis acid. In order to examine their interactions with a protein, N-methylacetamide (NMA), a model of the peptide linkage was used as the base. These noncovalent bonds were compared by computational means with H-bonds formed by NMA with XH molecules (X = F, Cl, Br, I). In all cases, the A–F bond, which lies opposite the base and is responsible for the σ-hole on the A atom (A refers to the bridging atom), elongates and its stretching frequency undergoes a shift to the red with a band intensification, much as what occurs for the X–H bond in a H-bond (HB). Unlike the NMR shielding decrease seen in the bridging proton of a H-bond, the shielding of the bridging A atom is increased. The spectroscopic changes within NMA are similar for H-bonds and the other noncovalent bonds. The C=O bond of the amide is lengthened and its stretching frequency red-shifted and intensified. The amide II band shifts to higher frequency and undergoes a small band weakening. The NMR shielding of the O atom directly involved in the bond rises, whereas the C and N atoms both undergo a shielding decrease. The frequency shifts of the amide I and II bands of the base as well as the shielding changes of the three pertinent NMA atoms correlate well with the strength of the noncovalent bond.

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Inter‐ and intramolecular CF···co interactions on aliphatic and cyclohexane carbonyl derivatives

Cited by 18 publications

References 44 publications

Tetrel Bond between 6-OTX3-Fulvene and NH3: Substituents and Aromaticity

Tetrel Bond between 6-OTX3-Fulvene and NH3: Substituents and Aromaticity

Effects of Halogen, Chalcogen, Pnicogen, and Tetrel Bonds on IR and NMR Spectra

Theoretical Studies of IR and NMR Spectral Changes Induced by Sigma-Hole Hydrogen, Halogen, Chalcogen, Pnicogen, and Tetrel Bonds in a Model Protein Environment

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