Pushing the limits of the hydrogen bond enhanced halogen bond—the case of the C–H hydrogen bond

Decato, Daniel A.; Sun, Jiyu; Boller, Madeleine R.; Berryman, Orion B.

doi:10.1039/d2sc03792k

Cited by 19 publications

(14 citation statements)

References 38 publications

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“…A similar phenomenon was observed when the NH group is part of an amide . Even a relatively weak HB involving a CH donor can strengthen a XB, although this HB was again accentuated by charge assistance due to the overall positive charge on the Lewis acid. Another internal NH···X HB was found to activate a series of vinyl phosphonates for enantioselective Michael addition …”

Section: Discussionmentioning

confidence: 52%

“…41,53 As one example drawn from the biological sphere, adding a Cl atom to Tyr 50 raised the activity of the pertinent enzyme as this Cl atom formed a XB with the carbonyl O of a neighboring Gly. This XB 48 Even a relatively weak HB involving a CH donor can strengthen a XB, 49 although this HB was again accentuated by charge assistance due to the overall positive charge on the Lewis acid. Another internal NH•••X HB was found to activate a series of vinyl phosphonates for enantioselective Michael addition.…”

Section: ■ Discussionmentioning

confidence: 99%

“…Although still sparse, previous work is highly suggestive that such a scenario might be fairly common. Experimental and theoretical data ,− indicate an arrangement of this sort within the specialized framework of cation–anion interactions involved in halide binding. This HB/XB cooperativity has also been shown to play an active role in protein structure and function , and catalysis. , …”

Section: Introductionmentioning

confidence: 99%

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Enhancement of Halogen Bond Strength by Intramolecular H-Bonds

Scheiner

2023

J. Phys. Chem. A

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Quantum calculations study the potential of an intramolecular H-bond between the halogen atom (X) of a halobenzene and a substituent placed ortho to it, to amplify the ability of X to engage in a halogen bond (XB) with a Lewis base. H-bonding substituents NH2, CH2CH2OH, CH2OH, OH, and COOH were added to halobenzenes (X = Cl, Br, I). The amino group had little effect, but those containing OH increased the CX···N XB energy to a NH3 nucleophile by about 0.5 kcal/mol; the increment associated with COOH is larger, nearly 2 kcal/mol. These energy increments were approximately doubled if two such H-bonding substituents are present. Combining a pair of ortho COOH groups with an electron-withdrawing NO2 group in the para position has a particularly large effect, raising the XB energy by about 4 kcal/mol, which can amount to as much as a 4-fold magnification.

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Section: Discussionmentioning

confidence: 52%

Section: ■ Discussionmentioning

confidence: 99%

Section: Introductionmentioning

confidence: 99%

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Enhancement of Halogen Bond Strength by Intramolecular H-Bonds

Scheiner

2023

J. Phys. Chem. A

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“…The same sort of functional change occurred for an intramolecular NH••I wherein NH was part of an amide group 49 which bears direct applicability to protein function. Even a relatively weak HB such as that involving a CH group can provoke a stronger XB, 50 again within the context of an overall positive charge on the Lewis acid. Additional support arises from the study of enantioselective Michael addition 53 where an internal NH••X halogen bond activates a series of vinyl phosphonates.…”

Section: ■ Discussionmentioning

confidence: 99%

“…Although still sparse, the body of previous work suggests that participation of a halogen atom as electron donor within a HB can activate this atom as electron acceptor in an accompanying XB. Experimental and theoretical data ,− indicate just such a concept, albeit within the specialized framework of cation–anion interactions involved in halide binding. This HB/XB cooperativity has demonstrated implications for protein structure and function , and catalysis. , …”

Section: Introductionmentioning

confidence: 99%

Ability of Peripheral H Bonds to Strengthen a Halogen Bond

Scheiner

2022

J. Phys. Chem. A

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Quantum calculations study the manner in which the involvement of a halogen atom as a proton acceptor in one or more H bonds (HBs) affects the strength of the halogen bond (XB) it can form with a nucleophile aligned with the X σ-hole. A variety of Lewis acids wherein X = F, Cl, Br, and I are attached to a tetrel atom C or Ge engaged in a XB with nucleophile NH3. One, two, and three HF molecules were positioned perpendicular to the XB axis so that they could form a HB to the X atom. Each such HB strengthened the XB by an increment of 1 kcal/mol or more that does not attenuate as each new HB is added, potentially increasing the interaction energy manyfold. Additionally, the presence of one or more HBs facilitates the formation of a XB by molecules which are reluctant to engage in such a bond in the absence of these auxiliary interactions. Even the F atom, which avoids such a XB, can be coaxed to participate in a XB of moderate strength by one or more of these external HBs.

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Solvent Acts as the Referee in a Match‐Up Between Charged and Preorganized Receptors

Bhattacharjee,

Gao,

Nathani

et al. 2023

Chemistry A European J

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The prevalence of cation‐anion contacts in biomolecular recognition under aqueous conditions suggests that ionic interactions should dominate the binding of anions in solvents across both high and low polarities. Investigations of this idea using titrations in low polarity solvents are impaired by interferences from ion pairing that prevent a clear picture of binding. To address this limitation and test the impact of ion‐ion interactions across multiple solvents, we quantified chloride binding to a cationic receptor after accounting for ion pairing. In these studies, we created a chelate receptor using aryl‐triazole CH donors and a quinolinium that directs its cationic methyl inside the binding pocket. In low‐polarity dichloromethane, the 1:1 complex (log K1:1 ~ 7.3) is more stable than neutral chelates, but fortuitously comparable to a preorganized macrocycle (log K1:1 ~ 6.9). Polar acetonitrile and DMSO diminish stabilities of the charged receptor (log K1:1 ~3.7 and 1.9) but surprisingly 100‐fold more than the macrocycle. While both receptors lose stability by dielectric screening of electrostatic stability, the cationic receptor also pays additional costs of organization. Even though the charged and disorganized receptor has stronger binding in apolar solvents, the organized but uncharged receptor has more anion affinity in polar solvents.

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Pushing the limits of the hydrogen bond enhanced halogen bond—the case of the C–H hydrogen bond

Abstract: C–H hydrogen bonds have remarkable impacts on various chemical systems. Here we consider the influence of C–H hydrogen bonds to iodine atoms. Positioning a methyl group between two iodine halogen...

Cited by 19 publications

References 38 publications

Enhancement of Halogen Bond Strength by Intramolecular H-Bonds

Enhancement of Halogen Bond Strength by Intramolecular H-Bonds

Ability of Peripheral H Bonds to Strengthen a Halogen Bond

Solvent Acts as the Referee in a Match‐Up Between Charged and Preorganized Receptors

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