Comparison between Hydrogen and Halogen Bonds in Complexes of 6‐OX‐Fulvene with Pnicogen and Chalcogen Electron Donors

Hou, Mingchang; Scheiner, Steve

doi:10.1002/cphc.201900340

Cited by 15 publications

(19 citation statements)

References 58 publications

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“…Beyond the well documented issue of the nature of the Lewis acid and base, [44] there are other important factors such as solvent polarity. Beyond the well documented issue of the nature of the Lewis acid and base, [44] there are other important factors such as solvent polarity.…”

Section: Introductionmentioning

confidence: 99%

“…The question of how to precisely regulate the intensity of various noncovalent bonds has become the focus of extensive research. Beyond the well documented issue of the nature of the Lewis acid and base, [44] there are other important factors such as solvent polarity. [45] As an added factor, cooperative interactions between two or more such bonds can also affect their strengths.…”

Section: Introductionmentioning

confidence: 99%

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Tuning the Competition between Hydrogen and Tetrel Bonds by a Magnesium Bond

2020

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A computational study of the complexes formed by TF 3 OH (T=C, Si, Ge) with three nitrogen-containing bases NCH, NH 3 , and imidazole (IM) is carried out at the MP2/aug-cc-pVTZ level. TF 3 OH can participate in two different types of noncovalent interactions: a hydrogen bond (HB) involving the hydroxyl proton and a tetrel bond (TB) with the tetel atom T. The strength of the HB is largely unaffected by the identity of T while the TB is enhanced as T grows larger. The HB is preferred over the TB for most systems, with the exception of GeF 3 OH with either NH 3 or IM. MgCl 2 engages in a Mg···O Magnesium bond (Mg-bond) with the TF 3 OH O atom, which cooperatively enhances both the HB and TB. The HB strengthening is particularly large for the NH 3 or IM bases, and especially for CF 3 OH, but is slowly reduced as the T atom grows larger. The TB enhancement, on the other hand, behaves in the opposite fashion, accelerating for the larger T atoms. As a bottom line, the Mg-bond generally reinforces and accentuates the preference for the HB or TB that is already present in the dimer. The Mg-bond is also responsible for a proton transfer in the HB configurations with NH 3 and IM.[a] Dr.

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Section: Introductionmentioning

confidence: 99%

Section: Introductionmentioning

confidence: 99%

Tuning the Competition between Hydrogen and Tetrel Bonds by a Magnesium Bond

2020

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“…However, the reverse of this order was observed in complexes between H 2 Te and 6‐OX‐fulvene (X = H, Cl, Br, and I). [ 54 ] Moreover, the halogen bond is particularly strong for X = Cl, much stronger than the corresponding hydrogen bond. [ 54 ] A similar trend was also noted in the complexes between H 2 Te and XF (X = H, Cl, Br, and I).…”

Section: Discussionmentioning

confidence: 99%

Unusual substituent effects in the Tr···Te triel bond

Wang

Luo

Scheiner

2020

Int J of Quantum Chemistry

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The triel bond between the π‐hole on the triel atom of TrR3 (Tr = B, Al, Ga; R = H, F, Cl, Br) and a lone pair on the Te atom of H2Te is examined using ab initio methods. For Tr = B, the triel bond is weakened as the R substituent becomes more electronegative, while the opposite pattern is noted for Al and Ga. The weakest triel bond of all occurs in H2Te‐BF3 (2.9 kcal/mol) but is much stronger for all the other complexes (>11 kcal/mol). The placement of electron‐releasing OH, NH2, and CH3 R′ substituents on the R′2Te base strengthens the triel bond, whereas the opposite occurs for the electron‐withdrawing CN. Despite its high electronegativity, the F substituent causes a strengthening of the interaction, which is due in large part to the formation of secondary chalcogen bonds that involve the σ‐holes on Te in F2Te. However, the F atom on TrF3 is unable to act as an electron donor in these chalcogen bonds, leading to weakened F2Te··TrF3 interactions.

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“…Thioformaldehyde can reduce the difference in the binding strength between XB and HB in the HOBr complex (Li et al, 2011). If TeH 2 acts as the electron donor, the XB is more favorable than the HB in complexes with 6-OX-fulvene (X = H, Cl, Br, I) (Hou et al, 2019b). This shows that introduction of a fulvene skeleton to an atom/group may cause an interesting result when this atom/group participates in an intermolecular interaction.…”

Section: Introductionmentioning

confidence: 99%

Reliable Comparison of Pnicogen, Chalcogen, and Halogen Bonds in Complexes of 6-OXF2-Fulvene (X = As, Sb, Se, Te, Be, I) With Three Electron Donors

Liu

McDowell

2020

Front. Chem.

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The pnicogen, chalcogen, and halogen bonds between 6-OXF2-fulvene (X = As, Sb, Se, Te, Br, and I) and three nitrogen-containing bases (FCN, HCN, and NH3) are compared. For each nitrogen base, the halogen bond is strongest, followed by the pnicogen bond, and the chalcogen bond is weakest. For each type of bond, the binding increases in the FCN < HCN < NH3 pattern. Both FCN and HCN engage in a bond with comparable strengths and the interaction energies of most bonds are < −6 kcal/mol. However, the strongest base NH3 forms a much more stable complex, particularly for the halogen bond with the interaction energy going up to −18 kcal/mol. For the same type of interaction, its strength increases as the mass of the central X atom increases. These bonds are different in strength, but all of them are dominated by the electrostatic interaction, with the polarization contribution important for the stronger interaction. The presence of these bonds changes the geometries of 6-OXF2-fulvene, particularly for the halogen bond formed by NH3, where the F-X-F arrangement is almost vertical to the fulvene ring.

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Comparison between Hydrogen and Halogen Bonds in Complexes of 6‐OX‐Fulvene with Pnicogen and Chalcogen Electron Donors

Cited by 15 publications

References 58 publications

Tuning the Competition between Hydrogen and Tetrel Bonds by a Magnesium Bond

Tuning the Competition between Hydrogen and Tetrel Bonds by a Magnesium Bond

Unusual substituent effects in the Tr···Te triel bond

Reliable Comparison of Pnicogen, Chalcogen, and Halogen Bonds in Complexes of 6-OXF2-Fulvene (X = As, Sb, Se, Te, Be, I) With Three Electron Donors

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