Orthogonal interactions between nitryl derivatives and electron donors: pnictogen bonds

Sánchez‐Sanz, Goar; Trujillo, Cristina; Solimannejad, Mohammad; Alkorta, Ibón; Elguero, José

doi:10.1039/c3cp52312h

Cited by 80 publications

(87 citation statements)

References 77 publications

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“…We have previously reported the structural data of XNO 2 monomers with X = F, Cl, Br and I 50,52 and shown that theoretical results are in good agreement with the experimental data found in literature. For comparison purposes the electronic characteristics of those monomers have been studied, especially their molecular electrostatic potential, MEP (Table 1).…”

Section: Monomerssupporting

confidence: 91%

“…It is worth noting that nitryl fluoride does not have a σ-hole along the F-N axis, as was observed in previous studies. 50,52 Regarding the minima values of the MEP on the vdW isosurface, those associated with the halogen lone pair decrease with the size of X 5 atom. Two different electron lone pairs belonging to the oxygen atoms were located, the one closest to the halogen bond (b) and the furthest respect to the X (c).…”

Section: Monomersmentioning

confidence: 98%

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Halogen, chalcogen and pnictogen interactions in (XNO₂)₂homodimers (X = F, Cl, Br, I)

et al. 2015

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Keywords Halogen bond, chalcogen bond, pnictogen bond, non covalent interactions Graphical Abstract Abstract A theoretical study of the XNO 2 homodimers (X = F, Cl, Br and I) has been carried out by means of the Møller-Plesset (MP2) methodology. Twenty-two different minimum structures have been found, involving pnictogen, chalcogen and halogen bonds. MP2 interaction energies range between -0.4 to -17.5 kJ·mol -1 . Atoms in Molecules (AIM) and Natural Bond Orbital (NBO) approaches have been used to analyse the nature of the interaction within both monomers, obtaining good correlations between Laplacian values and bond distances. NBO E (2) orbital interaction energies are found to be up to 39.0 kJ·mol -1 . Charge transfer between monomers are in agreement with those in AIM and NBO findings, showing the highest charge transferred in those asymmetric dimers which involve pure halogen bonds. Symmetry Adapted Perturbation Theory (SAPT-DFT) results show that the interactions are driven by the dispersion term, followed by the electrostatic one. The induction term present the lowest contribution with the exception of complexes 1 and 5 of the iodine derivative in which E i(2) shows the maximum contribution to the total forces.

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Section: Monomerssupporting

confidence: 91%

Section: Monomersmentioning

confidence: 98%

Halogen, chalcogen and pnictogen interactions in (XNO₂)₂homodimers (X = F, Cl, Br, I)

et al. 2015

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“…In phosphorus derivatives, the range of r is slightly wider (0.019-0.049) than in the arsenic ones (0.019-0.038). 42,80,83,102,[104][105][106][107][108][109][110][111] The electron density shift maps (EDS) of the intramolecular interactions have been obtained following the procedure reported in ref. suggest closed shell regimen interactions, being this range wider in P derivatives (0.028-0.046 a.u.)…”

Section: Electronic Properties (Aim Nbo Eds Nci)mentioning

confidence: 99%

Intramolecular pnicogen interactions in phosphorus and arsenic analogues of proton sponges

Sánchez‐Sanz

Trujillo

Alkorta

et al. 2014

Phys. Chem. Chem. Phys.

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A computational study of the intramolecular pnicogen bond in 1,8-bis-substituted naphthalene derivatives (ZXH and ZX2 with Z = P, As and X = H, F, Cl, and Br), structurally related to proton sponges, has been carried out. The aim of this paper is the study of their structural parameters, interaction energies and electronic properties such as electron density on the intramolecular interaction. The calculated geometrical parameters associated to the P···P interaction are in reasonably good agreement with the crystal structures found in a CSD search, in particular those of the halogen derivatives. Isodesmic reactions where the 1,8-bis-substituted derivatives are compared to monosubstituted derivatives have been calculated, indicating that the 1,8 derivatives are more stable than the monosubstituted ones for those cases with X-Z···Z-X and F-Z···Z-H alignments. Electron densities and Laplacians at the BCP on the pnicogen interactions suggest that they can be classified as pure closed shell interactions with a partial covalent character. Electron density shift maps are consistent with the results for intermolecular pnicogen interactions. Relationships between interatomic distance and electron density at the bond critical points and between interatomic distance and the orbital charge transfer stabilization energies have been found.

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“…18 Furthermore, sp 2 hybridized phosphorus compound H 2 CP==X (X = F, Cl, OH, CN, NC, CCH, H, and BH 2 ) is also able to form ZBs. 19,20 On the other hand, NO 2 X (X = F, Cl, CN, and NO 2 ) 21 and PO 2 X (X = F, Cl, and Br) 22 provide a π-hole to participate in pnicogen bond interactions with Lewis bases, and in most cases, the π-hole is a stronger Lewis acid than a) Author to whom correspondence should be addressed. Electronic mail:…”

Section: Introductionmentioning

confidence: 99%

Non-additivity between substitution and cooperative effects in enhancing hydrogen bonds

Zhuo

Cheng

2014

The Journal of Chemical Physics

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Ternary systems XO2F:NCH:NCY and XO2F:CNH:CNY (X = P and As; Y = H and Li) as well as the corresponding binary ones were studied at the MP2/aug-cc-pVTZ level. Interestingly, the π-hole pnicogen bond in the PO2F complex is stronger than that in the AsO2F counterpart. The substituent Li in the Lewis base strengthens the hydrogen bond and pnicogen bond, but the more prominent enhancing effect is found for the pnicogen bond. The substitution effect is governed mainly through electrostatic interaction for the hydrogen bond but a combination of electrostatic and polarization interactions for the pnicogen bond. In the ternary systems, the π-hole pnicogen bond exhibits a positive cooperative effect with the hydrogen bond. Energy decomposition analysis indicates that the cooperativity is mainly attributed to the polarization energy. There is positive non-additivity between the substitution and cooperative effects, which is an effective measure for strengthening the hydrogen bond. The largest interaction energies occur in AsO2F:CNH:CNLi, amounting to -130.24 kJ/mol for the pnicogen bond and -119.90 kJ/mol for the hydrogen bond, and the former is a covalent interaction and the latter is an ion-pair hydrogen bond.

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Orthogonal interactions between nitryl derivatives and electron donors: pnictogen bonds

Cited by 80 publications

References 77 publications

Halogen, chalcogen and pnictogen interactions in (XNO₂)₂homodimers (X = F, Cl, Br, I)

Halogen, chalcogen and pnictogen interactions in (XNO₂)₂homodimers (X = F, Cl, Br, I)

Intramolecular pnicogen interactions in phosphorus and arsenic analogues of proton sponges

Non-additivity between substitution and cooperative effects in enhancing hydrogen bonds

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Orthogonal interactions between nitryl derivatives and electron donors: pnictogen bonds

Cited by 80 publications

References 77 publications

Halogen, chalcogen and pnictogen interactions in (XNO2)2homodimers (X = F, Cl, Br, I)

Halogen, chalcogen and pnictogen interactions in (XNO2)2homodimers (X = F, Cl, Br, I)

Intramolecular pnicogen interactions in phosphorus and arsenic analogues of proton sponges

Non-additivity between substitution and cooperative effects in enhancing hydrogen bonds

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Product

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Halogen, chalcogen and pnictogen interactions in (XNO₂)₂homodimers (X = F, Cl, Br, I)

Halogen, chalcogen and pnictogen interactions in (XNO₂)₂homodimers (X = F, Cl, Br, I)