Influence of Substituent Effects on the Formation of P···Cl Pnicogen Bonds or Halogen Bonds

Bene, Janet E. Del; Alkorta, Ibón; Elguero, José

doi:10.1021/jp500915c

Cited by 75 publications

(101 citation statements)

References 35 publications

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“…For these calculations, the Ahlrichs 49 qzp basis set was placed on 13 C, 15 N, 17 O, and 19 F, and the qz2p basis set on 31 P and 35 Cl. The Dunning cc-pVDZ basis was placed on all 1 H atoms.…”

Section: ■ Methodsmentioning

confidence: 99%

Properties of Cationic Pnicogen-Bonded Complexes F_4–nH_nP⁺:N-Base with F–P···N Linear and n = 0–3

2015

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Ab initio MP2/aug′-cc-pVTZ calculations were performed to investigate the pnicogen-bonded complexes F 4−n H n P + :N-base, for n = 0−3, each with a linear or nearly linear F−P•••N alignment. The nitrogen bases include the sp 3 bases NH 3 , NClH 2 , NFH 2 , NCl 2 H, NCl 3 , NFCl 2 , NF 2 H, NF 2 Cl, and NF 3 and the sp bases NCNH 2 , NCCH 3 , NP, NCOH, NCCl, NCH, NCF, NCCN, and N 2 . The binding energies vary between −20 and −180 kJ•mol −1 , while the P−N distances vary from 1.89 to 3.01 Å. In each series of complexes, binding energies decrease exponentially as the P−N distance increases, provided that complexes with sp 3 and sp hybridized bases are treated separately. Different patterns are observed for the change in the binding energies of complexes with a particular base as the number of F atoms in the acid changes. Thus, the particular acid−base pair is a factor in determining the binding energies of these complexes. Three different charge-transfer interactions stabilize these complexes. These arise from the nitrogen lone pair to the σ*P−F ax , σ*P−F eq , and σ*P−H eq orbitals. The dominant single charge-transfer energy in all complexes is N lp → σ*P−F ax . However, since there are three N lp → σ*P−F eq charge-transfer interactions in complexes with F 4 P + and two in complexes with F 3 HP + , the sum of the N lp → σ*P−F eq charge-transfer energies is greater than the N lp → σ*P− F ax charge-transfer energies in the former complexes, and similar to the N lp → σ*P−F ax energies in the latter. The total chargetransfer energies of all complexes decrease exponentially as the P−N distance increases. Coupling constants 1p J(P−N) across the pnicogen bond vary with the P−N distance, but different patterns are observed for complexes with F 4 P + and complexes of the sp 3 bases with F 3 HP + . These initially increase as the P−N distance decreases, reach a maximum, and then decrease with decreasing P−N distance as the P•••N bond acquires increased covalent character. For the remaining complexes, 1p J(P−N) increases with decreasing P−N distance. Complexation increases the P−F ax distance and 1 J(P−F ax ) relative to the corresponding isolated ion. 1 J(P−F ax ) correlates quadratically with the P−N distance.

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Section: ■ Methodsmentioning

confidence: 99%

Properties of Cationic Pnicogen-Bonded Complexes F_4–nH_nP⁺:N-Base with F–P···N Linear and n = 0–3

2015

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“…Three different types of halogen bonds (traditional, chlorine-shared, and ion-pair) were identified, as were two pnictogen bonds ( Figure 5). 84 With electronegative substituents Y = F or CN, X-bonded complexes were identified (sketches XB-T, XB-S, and XB-IP), whereas when Y = Me or H pnictogen-bonded complexes resulted (sketches ZB-1 and ZB-2). The authors also used NBO analyses to show that charge-transfer contributions stabilized both pnictogen-bonded and halogen-bonded complexes; the dominant XB charge-transfer interaction involved P lone pair donation to the antibonding σ* Cl−Y orbital.…”

Section: Other Contributions To the Nature Of Halogen Bondingmentioning

confidence: 99%

Halogen Bonding in Supramolecular Chemistry

et al. 2015

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CONTENTS 1. Introduction to Halogen Bonding 7119 1.1. Nature of the Halogen Bond 7119 1.2. Scope of the Review 7120 2. Computational and Theoretical Investigations of Halogen Bonding 7120 2.1.Quantum Mechanics Methods 7120 2.2. σ-Hole Model of Halogen Bonding 7120 2.3. Other Contributions to the Nature of Halogen Bonding 7122 2.4. Recent Examples of Computationally Investigated Halogen-Bonded Complexes 7123 2.4.1. XB to Neutral Species 7123 2.4.2. XB to Anions 7126 2.4.3. XB in Protein−Ligand Complexes 7127 2.4.4. Electron-Transfer Processes Affected by XB Interactions 7127 2.5. Classical Force Field Calculations 7127 2.6. Conclusions and Outlook 7129 3. Gas-Phase Studies of Halogen-Bonding Interactions 7130 4. Halogen Bonding in the Solid State 7131 4.1. Introduction to Crystal Engineering and Functional Materials 7131 4.2. Fundamentals 7132 4.3. Halogen-Bonding Hierarchy 7134 4.3.1. Ranking Halogen-Bond Donors 7134 4.3.2. HB/XB Complementarity/Competition 7136 4.3.3. Predicting XBs 7138 4.4. Control of Solid-State Supramolecular Architectures 7138 4.4.1. Polymorphism 7138 4.4.2. Stoichiometry 7139 4.4.3. Tautomeric Control 7140 4.4.4. XBs Involving Metals and Metal-Bound XBs 7140 4.4.5. XB with Anions in the Solid State 4.5. Solid-State Architectures 4.6.

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“…It is well‐known that an sp 3 ‐hybridized P atom in a molecule can act as a base and donate a pair of electrons to another molecule to form various intermolecular bonds, such as hydrogen bonds (HB) and halogen bonds (XB) . The recent literature has focused on a second type of intermolecular bond involving phosphorus in which this atom acts as an acid by accepting a pair of electrons to form a pnicogen bond (ZB) .…”

Section: Introductionmentioning

confidence: 99%

Using (FH)₂ and (FH)₃ to Bridge the σ‐Hole and the Lone Pair at P in Complexes with H₂XP, for X=CH₃, OH, H, CCH, F, Cl, NC, and CN

2016

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Ab initio MP2/aug′‐cc‐pVTZ calculations are used to investigate the binary complexes H2XP:HF, the ternary complexes H2XP:(FH)2, and the quaternary complexes H2XP:(FH)3, for X=CH3, OH, H, CCH, F, Cl, NC, and CN. Hydrogen‐bonded (HB) binary complexes are formed between all H2XP molecules and FH, but only H2FP, H2ClP, and H2(NC)P form pnicogen‐bonded (ZB) complexes with FH. Ternary complexes with (FH)2 are stabilized by F−H⋅⋅⋅P and F−H⋅⋅⋅F hydrogen bonds and F⋅⋅⋅P pnicogen bonds, except for H2(CH3)P:(FH)2 and H3P:(FH)2, which do not have pnicogen bonds. All quaternary complexes H2XP:(FH)3 are stabilized by both F−H⋅⋅⋅P and F−H⋅⋅⋅F hydrogen bonds and P⋅⋅⋅F pnicogen bonds. Thus, (FH)2 with two exceptions, and (FH)3 can bridge the σ‐hole and the lone pair at P in these complexes. The binding energies of H2XP:(FH)3 complexes are significantly greater than the binding energies of H2XP:(FH)2 complexes, and nonadditivities are synergistic in both series. Charge transfer occurs across all intermolecular bonds from the lone‐pair donor atom to an antibonding σ* orbital of the acceptor molecule, and stabilizes these complexes. Charge‐transfer energies across the pnicogen bond correlate with the intermolecular P−F distance, while charge‐transfer energies across F−H⋅⋅⋅P and F−H⋅⋅⋅F hydrogen bonds correlate with the distance between the lone‐pair donor atom and the hydrogen‐bonded H atom. In binary and quaternary complexes, charge transfer energies also correlate with the distance between the electron‐donor atom and the hydrogen‐bonded F atom. EOM‐CCSD spin‐spin coupling constants 2hJ(F–P) across F−H⋅⋅⋅P hydrogen bonds, and 1pJ(P–F) across pnicogen bonds in binary, ternary, and quaternary complexes exhibit strong correlations with the corresponding intermolecular distances. Hydrogen bonds are better transmitters of F–P coupling data than pnicogen bonds, despite the longer F⋅⋅⋅P distances in F−H⋅⋅⋅P hydrogen bonds compared to P⋅⋅⋅F pnicogen bonds. There is a correlation between the two bond coupling constants 2hJ(F–F) in the quaternary complexes and the corresponding intermolecular distances, but not in the ternary complexes, a reflection of the distorted geometries of the bridging dimers in ternary complexes.

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Influence of Substituent Effects on the Formation of P···Cl Pnicogen Bonds or Halogen Bonds

Cited by 75 publications

References 35 publications

Properties of Cationic Pnicogen-Bonded Complexes F_4–nH_nP⁺:N-Base with F–P···N Linear and n = 0–3

Properties of Cationic Pnicogen-Bonded Complexes F_4–nH_nP⁺:N-Base with F–P···N Linear and n = 0–3

Halogen Bonding in Supramolecular Chemistry

Using (FH)₂ and (FH)₃ to Bridge the σ‐Hole and the Lone Pair at P in Complexes with H₂XP, for X=CH₃, OH, H, CCH, F, Cl, NC, and CN

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Influence of Substituent Effects on the Formation of P···Cl Pnicogen Bonds or Halogen Bonds

Cited by 75 publications

References 35 publications

Properties of Cationic Pnicogen-Bonded Complexes F4–nHnP+:N-Base with F–P···N Linear and n = 0–3

Properties of Cationic Pnicogen-Bonded Complexes F4–nHnP+:N-Base with F–P···N Linear and n = 0–3

Halogen Bonding in Supramolecular Chemistry

Using (FH)2 and (FH)3 to Bridge the σ‐Hole and the Lone Pair at P in Complexes with H2XP, for X=CH3, OH, H, CCH, F, Cl, NC, and CN

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Properties of Cationic Pnicogen-Bonded Complexes F_4–nH_nP⁺:N-Base with F–P···N Linear and n = 0–3

Properties of Cationic Pnicogen-Bonded Complexes F_4–nH_nP⁺:N-Base with F–P···N Linear and n = 0–3

Using (FH)₂ and (FH)₃ to Bridge the σ‐Hole and the Lone Pair at P in Complexes with H₂XP, for X=CH₃, OH, H, CCH, F, Cl, NC, and CN