Dihalogens as Halogen Bond Donors

Haukka, Matti; Hirva, Pipsa; Rissanen, Kari

doi:10.1002/9781119113874.ch10

Cited by 4 publications

(6 citation statements)

References 89 publications

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“…First, we observed that the electron belt of molecular iodine forms noncovalent contacts with the nickel(II) center to give a Ni II ···I–I semicoordination bond (97% from the sum of Bondi’s vdW radii for Ni and I; estimated strength is 2.2 kcal/mol at the M06/DZP-DKH level of theory within the framework of QTAIM approach). Although I 2 quite rarely behaves as a ligand, binding through its electron belt to Ag I , Pb II , and Rh II centers and the relevant ability to serve as a hydrogen and halogen bond acceptor have been reported, and our observation is the first example of electron belt semicoordination of I 2 to a nickel(II) center.…”

Section: Discussionmentioning

confidence: 59%

Electrophilic–Nucleophilic Dualism of Nickel(II) toward Ni···I Noncovalent Interactions: Semicoordination of Iodine Centers via Electron Belt and Halogen Bonding via σ-Hole

et al. 2017

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The nitrosoguanidinate complex [Ni{NH═C(NMe)NN(O)}] (1) was cocrystallized with I and sym-trifluorotriiodobenzene (FIB) to give associates 1·2I and 1·2FIB. Structures of these solid species were studied by XRD followed by topological analysis of the electron density distribution within the framework of Bader's approach (QTAIM) at the M06/DZP-DKH level of theory and Hirshfeld surface analysis. Our results along with inspection of XRD (CCDC) data, accompanied by the theoretical calculations, allowed the identification of three types of Ni···I contacts. The Ni···I semicoordination of the electrophilic nickel(II) center with electron belt of I was observed in 1·2I, the metal-involving halogen bonding between the nucleophilic nickel(II)-d center and σ-hole of iodine center was recognized and confirmed theoretically in the structure of [FeNi(CN)(IPz)(HO)] (IPz = 4-N-coordinated 2-I-pyrazine), whereas the arrangement of FIB in 1·2FIB provides a boundary case between the semicoordination and the halogen Ni···I bondings. In 1·2I and 1·2FIB, noncovalent interactions were studied by variable temperature XRD detecting the expansion of noncovalent contacts with preservation of covalent bond lengths upon the temperature increase from 100 to 300 K. The nature and energies of all identified types of the Ni···I noncovalent interactions in the obtained (1·2I and 1·2FIB) and in the previously reported ([FeNi(CN)(IPz)(HO)], [NiL](I)·2I (L = o-phenylene-bis(dimethylphosphine), [NiL]I (L = 1,4,8,11-tetra-azacyclotetradecane), Ni(en)][AgI] (en = ethylenediamine), and [NiL](ClO) (L = 4-iodo-2-((2-(2-(2-pyridyl)ethylsulfanyl)ethylimino)methyl)-phenolate)) structures were studied theoretically. The estimated strengths of these Ni···I noncovalent contacts vary from 1.6 to 4.1 kcal/mol and, as expected, become weaker on heating. This work is the first emphasizing electrophilic-nucleophilic dualism of any metal center toward noncovalent interactions.

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Section: Discussionmentioning

confidence: 59%

Electrophilic–Nucleophilic Dualism of Nickel(II) toward Ni···I Noncovalent Interactions: Semicoordination of Iodine Centers via Electron Belt and Halogen Bonding via σ-Hole

et al. 2017

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“…It has been shown that highly directional halogen bonds are stronger than those that deviate significantly from 180° [7,109]. High directionality, together with the involvement between a positive and a negative site, is the primary requirement for the formation of a type-II halogen bonding topology, while such a requirement is not necessary for the formation of type-I interactions [110,111].…”

Section: Resultsmentioning

confidence: 99%

“…This shows that the definition of type-II halogen bonding illustrated in Scheme 2 is not applicable to the intermolecular interactions found for complexes in Figure 2. Also, the Y···F–R interactions in the complexes of Figure 2 (except (NF 3 ) 2 ) cannot be called halogen···halogen type-I interactions [110,111] because the angles of interaction (θ = ∠Y···F–R) for these dimers of Figure 2 lie in the range 170° < θ < 180°; for type-I halogen bonding the angle is generally 90° < θ < 150° [110,111].…”

Section: Resultsmentioning

confidence: 99%

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Is the Fluorine in Molecules Dispersive? Is Molecular Electrostatic Potential a Valid Property to Explore Fluorine-Centered Non-Covalent Interactions?

2019

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Can two sites of positive electrostatic potential localized on the outer surfaces of two halogen atoms (and especially fluorine) in different molecular domains attract each other to form a non-covalent engagement? The answer, perhaps counterintuitive, is yes as shown here using the electronic structures and binding energies of the interactions for a series of 22 binary complexes formed between identical or different atomic domains in similar or related halogen-substituted molecules containing fluorine. These were obtained using various computational approaches, including density functional and ab initio first-principles theories with M06-2X, RHF, MP2 and CCSD(T). The physical chemistry of non-covalent bonding interactions in these complexes was explored using both Quantum Theory of Atoms in Molecules and Symmetry Adapted Perturbation Theories. The surface reactivity of the 17 monomers was examined using the Molecular Electrostatic Surface Potential approach. We have demonstrated inter alia that the dispersion term, the significance of which is not always appreciated, which emerges either from an energy decomposition analysis, or from a correlated calculation, plays a structure-determining role, although other contributions arising from electrostatic, exchange-repulsion and polarization effects are also important. The 0.0010 a.u. isodensity envelope, often used for mapping the electrostatic potential is found to provide incorrect information about the complete nature of the surface reactive sites on some of the isolated monomers, and can lead to a misinterpretation of the results obtained.

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“…The halogen bond (XB) was first discovered in 1863, some 50 years before its conceptual congener, the hydrogen bond . While the latter concept has drawn significantly more attention during the last century, the past few decades have also witnessed increasing interest toward both theoretical − and practical aspects of XB, especially through utilization of halogen bonds in building functional materials. − Accordingly, numerous applications in a variety of fields such as ion recognition, − optical materials, − organic synthesis and catalysis, medicinal chemistry, − and crystal engineering and supramolecular chemistry − have been reported. It is evident that the halogen-bonding concept has grown from infancy to maturity.…”

Section: Introductionmentioning

confidence: 99%

Reactivity of 4-Aminopyridine with Halogens and Interhalogens: Weak Interactions Supported Networks of 4-Aminopyridine and 4-Aminopyridinium

Malinen

Haukka

Konu

2019

Crystal Growth & Design

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The reaction of 4-aminopyridine (4-AP) with ICl in a 1:1 molar ratio in CH2Cl2 produced the expected charge-transfer complex [4-NH2-1λ 4-C5H4N-1-ICl] (1·ICl) and the ionic species [(4-NH2-1λ 4-C5H4N)2-1μ-I+][Cl–] (2·Cl–) in a 2:1 relation, as indicated by 1H NMR spectroscopy in solution. In contrast, only the ionic compound [(4-NH2-1λ 4-C5H4N)2-1μ-I+][IBr2 –] (2·IBr2 –) was observed in the analogous reaction with IBr. The reaction between 4-AP and I2 in a 1:1 molar ratio also afforded two components, one of which was identified as the congeneric cation in [(4-NH2-1λ 4-C5H4N)2-1μ-I+][I7 –] (2·I7 –) that contains a polyiodide anion as a result of transformation in a 1:2 molar ratio between the starting materials. In all of these ionic products, the crystal structures feature an iodonium ion, I+, trapped between two 4-AP rings through N···I+···N contact. Surprisingly, the reaction of 4-AP with Br2 in CH2Cl2 resulted in an immediate protonation of the 4-aminopyridine (1H NMR) and [4-NH2-1λ 4-C5H4N-1-H+][Br–] (3·Br–) was characterized as the main product. A subsequent peculiar bromination–dimerization process afforded the novel pyridyl-pyridinium cations {3,3′,5′-Br3-1λ 4-[1,2′-(C5H4N)2]-4,4′-(NH2)2}+[X–] (4·Br–, 4·Br3 –) and {3′,5′-Br2-1λ 4-[1,2′-(C5H4N)2]-4,4′-(NH2)2}+[X–] (5·Br–, 5·Br3 –). Compounds 1–5 as well as two protonated species, [4-NH2-1λ 4-C5H4N-1-H+]2[Cl–][I3 –] (3 2·Cl–·I3 –) and [(4-NH2-1λ 4-C5H4N)2-1μ-H+][I–] (6·I–), all display extended 3D networks supported by halogen and hydrogen bonding in the solid state.

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Dihalogens as Halogen Bond Donors

Cited by 4 publications

References 89 publications

Electrophilic–Nucleophilic Dualism of Nickel(II) toward Ni···I Noncovalent Interactions: Semicoordination of Iodine Centers via Electron Belt and Halogen Bonding via σ-Hole

Electrophilic–Nucleophilic Dualism of Nickel(II) toward Ni···I Noncovalent Interactions: Semicoordination of Iodine Centers via Electron Belt and Halogen Bonding via σ-Hole

Is the Fluorine in Molecules Dispersive? Is Molecular Electrostatic Potential a Valid Property to Explore Fluorine-Centered Non-Covalent Interactions?

Reactivity of 4-Aminopyridine with Halogens and Interhalogens: Weak Interactions Supported Networks of 4-Aminopyridine and 4-Aminopyridinium

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