Dataset Information

Multicenter (FX)n/NH? Halogen Bonds (X = Cl, Br and n = 1-5). QTAIM Descriptors of the Strength of the X???N Interaction.

ABSTRACT: In the present work an in depth deep electronic study of multicenter XBs (FX)n/NH? (X = Cl, Br and n = 1-5) is conducted. The ways in which X???X lateral contacts affect the electrostatic or covalent nature of the X???N interactions are explored at the CCSD(T)/aug-cc-pVTZ level and in the framework of the quantum theory of atoms in molecules (QTAIM). Calculations show that relatively strong XBs have been found with interaction energies lying between -41 and -90 kJ mol-1 for chlorine complexes, and between -56 and -113 kJ mol-1 for bromine complexes. QTAIM parameters reveal that in these complexes: (i) local (kinetics and potential) energy densities measure the ability that the system has to concentrate electron charge density at the intermolecular X???N region; (ii) the delocalization indices [?(A,B)] and the exchange contribution [VEX(X,N)] of the interacting quantum atoms (IQA) scheme, could constitute a quantitative measure of the covalence of these molecular interactions; (iii) both classical electrostatic and quantum exchange show high values, indicating that strong ionic and covalent contributions are not mutually exclusive.

SUBMITTER: Buralli GJ

PROVIDER: S-EPMC6150306 | biostudies-literature | 2017 Nov

REPOSITORIES: biostudies-literature

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Publications

Multicenter (FX)n/NH₃ Halogen Bonds (X = Cl, Br and n = 1-5). QTAIM Descriptors of the Strength of the X∙∙∙N Interaction.

Buralli Gabriel J GJ Petelski Andre N AN Peruchena Nélida M NM Sosa Gladis L GL Duarte Darío J R DJR

Molecules (Basel, Switzerland) 20171122 11

In the present work an in depth deep electronic study of multicenter XBs (FX)n/NH₃ (X = Cl, Br and n = 1-5) is conducted. The ways in which X∙∙∙X lateral contacts affect the electrostatic or covalent nature of the X∙∙∙N interactions are explored at the CCSD(T)/aug-cc-pVTZ level and in the framework of the quantum theory of atoms in molecules (QTAIM). Calculations show that relatively strong XBs have been found with interaction energies lying between -41 and -90 kJ mol-1 for ...[more]

PMID: 29165403

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Project description:The behavior of a sterically crowded neutral pincer {2,6-bis[(di-t-butylphosphino)methyl]-phenyl}palladium (PCPPd) halides, PCPPdX (X = Cl, Br or I), as XB acceptors with strong halogen bond (XB) donors, iodine (I(2)), 1,4-diiodotetrafluorobenzene (F4DIBz), and 1,4-diiodooctafluorobutane (F8DIBu) were studied in the solid state. The co-crystallization experiments afforded high-quality single crystals of XB complexes PCPPdCl-I(2) (1a), PCPPdBr-I(2) (2a), PCPPdI-I(2)(3a), PCPPdCl-F4DIBz (1b), PCPPdBr-F4DIBz (2b), and PCPPdBr-F8DIBu (2c). The 1:1 iodine complexes (1a, 2a, and 3a) all showed a strong halogen bonding interaction, the reduction of the sum of the van der Waals radii of halogen to iodine being 24.6 (1a), 23.9 (2a), and 19.4% (3a) with X···I-I angles of 177, 176, and 179°, respectively. While the pincer palladium chloride 1 and bromide 2 were crystallographically isomorphous and showed similar XB behavior, the palladium iodide complex, 3, exhibited markedly different properties, and unlike 1 and 2 it does not, under similar conditions, result in XB complexes with the weaker XB donors F4DIBz and F8DIBu. The results indicate that PCPPdI is not nucleophilic enough to have XB interactions with other donors than iodine. However, the weaker XB donors F4DIBz and F8DIBu form XB complexes with the chloride 1 and especially with the bromide 2. The prevalence of the halogen bonding with 2 is probably not only electronic in origin, and it seems to offer the best balance between electron poorness and steric availability. The XB interactions with F4DIBz and F8DIBu are much weaker than with iodine, the reduction of the sum of the van der Waals radii of halogen to iodine being 13.5, 12.3, and 14.6% with C-I···X angles between 163 and 179° for 1b, 2b, and 2c, respectively, and results in polymeric (···1···F4DIBz···1···F4DIBz···)(n), (···2···F4DIBz···2···F4DIBz···)(n), and (···2···F8DIBu···2···F8DIBu···)(n) one-dimensional zigzag chains in the solid state.

Dataset Information

Multicenter (FX)n/NH? Halogen Bonds (X = Cl, Br and n = 1-5). QTAIM Descriptors of the Strength of the X???N Interaction.

Publications

Multicenter (FX)<sub>n</sub>/NH₃ Halogen Bonds (X = Cl, Br and n = 1-5). QTAIM Descriptors of the Strength of the X∙∙∙N Interaction.

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