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Relationships between Interaction Energy and Electron Density Properties for Homo Halogen Bonds of the [(A)nY-X···X-Z(B)m] Type (X = Cl, Br, I).

ABSTRACT: Relationships between interaction energy (Eint) and electron density properties at the X···X bond critical point or the d(X···X) distance were established for the large set of structures [(A)nY-X···X-Z(B)m] bearing the halogen bonds Cl···Cl, Br···Br, and I···I (640 structures in total). The best estimator of Eint is the kinetic energy density (Gb), which reasonably approximates the whole set of the structures as -Eint = 0.128Gb2 - 0.82Gb + 1.66 (R2 = 0.91, mean absolute deviation 0.39 kcal/mol) and demonstrates low dispersion. The potential and kinetic energy densities, electron density, and the d(X···X) distance behave similarly as estimators of Eint for the individual series Cl···Cl, Br···Br, and I···I. A number of the Eint(property) correlations are recommended for the practical application in the express estimates of the strength of the homo-halogen bonds.

SUBMITTER: Kuznetsov ML

PROVIDER: S-EPMC6695802 | biostudies-literature | 2019 Jul

REPOSITORIES: biostudies-literature

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Relationships between Interaction Energy and Electron Density Properties for Homo Halogen Bonds of the [(A)nY-X···X-Z(B)m] Type (X = Cl, Br, I).

Kuznetsov Maxim L ML

Molecules (Basel, Switzerland) 20190727 15

Relationships between interaction energy (Eint) and electron density properties at the X···X bond critical point or the d(X···X) distance were established for the large set of structures [(A)nY-X···X-Z(B)m] bearing the halogen bonds Cl···Cl, Br···Br, and I···I (640 structures in total). The best estimator of Eint is the kinetic energy density (Gb), which reasonably approximates the whole set of the structures as -Eint</sub ...[more]

PMID: 31357615

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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

Relationships between Interaction Energy and Electron Density Properties for Homo Halogen Bonds of the [(A)nY-X···X-Z(B)m] Type (X = Cl, Br, I).

Publications

Relationships between Interaction Energy and Electron Density Properties for Homo Halogen Bonds of the [(A)<i><sub>n</sub></i>Y-X···X-Z(B)<i><sub>m</sub></i>] Type (X = Cl, Br, I).

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