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Evaluation of dispersion type metal···? arene interaction in arylbismuth compounds - an experimental and theoretical study.

ABSTRACT: The dispersion type Bi···? arene interaction is one of the important structural features in the assembly process of arylbismuth compounds. Several triarylbismuth compounds and polymorphs are discussed and compared based on the analysis of single crystal X-ray diffraction data and computational studies. First, the crystal structures of polymorphs of Ph₃Bi (1) are described emphasizing on the description of London dispersion type bismuth···? arene interactions and other van der Waals interactions in the solid state and the effect of it on polymorphism. For comparison we have chosen the substituted arylbismuth compounds (C₆H₄-CH?CH₂-4)₃Bi (2), (C₆H₄-OMe-4)₃Bi (3), (C₆H₃-t-Bu₂-3,5)₃Bi (4) and (C₆H₃-t-Bu₂-3,5)₂BiCl (5). The structural analyses revealed that only two of them show London dispersion type bismuth···? arene interactions. One of them is the styryl derivative 2, for which two polymorphs were isolated. Polymorph 2a crystallizes in the orthorhombic space group P2₁2₁2₁, while polymorph 2b exhibits the monoclinic space group P2₁/c. The general structure of 2a is similar to the monoclinic C2/c modification of Ph₃Bi (1a), which leads to the formation of zig-zag Bi-arene_centroid ribbons formed as a result of bismuth···? arene interactions and ?···? intermolecular contacts. In the crystal structures of the polymorph 2b as well as for 4 bismuth···? arene interactions are not observed, but both compounds revealed C-H_Ph···? intermolecular contacts, as likewise observed in all of the three described polymorphs of Ph₃Bi. For compound 3 intermolecular contacts as a result of coordination of the methoxy group to neighboring bismuth atoms are observed overruling Bi···? arene contacts. Compound 5 shows a combination of donor acceptor Bi···Cl and Bi···? arene interactions, resulting in an intermolecular pincer-type coordination at the bismuth atom. A detailed analysis of three polymorphs of Ph₃Bi (1), which were chosen as model systems, at the DFT-D level of theory supported by DLPNO-CCSD(T) calculations reveals how van der Waals interactions between different structural features balance in order to stabilize molecular arrangements present in the crystal structure. Furthermore, the computational results allow to group this class of compounds into the range of heavy main group element compounds which have been characterized as dispersion energy donors in previous work.

SUBMITTER: Preda AM

PROVIDER: S-EPMC6122404 | biostudies-literature | 2018

REPOSITORIES: biostudies-literature

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Evaluation of dispersion type metal···π arene interaction in arylbismuth compounds - an experimental and theoretical study.

Preda Ana-Maria AM Krasowska Małgorzata M Wrobel Lydia L Kitschke Philipp P Andrews Phil C PC MacLellan Jonathan G JG Mertens Lutz L Korb Marcus M Rüffer Tobias T Lang Heinrich H Auer Alexander A AA Mehring Michael M

Beilstein journal of organic chemistry 20180815

The dispersion type Bi···π arene interaction is one of the important structural features in the assembly process of arylbismuth compounds. Several triarylbismuth compounds and polymorphs are discussed and compared based on the analysis of single crystal X-ray diffraction data and computational studies. First, the crystal structures of polymorphs of Ph<sub>3</sub>Bi (<b>1</b>) are described emphasizing on the description of London dispersion type bismuth···π arene interactions and other van der W ...[more]

PMID: 30202466

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Project description:Two stable nitronyl nitroxide free radicals {R 1 = 4'-methoxy-phenyl-4,4,5,5,-tetramethylimidazoline-1-oxyl-3-oxide (NNPhOMe) and R 2 = 2-(2'-thienyl)-4,4,5,5-tetramethylimidazoline 3-oxide 1-oxyl (NNT)} are successfully synthesized using Ullmann condensation. The reactions of these two radicals with 3d transition metal ions, in the form of M(hfac)2 (where M = Co or Mn, hfac: hexafluoroacetylacetone), result in four metal-organic complexes Co(hfac)2(NNPhOMe)2, 1; Co(hfac)2(NNT)2·(H2O), 2; Mn(hfac)2(NNPhOMe)·x(C7H16), 3; and Mn(hfac)2(NNT)2, 4. The crystal structure and magnetic properties of these complexes are investigated by single-crystal X-ray diffraction, dc magnetization, infrared, and electron paramagnetic resonance spectroscopies. The compounds 1 and 4 crystallize in the triclinic, P1̅, space group, whereas complex 3 crystallizes in the monoclinic structure with the C2/c space group and forms chain-like structure along the c direction. The complex 2 crystallizes in the monoclinic symmetry with the P21/c space group in which the N-O unit of the radical coordinates with the Co ion through hydrogen bonding of a water molecule. All compounds exhibit antiferromagnetic interactions between the transition metal ions and nitronyl nitroxide radicals. The magnetic exchange interactions (J/K B) are derived using isotropic spin Hamiltonian H = -2J∑(S metal S radical) for the model fitting to the magnetic susceptibility data for 1, 2, 3, and 4. The exchange interaction strengths are found to be -328, -1.25, -248, and -256 K, for the 1, 2, 3, and 4 metal-organic complexes, respectively. Quantum chemical density functional theory (DFT) computations are carried out on several models of the metal-radical complexes to elucidate the magnetic interactions at the molecular level. The calculations show that a small part of the inorganic spins are delocalized over the oxygens from hfac {∼0.03 for Co(II) and ∼0.015 for Mn(II)}, whereas a more significant fraction {∼0.24 for Mn(II) and ∼0.13 for Co(II)} of delocalized spins from the metal ion is transferred to the coordinated oxygen atom(s) of nitronyl nitroxide.

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Evaluation of dispersion type metal···? arene interaction in arylbismuth compounds - an experimental and theoretical study.

Publications

Evaluation of dispersion type metal···π arene interaction in arylbismuth compounds - an experimental and theoretical study.

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