Crown compounds for anions. Unusual complex of trimetric perfluoro-o-phenylenemercury with the bromide anion having a polydecker sandwich structure

Shur, V. B.; Tikhonova, I. A.; Yanovsky, A. I.; Struchkov, Yu. T.; Petrovskii, P. V.; Panov, S. Yu.; Fürin, G. G.; Vol'pin, M. E.

doi:10.1016/0022-328x(91)80228-c

Cited by 76 publications

(41 citation statements)

References 10 publications

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“…The role of chloride ions in these reactions consists in their coordination with the macrocycle (see [18][19][20]) to form lipophilic complex anions capable of extracting cationic electrophiles (responsible for occurring the process of the nitration) from an acidic aqueous phase to an organic phase. One may suggest that nitrate anions either are unable to form complexes with 1 or these complexes are insufficiently lipophilic for the effective transfer of cationic electrophilic species through an interface.…”

Section: Resultsmentioning

confidence: 99%

“…This macrocycle readily reacts with halide (Cl − , Br − , I − ) [18][19][20] and some other anions [10,11,13] to form quite stable and isolable complexes having unusual sandwich, halfsandwich or bipyramidal structures. A high affinity of macrocycle 1 towards anions is due to the presence of the electronwithdrawing fluorine substituents in its molecule which increase the Lewis acidity of the mercury atoms.…”

Section: Introductionmentioning

confidence: 99%

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Cyclic trimeric perfluoro-o-phenylenemercury: a highly efficient phase transfer catalyst for nitration of aromatic substrates with dilute nitric acid

Zaraisky

Kachurin

Velichko

et al. 2005

Journal of Molecular Catalysis A: Chemical

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Section: Resultsmentioning

confidence: 99%

Section: Introductionmentioning

confidence: 99%

Cyclic trimeric perfluoro-o-phenylenemercury: a highly efficient phase transfer catalyst for nitration of aromatic substrates with dilute nitric acid

Zaraisky

Kachurin

Velichko

et al. 2005

Journal of Molecular Catalysis A: Chemical

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“…Silver z-complexes with the Ag+ ion trapped as a guest in a calix [4]arene cone have been reported and structurally characterized by X-ray diffraction [ 173-1753. A more comprehensive review on metal-containing calixarenes is available [ 1641.…”

Section: Calixarene Receptors Modified With Organometallic Groupsmentioning

confidence: 99%

“…With ferrocene-and ruthenoceiie dicarboxylic acids two calix [4]arenes were connected to give 90 [179].…”

mentioning

confidence: 99%

Molecular Recognition and Host–Guest Interactions

Haiduc

Edelmann

1999

Supramolecular Organometallic Chemistry

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Macrocyclic organomercury compounds have been known for some time, but their ability to bind anionic guests in their cavity was demonstrated relatively recently. This molecular recognition process is somewhat similar to the formation of the crown ether complexes, except that the binding sites of the macrocycle are occupied by metal atoms, able to function as Lewis acids, and therefore to bind halogen and other Lewis base anions. This approach is only in its beginnings and the recent discovery of mercuracarbaboranes as anion binding cyclic receptors gave a new impetus to research in the field.One of the earliest known organomercury macrocycles was the trimer of ovthophenylene mercury, (o-CgH4Hg)3, known from X-ray diffraction studies to have a planar cyclic structure, 1 [I, 21. It has recently been found, with the aid of 199Hg NMR spectroscopy, that this compound forms complexes with halide anions (Cl-, Br-and I-) in dichloromethane solution, but the complexes could not be isolated in solid state [3]. The fluorinated analog (o-CgF4Hg)3, 2, is a much better electron acceptor and forms stable complexes with the same halide anions; these could be 1 2 2.

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“…Besides, close disposition of mercury atoms promotes polydentate linkage with nucleophilic centres of a guest molecule. Thus, the macrocycle 1 was found to be able to interact with both anions [9][10][11][12][13] and neutral electron-rich molecules (see reviews [4,8,14] and recent studies cited in Refs. [15][16][17][18][19][20][21][22][23][24]).…”

Section: Introductionmentioning

confidence: 96%

Intermolecular interactions in polymorphs of the cyclic trimeric perfluoro-ortho-phenylene mercury from geometric, energetic and AIM viewpoints: DFT study and Hirshfeld surface analysis

et al. 2015

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Macrocyclic polydentate Lewis acids are of ongoing interest owing to their ability for molecular recognition of anions; however, deep understanding of the nature of supramolecular bonding in their crystals is still lacking. To solve this problem, we have analysed four polymorphic modifications A-D of cyclic trimeric perfluoro-ortho-phenylene mercury (1) by quantum chemical calculations of intermolecular pair interactions energy. In all polymorphs, the main structural motif is stacked columns, which are further connected to a three-dimensional structure with either ladder-shape interactions between parallel macrocycles or T-shape interactions between nearly perpendicular macrocycles. Both arrangements contribute almost equally to the stabilization of the crystal structure. According to DFT computational study of isolated dimers that correspond to the most energetically favourable molecular pairs, and topological analysis of electron density distribution, the stabilization of these dimers is governed by HgÁÁÁC and CÁÁÁC interactions.Significant contribution also comes from FÁÁÁC and HgÁÁÁF interactions, while the role of mercurophilic interactions and FÁÁÁF contacts seems negligible. Statistical analysis of crystal structures of host-guest complexes of the macrocycle 1 using Voronoi polyhedra and Hirshfeld surfaces showed the same types of intermolecular interactions to be responsible for stabilization of its polymorphs and cocrystals.

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Crown compounds for anions. Unusual complex of trimetric perfluoro-o-phenylenemercury with the bromide anion having a polydecker sandwich structure

Cited by 76 publications

References 10 publications

Cyclic trimeric perfluoro-o-phenylenemercury: a highly efficient phase transfer catalyst for nitration of aromatic substrates with dilute nitric acid

Cyclic trimeric perfluoro-o-phenylenemercury: a highly efficient phase transfer catalyst for nitration of aromatic substrates with dilute nitric acid

Molecular Recognition and Host–Guest Interactions

Intermolecular interactions in polymorphs of the cyclic trimeric perfluoro-ortho-phenylene mercury from geometric, energetic and AIM viewpoints: DFT study and Hirshfeld surface analysis

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