μ6-η2:η2:η2:η2:η2:η2 As a New Bonding Mode for Benzene

Tsunoda, M.; Gabbaı̈, François P.

doi:10.1021/ja0016598

Cited by 105 publications

(80 citation statements)

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“…Even in solution the large quadrupole interaction provides a very efficient relaxation mechanism which results in resonance lines often broadened beyond observation. Although Wu and Wasylishen [11] reported the solid state 201 Hg spectrum for K 2 Hg(CN) 4 in which the electric field gradient vanishes at the center of the Hg(CN) 4 Table 1.…”

Section: Resultsmentioning

confidence: 99%

“…For example, free trimer forms compact cofacial dimers whose structure has been determined by single crystal Xray diffraction. As shown by recent developments, the trimer is also a remarkable supramolecular building block which readily forms binary stacks with various arenes including benzene and naphthalene [3,4]. The formation of these stacks, which results from secondary interactions occurring between the mercury centers and the -system of the arene, is likely assisted by attractive electrostatic and dispersion forces between the individual components.…”

Section: Introductionmentioning

confidence: 99%

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19F and 199Hg NMR of trimeric perfluoro-ortho-phenylenemercury

Taylor

Gabbaı̈

2007

Journal of Molecular Structure

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Abstract:19 F and 199 Hg high-resolution solution NMR spectra were acquired for cyclic trimeric perfluoro-ortho-phenylenemercury. Even with the high superconducting magnetic fields currently available, the 19 F spectrum was not interpretable with a simple first-order analysis. Spectroscopic parameters for chemical shift and scalar coupling interactions in the NMR spectra were extracted from four-and five-spin simulations. Differential line widths in the 19 F spectrum result from scalar coupling to the 199 Hg.

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Section: Resultsmentioning

confidence: 99%

Section: Introductionmentioning

confidence: 99%

19F and 199Hg NMR of trimeric perfluoro-ortho-phenylenemercury

Taylor

Gabbaı̈

2007

Journal of Molecular Structure

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“…[15,16,28,29] The {(1)(Mes)} unit sits on a threefold rotation axis. The 1-Mes-1-Mes planes are separated by 3.32, 3.19, and 3.32 which indicates relatively tight contacts.…”

Section: 2037(4)mentioning

confidence: 99%

“…Similar strong binding has been seen between [{(o-C 6 F 4 )Hg} 3 ] and arenes. [15,20] These contacts between the arene carbon atoms and the complex 1 are longer than the Ag I À C bonds of the arene adducts of ionic silver salts that usually show h 1 -or h 2 -bonded arenes with AgÀC distances ranging from 2.16(3) to 2.921 (9) . [30] Crystals of [(C 6 H 6 )(1)(C 6 H 6 )] lose some of the benzene molecules under reduced pressure at room temperature, thus In summary, herein we have described the isolation of sandwich molecules and supramolecular stacks which contain the acidic [{[3,5-(CF 3 ) 2 pz]Ag} 3 ] moiety and electron-rich aromatic p systems and in which the aggregation patterns depend on the solvent and the arene.…”

Section: 2037(4)mentioning

confidence: 99%

“…The most widely explored trinuclear d 10 p acid in arene chemistry concerns a Hg II complex [{(o-C 6 F 4 )Hg} 3 ]. [15][16][17][18][19] The research group of Gabbaï has demonstrated its use in the isolation of a series of one-dimensional organometallic polymers (type A) which contain arene donors such as benzene, naphthalene, and pyrene. [20][21][22] During the synthesis of 1, [14] we observed that it was difficult to remove the aromatic solvent from the final product.…”

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Arene‐Sandwiched Silver(I) Pyrazolates

Dias

Gamage

2007

Angew Chem Int Ed

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Modular Self-Assembly of a Microporous Solid Based upon Mercuracarborand-4 and a New Bonding Motif

2001

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Mercuracarborands [1] comprise a class of novel macrocyclic multidentate Lewis acids [2] and possess useful properties in molecular recognition, [1,3] optical sensors, [4] and catalysis. [5] Macrocyclic mercuracarborands are composed of alternating ortho-carborane icosahedra and mercury atoms linked by C-Hg-C moieties. The electron-withdrawing character of the o-carborane cage strengthens the Lewis acidity of the mercury centers, thereby enhancing the ability of the mercuracycle to function as a host for electron-rich guests. [2] An added benefit derived from the carborane cage is the fact that the boron vertices can be selectively functionalized to manipulate solubility [6,7] and/or structural features required for supramolecular self-assembly. [8] The majority of carborane selfassembly chemistry is directed by the acidic C ± H vertices of the carborane [9] and examples in which nonacidic B ± H vertices direct self-assembly are limited. [10] As part of our ongoing investigation of mercuracarborand chemistry, we now report the synthesis and solid-state structure of Li 2 [(HgC 2 B 10 H 8 I 2 ) 4´I2 ] (Li 2 [1´I 2 ]), an example of self-assembly directed by novel BÀI´´´Li´´´IÀB linkages which form microporous channels subsequently occupied by solvent molecules.Electrophilic iodination at the electron-rich 9,12-vertices of ortho-carborane [6] followed by lithiation of the C ± H vertices [11] provided the corresponding dilithium reagent, Li 2 C 2 B 10 -H 8 I 2 . The reaction of Li 2 C 2 B 10 H 8 I 2 with one molar equivalent of HgI 2 in dry diethyl ether at room temperature afforded the diiodide ion complex, Li 2 [1´I 2 ], of the bis-iodo-tetrameric cycle, 1, in 78 % yield. The resulting Li 2 [1´I 2 ] species is an airand moisture-stable crystalline solid that is soluble in a variety of organic solvents such as acetone, acetonitrile, diethyl ether, and dichloromethane. The 1 H, 13 C, and 11 B NMR spectra of Li 2 [1´I 2 ] revealed a highly symmetrical structure in solution. The 199 Hg NMR spectrum of Li 2 [1´I 2 ] in acetone exhibits a sharp singlet at d À 622 which is essentially independent of concentration at room temperature. The negative-ion fast atom bombardment mass spectrum exhibits a peak centered at m/z 2640, with the isotopic pattern expected for Li[1´I 2 ] À , and an anion envelope at m/z 2505, which corresponds to [1´I] À . The species at m/z 2505 is presumed to arise through the elimination of LiI from Li[1´I 2 ] À , since a second resonance signal was not observed in the 199 Hg NMR spectrum of the latter.A single crystal of [Li 2 {(CH 3 ) 2 CO} 6 ][1´I 2 ] ' 4 H 2 O, grown from an acetone/dichloromethane solution, was selected for an X-ray diffraction study. [12] It crystallized in the monoclinic space group C2/m. The Li 2 [1´I 2 ] structure consists of four divalent 9,12-I 2 -1,2-C 2 B 10 H 8 cages linked at carbon by four Hg atoms in a cyclic tetramer with an iodide ion located above and below the tetramer cavity ( Figure 1). The four Hg atoms [*] Prof.

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μ₆-η²:η²:η²:η²:η²:η² As a New Bonding Mode for Benzene

Cited by 105 publications

References 37 publications

19F and 199Hg NMR of trimeric perfluoro-ortho-phenylenemercury

19F and 199Hg NMR of trimeric perfluoro-ortho-phenylenemercury

Arene‐Sandwiched Silver(I) Pyrazolates

Modular Self-Assembly of a Microporous Solid Based upon Mercuracarborand-4 and a New Bonding Motif

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