[(CF3)2Hg(μ‐F)2Hg(CF3)2]2−: Synthesis, Structure, and Reactivity

Viets, Detlef; Lork, Enno; Watson, Paul G.; Mews, Rüdiger

doi:10.1002/anie.199706231

Cited by 23 publications

(5 citation statements)

References 24 publications

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“…These Hg−F distances are slightly longer than those found in [ II -μ 2 -F] - [2.589(2) Å], which possesses a less sterically hindered and possibly more Lewis acidic Hg center. Nevertheless, they remain within the range observed in other complexes such as [(CF 3 ) 2 Hg(μ 2 -F) 2 Hg(CF 3 ) 2 ] 2- (2.39 and 2.42 Å) or the fluoride adduct of a tetranuclear mercuracarborand (2.56 and 2.65 Å) . In comparison to [ II -μ 2 -F] - , it is also interesting to note that the longer Hg−F distances observed in [ 4 -μ 2 -F] correlate, as expected, with a smaller 1 J Hg - F .…”

Section: Resultssupporting

confidence: 79%

Synthesis and Properties of a Cationic Bidentate Lewis Acid

Lee

Gabbaı̈

2007

Inorg. Chem.

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As part of our efforts to increase the fluoride affinity of bidentate Lewis acids, we have set out to determine if the F(-) anion chelation occurring in such systems can be complemented by favorable Coulombic attractions. To explore this idea, the neutral B/Hg bidentate Lewis acid 1-{Mes(2)B}-8-{(2,6-Me(2)-4-Me(2)NC(6)H(2))Hg}C(10)H(6) (3) and its cationic analogue [1-{Mes(2)B}-8-{(2,6-Me2-4-Me(3)NC(6)H(2))Hg}C(10)H(6)]+ ([4]+) have been synthesized and studied. Compound 3 as well as the triflate salt of [4]+ react with [S(NMe(2))3][Me(3)SiF(2)] to afford the corresponding fluoride complexes [3-micro(2)-F]- and [4-micro(2)-F]. Spectroscopic and structural studies confirm that the F- anion bridges the two Lewis acidic centers in both [3-micro(2)-F]- and [4-micro(2)-F]. UV-vis titration experiments carried out in tetrahydrofuran/water (9/1, v/v) mixtures indicate that the fluoride binding constants of 3 and [4]+ are clearly differentiated and are equal to 1.3 (+/-0.1) x 10(2) M(-1) and 6.2 (+/-0.2) x 10(4) M(-1), respectively. The enhanced fluoride binding constant of [4]+, when compared to 3, confirms that the chelate effect occurring in these types of fluoride receptors can be combined with favorable Coulombic attractions to strengthen the host-guest interaction. Cation [4]+ remains highly selective for F- over other environmentally abundant anions including Cl-, Br-, NO(3)(-), H(2)PO(4)(-), and HSO(4)(-) and shows only a weak response to OAc(-). Finally, the addition of an aqueous solution of Al3+ to a solution containing [4-micro(2)-F] leads to complete regeneration of [4]+, showing that F(-) binding is reversible.

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Section: Resultssupporting

confidence: 79%

Synthesis and Properties of a Cationic Bidentate Lewis Acid

Lee

Gabbaı̈

2007

Inorg. Chem.

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“…[11] The importance of this electronic effect is nicely illustrated by the relative halophilicity of 1 and that of its nonfluorinated analogue trimeric ortho-phenylenemercury ([(o-C 6 H 4 Hg) 3 ]). [11] The importance of this electronic effect is nicely illustrated by the relative halophilicity of 1 and that of its nonfluorinated analogue trimeric ortho-phenylenemercury ([(o-C 6 H 4 Hg) 3 ]).…”

Section: Synthesismentioning

confidence: 99%

Trimeric Perfluoro‐ortho‐phenylenemercury: A Versatile Lewis Acidic Host

Haneline

Taylor

Gabbaı̈

2003

Chemistry A European J

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Trimeric perfluoro-ortho-phenylenemercury (1) constitutes one of the simplest trifunctional Lewis acidic hosts. In addition to cooperative effects arising from the proximity of the mercury(II) centers, the electron-withdrawing properties of the backbone and the accessibility of the electrophilic sites lead to the facile complexation of neutral and electron rich substrates. The planarity of the structure as well as its overall polarizability compounded with relativistic effects at mercury also permits the occurrence of non-covalent interactions and accounts for the tendency of this compound to form cofacial dimers. Collectively, the Lewis acidic properties of 1 as well as its ability to engage in non-covalent interactions can be held responsible for its ability to form extended binary supramolecular stacks with arenes. The photoluminescence observed in some of these supramolecular complexes corresponds to the phosphorescence of the aromatic substrate and indicate the occurrence of a mercury heavy atom effect.

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“…In contrast the fluoro analogue RuHX(CO)(PBu t 2 Me) 2 displays reactivity at both the Ru-H and the Ru-F bonds. 220 Tetrameric [RuF(µ-F)(CO) 3 ] 4 (258) is one of the earlier carbonyl fluorides to be structurally characterized. Compound 258 is isolated on reaction of ruthenium pentafluoride with carbon monoxide.…”

Section: A Ruthenium and Osmiummentioning

confidence: 99%

“…The presence of fluoride ion in 308 leads to labilization of the Hg-C(CF 3 ) bond. 258 In contrast Hg(CF 3 ) 2 cannot be used for nucleophilic transfer of CF 3 -due to the very strong Hg-C bond.…”

Section: Groups 11 and 12mentioning

confidence: 99%