“…Trimeric perfluoro- ortho -phenylenemercury ( 7 , Chart ) has been widely investigated as a host for a variety of anions. ,− This molecule, which can be obtained in a crystalline form by recrystallization from CH 2 Cl 2 or sublimation, features a planar structure with readily accessible mercury centers. 6 7 Structures and Stoichiometry Adopted by Adducts of 7 with Aldehydes, Ketones, Amides, Nitriles, Phosphoramides, and Sulfoxides…”
Section: Lewis Acidic Properties Of Trimeric
Perfluoro-ortho-phenylen...mentioning
Owing to their unusual Lewis acidic properties, the coordination chemistry of fluorinated organomercurials is attracting increasing interest. In this review, the authors focus on the synthesis, structures, and properties of neutral Lewis adducts involving fluorinated organomercurials such as (CF 3 ) 2 Hg, (C 6 F 5 )HgCl, (C 6 F 5 ) 2 Hg, and [(o-C 6 F 4 )Hg] 3 . While most of these organomercurials form adducts with common Lewis basic organic substrates, [(o-C 6 F 4 )Hg] 3 also interacts with aromatic hydrocarbons, alkynes, N-heterocycles, and metallocenes to form π-complexes. In some cases, this complexation mode results in the formation of supramolecules with unusual luminescence properties or microporosity.
“…Trimeric perfluoro- ortho -phenylenemercury ( 7 , Chart ) has been widely investigated as a host for a variety of anions. ,− This molecule, which can be obtained in a crystalline form by recrystallization from CH 2 Cl 2 or sublimation, features a planar structure with readily accessible mercury centers. 6 7 Structures and Stoichiometry Adopted by Adducts of 7 with Aldehydes, Ketones, Amides, Nitriles, Phosphoramides, and Sulfoxides…”
Section: Lewis Acidic Properties Of Trimeric
Perfluoro-ortho-phenylen...mentioning
Owing to their unusual Lewis acidic properties, the coordination chemistry of fluorinated organomercurials is attracting increasing interest. In this review, the authors focus on the synthesis, structures, and properties of neutral Lewis adducts involving fluorinated organomercurials such as (CF 3 ) 2 Hg, (C 6 F 5 )HgCl, (C 6 F 5 ) 2 Hg, and [(o-C 6 F 4 )Hg] 3 . While most of these organomercurials form adducts with common Lewis basic organic substrates, [(o-C 6 F 4 )Hg] 3 also interacts with aromatic hydrocarbons, alkynes, N-heterocycles, and metallocenes to form π-complexes. In some cases, this complexation mode results in the formation of supramolecules with unusual luminescence properties or microporosity.
“…[13] With 1, however, a number of anionic complexes including bromide, iodide, and thiocyanide salts have been isolated. Synthesis of 1; 19 F and 199 H NMR spectroscopic features in CH 2 D 2 (CFCl 3 and Me 2 Hg external reference).…”
Section: ] Impedes Their Isolation Andmentioning
confidence: 99%
“…The importance of this electronic effect is nicely illustrated by the relative halophilicity of 1 and that of its non‐fluorinated analogue trimeric ortho ‐phenylenemercury ([( o ‐C 6 H 4 Hg) 3 ]) 12. As shown by Shur, while both molecules interact with halide ions in solution, the lability of the complex formed by [( o ‐C 6 H 4 Hg) 3 ] impedes their isolation and structural characterization 13. With 1 , however, a number of anionic complexes including bromide, iodide, and thiocyanide salts have been isolated 13–15.…”
Section: Cooperative Effects and Lewis Acidic Propertiesmentioning
confidence: 99%
“…As shown by Shur, while both molecules interact with halide ions in solution, the lability of the complex formed by [( o ‐C 6 H 4 Hg) 3 ] impedes their isolation and structural characterization 13. With 1 , however, a number of anionic complexes including bromide, iodide, and thiocyanide salts have been isolated 13–15. These anionic complexes adopt multidecker structures with the anions sandwiched between successive molecules of 1 (Figure 1).…”
Section: Cooperative Effects and Lewis Acidic Propertiesmentioning
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.
“…The first example of the successful application of a macrocyclic multidentate Lewis acid in phase transfer catalysis was described in 1989 when it was reported that cyclic trimeric o-phenylenemercury (o-C 6 H 4 Hg) 3 containing three Hg atoms in a planar nine-membered cycle is capable of forming complexes with halide anions and catalysing the azo-coupling reaction between benzenediazonium halides PhN 2 + X − (X = Cl, Br) and -naphthol in the two-phase H 2 O-CH 2 Br 2 system [15]. The resulting complexes could not be isolated here due to apparently their insufficient stability and the catalytic effect of the above polymercuramacrocycle in the azo-coupling reaction was not very strong.…”
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