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

Abstract

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.

Complexation of methylparathion and bis(2-hydroxyethyl)sulfide by the tridentate lewis acid [(o-C6F4Hg)3]

“…Fluorinated polyfunctional organomercurials such as pentameric perfluoroisopropylidenemercury [11], trimeric perfluoro-ortho-phenylene mercury ([(o-C 6 F 4 Hg) 3 ], 1), 5,6,12 and 1,2-bis(chloromercurio)tetrafluorobenzene [13][14][15][16][17][18] have attracted a great deal of attention because the electron withdrawing capacity of the fluorinated ligands leads to an increase in the Lewis acidity of the mercury centers. The trinuclear derivative 1 is one of the most studied examples of fluorinated polyfunctional organomercurials.…”

Binding of ferrocene by cyclic trimeric perfluoro-o-phenylenemercury. Synthesis and structure of the first double-decker sandwich complex of a sandwich

“…1,2 However, its high efficiency in the binding of vari ous anions and neutral Lewis bases has been revealed only relatively recently (see the reviews [3][4][5] In the present paper, we report on the ability of macrocycle 1 to bind fer rocene with the formation of the {[(o C 6 F 4 Hg) 3 ] 2 (Cp 2 Fe)} complex (2) having a unique structure of a sandwich complex of a sandwich. In this unusual sandwich, the ferrocene molecule is coordinated to the Hg atoms of the macrocycles by its η 5 Cp rings, whose C atoms bear 6 a partial negative charge.…”

Vibrational and DFT analysis of perfluoro-o-phenylenemercury compounds

“…This because their peculiar electrostatic properties, that favor quadrupolar interactions and the polarized CeF bonds that address directional intermolecular interactions. A significant molecule of this class is the (C 6 F 4 Hg) 3 , perfluoro-o-phenylenemercury (1) compound [1], that combine the properties of fluorinated aromatic ring with a strong Lewis acidity [2,3]. This make this molecule able to form easily molecular complex with electron rich systems.…”