Lewis Acidic Behavior of Fluorinated Organomercurials

Abstract

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.

A Mercury→Antimony Interaction

“…The crystal structure of 3 (Figure 1 a), which displays a virtually unchanged Hg À Sb separation of 3.073(1) , shows that the iodide anion is coordinated to the mercury center. [13] As nonfluorinated diarylmercury complexes do not form isolable adducts with any halides, [12,15] the coordination of the iodide ligand to the mercury atom of 3 constitutes a distinctive and noteworthy feature. The resulting mercury-iodine distance of 2.991(1) in 3 is also shorter than that observed in complexes involving highly Lewis acidic fluorinated organomercurials, such as [(C 6 F 5 ) 2 HgI] À (3.118 (2) ).…”

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

“…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]).…”

“…[15][16][17][18][19][20][21][22][23][24]). Coordination ability of 1 was utilized for molecular recognition in catalysis and organic synthesis [25][26][27], as well as for various ion-sensitive material chemistry, supramolecular self-assembly and design of crystalline materials [8,14]. Particularly, it was observed that macrocycle 1 is prone to form co-crystals with aromatic molecules and polyynes.…”

“…In these co-crystals, the guest molecules are sandwiched between mutually parallel neighbouring macrocycles that lead to forming of the socalled binary stacks as a main structural motif. This fact was proposed to be the reason of their photophysical properties [14,20,21,[28][29][30][31]. Typically, host-guest complexes of 1 are formed by means of weak secondary interactions that can be reliably detected only in a crystal.…”

Coordination chemistry of anticrowns. Complexation of cyclic trimeric perfluoro-o-phenylenemercury (o-C6F4Hg)3 with the cyanoborohydride anion [H3BCN]− and triethylamineborane Et3NBH3

“…There is also evidence that compound 1 shows promise in organic synthesis and catalysis, 1,2,11,12 for the molecular recognition, 13 as a ionophore for ion selective electrodes, 14 and for the design of new luminescent ma terials. 5 Earlier, 15 we have studied the reaction of macrocycle 1 with the borohydride anion in THF by IR (4), in which the anionic species is bound to the mercury centers of the anticrown by B-H-Hg bridges. According to quantum chemical calculations, 15 compounds 2, 3, and 4 should have pyramidal (half sandwich), bipyramidal, and sandwich structures, respectively (Fig.…”