A comparative study of the coordination behavior of cyclo-P₅ and cyclo-As₅ ligand complexes towards the trinuclear Lewis acid complex (perfluoro-ortho-phenylene)mercury

Abstract

Reactions of the cyclo-E5 sandwich complexes [Cp*Fe(η5-P5)] (1) and [Cp*Fe(η5-As5)] (2) with the planar Lewis acid [(o-C6F4Hg)3] (3) afford compounds that show distinctly different assemblies in the solid state.

Molecular Polyarsenides of the Rare‐Earth Elements

“…Although the solid-state and coordination chemistry of polyarsenides has been extensively explored, [10,13] no molecular rare-earth polyarsenide has ever been reported. [19] Thet reatment of the arsenic compound [Cp*Fe(h 5 -As 5 )] [18] with [Cp'' 2 Sm(thf)] (Cp'' = h 5 -1,3-(tBu) 2 C 5 H 3 ) [20] in toluene in a1:1 stoichiometric ratio leads to the isolation of the sandwich compound [(Cp'' 2 Sm)(m,h 4 :h 4 -As 4 )(Cp*Fe)] (1)asblack crystals in moderate yields (Scheme 1). [15] Herein, we report the synthesis and structural characterization of two mixed Fe/Sm polyarsenides obtained from reactions of [Cp*Fe(h 5 -As 5 )] with [Cp'' 2 Sm(thf)].T he products are the first rare-earth polyarsenides.Byexchanging the solvent the reaction either yields at rinuclear complex containing an orbornadiene-like As 7 3À anionic ligand or the first d-and f-metal triple-decker sandwich complex containing aplanar As 4 2À ring as the middle deck.…”

“…Recently,wereported the reactions of divalent samarium compounds with white phosphorus [16] or transition-metalcoordinated polyphosphides. [19] Thet reatment of the arsenic compound [Cp*Fe(h 5 -As 5 )] [18] with [Cp'' 2 Sm(thf)] (Cp'' = h 5 -1,3-(tBu) 2 C 5 H 3 ) [20] in toluene in a1:1 stoichiometric ratio leads to the isolation of the sandwich compound [(Cp'' 2 Sm)(m,h 4 :h 4 -As 4 )(Cp*Fe)] (1)asblack crystals in moderate yields (Scheme 1). [17b] Inspired by these findings,wehave been interested to compare this reaction behavior of [Cp*Fe(h 5 -P 5 )] towards the corresponding cyclo-As 5 analogue [Cp*Fe(h 5 -As 5 )], [18] since it is known for different behavior.…”

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

“…Those properties are usually encountered in systems stabilized by noncovalent interactions such as electrostatic, dispersion interactions or very weak hydrogen or halogen bonds [74][75][76][77]. Similar topological characteristics for multicentre cooperative bonding of electron-rich guest molecule with mercury atoms of macrocycle 1 were observed in hostguest complexes with oxygen or phosphorus containing compounds [16,24]. This allows us to suggest that energy of interaction of macrocycle with guest molecules is comparable to that in stacked dimers of macrocycles.…”

“…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]). 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].…”

Koordinationschemie und Bioanorganik

“…Scheer und Mitarbeiter untersuchten, wie die Substanzen mit der planaren trinuklearen Lewis-Säure [(o-C 6 F 4 Hg) 3 ] wechselwirken. 6 …”