Arene Adducts with Weak Interactions: Hexaethylbenzene–bis(tribromoarsane)

Schmidbaur, Hubert; Bublak, W.; Huber, Brigitte; Müller, Gerhard

doi:10.1002/anie.198702341

Cited by 35 publications

(27 citation statements)

References 19 publications

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“…Each antimony atom makes close contacts with three carbons of one phenyl ring and two carbons of the other phenyl ring. This asymmetric coordination of antimony by arenes has firm precedent in the Menshutkin complexes of antimony halides where Z 3 and Z 2 hapticity is often observed [30]. This preference is manifested in an unusual manner in the present dinuclear macrocycle, where a ''slipped sandwich'' geometry reduces the hapticity and provides coordination by two arenes.…”

Section: Sb 2 L 2 Cl 2 Macrocyclementioning

confidence: 90%

Self-assembled antimony-thiolate Sb₂L₃and Sb₂L₂Cl₂complexes

Vickaryous¹,

Zakharov²,

Johnson³

2006

Main Group Chemistry

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The synthesis and single crystal X-ray structures of two new self-assembled antimony(III)-thiolate complexes are described: Sb 2 L 3 (1) and ''anti''-Sb 2 L 2 Cl 2 (2), where H 2 L is a,a 0 -dimercaptoxylene. The Sb(III) ions in both complexes exhibit tripodal coordination geometries with stereochemically-active lone pairs. The extended structure of 1 in the crystalline state reveals numerous CÀ ÀHÁÁÁS interactions, while the packing in 2 is dominated by numerous antimony-sulfur and antimony-chlorine secondary bonding interactions. These structures demonstrate that a supramolecular design strategy can be developed to prepare self-assembled structures based on the coordination geometry of Sb(III) and the reversible formation of antimony-thiolate bonds in solution. This strategy offers promise in the specific chelation of toxic ions such as antimony, a contaminant of increasing environmental concern.

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Section: Sb 2 L 2 Cl 2 Macrocyclementioning

confidence: 90%

Self-assembled antimony-thiolate Sb₂L₃and Sb₂L₂Cl₂complexes

Vickaryous¹,

Zakharov²,

Johnson³

2006

Main Group Chemistry

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“…[16][17][18] To analyze this attractive interaction, DFT calculations were performed on the AsCl 3 -benzene dimer. [19] These studies revealed a lower limit for the binding energy of 7.4 kcal mol À1 for the arsenic-arene interaction, with CÀAs distances of 3.2-3.4 .…”

mentioning

confidence: 99%

Arsenic–π Interactions Stabilize a Self‐Assembled As₂L₃ Supramolecular Complex

2004

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The self-assembly of supramolecular coordination compounds has resulted in structures with a diverse range of properties, shapes, sizes, and stoichiometries, including helicates (M 2 L 2 , M 2 L 3 , etc.), triangles (M 3 L 3 ), squares (M 4 L 4 ), rings (e.g., M 6 L 6 ), and polyhedra (M 4 L 4 , M 4 L 6 , M 6 L 6 , M 8 L 12 , etc.).[1] These assemblies almost exclusively contain metals with square-planar, tetrahedral or octahedral coordination geometries. Metals that can exhibit more peculiar coordination geometries have typically been avoided as components for a supramolecular design strategy, [2] most likely because of their variable coordination spheres. Herein we describe a supramolecular design strategy for forming arsenic-based assemblies, which relies on the self-assembly of arsenic(iii) with thiol ligands-and hence the reversibility and lability of arsenic-sulfur bonds-and we report the first member of this class, [As 2 L 3 ] (H 2 L = a,a'-dimercapto-para-xylene). The design strategy incorporates the unusual, yet predictable trigonal-pyramidal coordination geometry of As III featuring a stereochemically active lone pair when coordinated by sulfurbased ligands (Figure 1 a). [3][4][5][6] We selected arsenic(iii) as a design component because of its unusual coordination geometry and a general lack of specific and powerful chelators for this highly toxic ion. [7] Arsenic compounds are legendary for their toxicity, and hydrated As III is recognized as a known human carcinogen. Arsenic is abundant in the earths crust and is all-toofrequently present as an environmental health hazard; [8][9][10] however, specific chelators for environmental and in vivo remediation and sensing applications are lacking. Furthermore, the stereochemically active lone pair of As III adds a novel feature to the targeted supramolecular assemblies: for instance, lone pairs directed into the cavity would provide a unique soft, Lewis-basic cavity environment (Figure 1 b). [11] Figure 1 illustrates the design strategy for forming C 3h -symmetric [As 2 L 3 ] assemblies, which is based on rigid, twofold symmetric dithiols capable of acting as bridging ligands. Dithiol ligand H 2 L[12] (Scheme 1) was the initial bridging ligand investigated, because it is easily prepared and thiolates show a well-known affinity for As III .[12] Using a ligand such as H 2 L allows for two possible orientations of the arsenic lone pairs: into or out of the cavity of the complex. Molecular models (CAChe, MM3) indicated that the lone pairs would be directed into the cavity with an AsÀAs distance of about 6 . [13] H 2 L, synthesized by a literature procedure, [12] forms a yellowish white solid in 52 % yield when treated with stoichiometric amounts of AsCl 3 and KOH in THF/methanol mixtures. The product has very simple 1 H and 13 C NMR spectra, indicative of formation of the desired high-symmetry C 3h complex, and the parent ion peak [H{As 2 L 3 }] + is present in the electrospray ionization mass spectrum. Interestingly, [As 2 L 3 ] also forms in the absence of any...

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“…Interestingly, [(HEB)TiCl 3 ][AlCl 4 ] ( 43 ) has also been reported, but in that case, although the molecular identity is evident, its C 3 v structure has been evaluated by ab initio calculations rather than determined experimentally . More impressively perhaps, the reaction of HEB with AsX 3 in toluene yields, in each case, the “inverted sandwich” structure [X 3 As(HEB)AsX 3 ] ( 44 : X=Cl, 45 : X=Br), exhibiting D 3 d symmetry . In the superficially similar system hexamethylbenzene–bis(trichlorobismuth), once again the BiCl 3 units generate the inverted sandwich structure, but the system is more complicated and consists of chloride‐bridged tetrameric units that are further coupled through Bi–arene–Bi coordination so as to build up a three‐dimensional network .…”

Section: Main Group Element and Related Complexes Of Hexaethylbenzenementioning

confidence: 72%

Hexaethylbenzene: A Sterically Crowded Arene and Conformationally Versatile Ligand

McGlinchey

2018

ChemPlusChem

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Arene Adducts with Weak Interactions: Hexaethylbenzene–bis(tribromoarsane)

Cited by 35 publications

References 19 publications

Self-assembled antimony-thiolate Sb₂L₃and Sb₂L₂Cl₂complexes

Self-assembled antimony-thiolate Sb₂L₃and Sb₂L₂Cl₂complexes

Arsenic–π Interactions Stabilize a Self‐Assembled As₂L₃ Supramolecular Complex

Hexaethylbenzene: A Sterically Crowded Arene and Conformationally Versatile Ligand

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Arene Adducts with Weak Interactions: Hexaethylbenzene–bis(tribromoarsane)

Cited by 35 publications

References 19 publications

Self-assembled antimony-thiolate Sb2L3and Sb2L2Cl2complexes

Self-assembled antimony-thiolate Sb2L3and Sb2L2Cl2complexes

Arsenic–π Interactions Stabilize a Self‐Assembled As2L3 Supramolecular Complex

Hexaethylbenzene: A Sterically Crowded Arene and Conformationally Versatile Ligand

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Self-assembled antimony-thiolate Sb₂L₃and Sb₂L₂Cl₂complexes

Self-assembled antimony-thiolate Sb₂L₃and Sb₂L₂Cl₂complexes

Arsenic–π Interactions Stabilize a Self‐Assembled As₂L₃ Supramolecular Complex