Structure and Reactivity of 1,8-Bis(naphthalenediyl)dipnictanes

Abstract

Syntheses and solid-state structures of diarsane Naph2As2 (Naph = 1,8-naphthalenediyl, 1) and (Naph)5Sb4Cl2 3 are reported and the σ-donor capacity of Naph2E2 (E = As 1, Sb 2) was studied in reactions with (coe)Cr(CO)5 (coe = Z-cyclooctene), yielding Naph2As2[Cr(CO )5]2 (4) and Naph2E2Cr(CO)5 (E = As 5, Sb 6). In contrast, reactions of 1 and 3 with Me2SAuCl proceed with oxidation and formation of elemental gold as well as Naph2(AsCl)2 ( 7) and [NaphSbCl2]2 8. All complexes were characterized by elemental analyses, heteronuclear ( 1 H, 13 C) NMR and FT-IR spectroscopy as well as single crystal X-ray diffraction. Intermolecular E•••π interactions (E = As, Sb), which were observed in 7 and 8, were quantified by use of density functional theory and local coupled cluster electronic structure theory calculations. These allow to assess the nature and relative importance of covalent and non-covalent interactions and illustrate how dispersion interactions change with the electronic structure of the series of compounds.

Comparing London dispersion pnictogen–π interactions in naphthyl-substituted dipnictanes

“…code HOJVAG). 12 However, 2 shows intermolecular As⋯As contacts in contrast to the initially reported structure, which are accompanied by π⋯π and CH⋯π contacts (Fig. 3).…”

“…More importantly, the molecular packing of 1 significantly deviates from their lighter homologues Pn 2 Naph 2 . 12,13 1 does not show any π⋯π contacts as was observed in the lighter homologues, but two Bi⋯π contacts per Bi atom were observed (Fig. 2D).…”

“…1)) 7–9 and heteroatomic Au⋯Sb and Hg⋯Sb naphthalene complexes, 10 peri -substituted species containing the heaviest and easily polarizable group 15 elements, Sb and Bi, 11 are still rare. Dipnictanes Pn 2 Naph 2 (Pn = As, Sb; type V ) were structurally characterized, 12 with Sb 2 Naph 2 forming dimers in the solid-state resulting from dispersion-dominated Sb⋯π interactions, whereas the corresponding diarsane and diphosphane Pn 2 Naph 2 (Pn = P, 13 As 12 b ) lack any Pn based LD interactions, most likely due to the poorer polarizability of As compared to Sb. In addition, Bi⋯π interactions were recently observed in Ph 2 Bi 2 Naph 2 (type IV ).…”

Dibismuthanes in catalysis: from synthesis and characterization to redox behavior towards oxidative cleavage of 1,2-diols

“… 6 Indeed, compared to the lighter counterparts in the group 15 ( e.g. N 7 and P 8 ), examples of dimetallic heavy pnictogens are really limited and mainly focus on As and Sb, 9,10 leaving dimetallic Bi compounds as boutique examples ( Fig. 1A ).…”

Hydrostibination

“…However,fusing the amino substituents with arigid naphthalene [13] backbone necessitates molecular distortion to fit the antimony atom within the NC 3 Nb ay, [14] causing the Nl one pairs to twist away from the plane of the Sb À N s*L UMO. This lowers the LUMO energy dramatically to À1.34 eV while retaining its localization at Sb ( Figure S1).…”