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

Dzialkowski, Kevin; Gehlhaar, Alexander; Wölper, Christoph; Auer, Alexander A.; Schulz, Stephan

doi:10.1021/acs.organomet.9b00269

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

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Auer, Alexander A.
Research Group Auer, Max-Planck-Institut für Kohlenforschung, Max Planck Society;

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Dzialkowski, K., Gehlhaar, A., Wölper, C., Auer, A. A., & Schulz, S. (2019). Structure and Reactivity of 1,8-Bis(naphthalenediyl)dipnictanes. Organometallics, 38(15), 2927-2942. doi:10.1021/acs.organomet.9b00269.

Cite as: https://hdl.handle.net/21.11116/0000-0004-96F7-C

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 [Naph₂E₂][Cr(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 (¹H, ¹³C) 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 noncovalent interactions and illustrate how dispersion interactions change with the electronic structure of the compounds.