title: Reversibility in Reactions of Linker-Bridged Distannenes with Terminal Alkynes at Ambient Temperature.
abstract: The linker-bridged distannene [(2,6-Mes2)C6H3Sn]2C12H8 (1) featuring an acenaphthene linker and the sterically demanding terphenyl substituent Ar(Me) (= C6H3-2,6-Mes2; Mes = C6H2-2,4,6-Me3) was prepared and characterized by single-crystal analysis, NMR spectroscopy, as well as elemental analysis. Furthermore, the reactivity of distannene 1 and previously reported distannenes 2 and 3, bearing either a naphthalene or a 9,9-dimethylxanthene backbone and the terphenyl substituent Ar(Me), as well as bis(stannylene) 4, featuring a 9,9-dimethylxanthene backbone and the terphenyl substituent Ar(iPr) (= C6H3-2,6-Trip2; Trip = C6H2-2,4,6-i-Pr3), toward terminal alkynes at ambient temperature was investigated, leading to the formal [2 + 2] cycloaddition products 5-9. The reactions of distannene 1 with trimethylsilylacetylene and phenylacetylene, the reaction of distannene 2 with trimethylsilyl-acetylene, as well as the reaction of bis(stannylene) 4 with phenylacetylene show reversibility, while distannenes 2 and 3 react irreversibly with phenylacetylene at room temperature. A van't Hoff analysis of variable-temperature (1)H NMR spectra of the cycloadduct of the reaction of distannene 1 with trimethylsilylacetylene afforded a dissociation enthalpy (ΔHdiss) of 71.6 kJ·mol(-1), which is in surprisingly good agreement with the results of accompanying DFT calculations (ΔHdiss = 70.9 kJ·mol(-1)).
authors.affiliation: Institut für Anorganische Chemie, Universität Tübingen, Auf der Morgenstelle 18, 72076 Tübingen, Germany.
authors.forename: Julia
authors.initials: J
authors.lastname: Schneider
authors.affiliation: Institut für Anorganische Chemie, Universität Tübingen, Auf der Morgenstelle 18, 72076 Tübingen, Germany.
authors.forename: Jens
authors.initials: J
authors.lastname: Henning
authors.affiliation: Institut für Anorganische Chemie, Universität Tübingen, Auf der Morgenstelle 18, 72076 Tübingen, Germany.
authors.forename: Jessica
authors.initials: J
authors.lastname: Edrich
authors.affiliation: Institut für Anorganische Chemie, Universität Tübingen, Auf der Morgenstelle 18, 72076 Tübingen, Germany.
authors.forename: Hartmut
authors.initials: H
authors.lastname: Schubert
authors.affiliation: Institut für Anorganische Chemie, Universität Tübingen, Auf der Morgenstelle 18, 72076 Tübingen, Germany.
authors.forename: Lars
authors.initials: L
authors.lastname: Wesemann