Chemistry - A European Journal
Chemistry - A European Journal
5 years ago

Bismuthanes as Hemilabile Donors in an O2-Activating Palladium(0) Complex

Bismuthanes as Hemilabile Donors in an O2-Activating Palladium(0) Complex
Christian Herwig, Karolin Materne, Christian Limberg, Nicolas Frank, Beatrice Braun-Cula
A xanthene-based bismuthane/phosphane chelating ligand has been accessed that has enabled the synthesis of a palladium(0) bismuthane complex. The bismuthane donor proved to be hemilabile as it switched to a dangling position upon addition of O2 that gave a palladium(II) peroxide complex. Unlike the corresponding 4,5-bis(diphenylphosphino)-9,9-dimethylxanthene (Xantphos) palladium peroxide, the bismuth analogue could be employed for catalytic phosphane oxidation and oxidative phenol coupling. New character trait of bismuthanes: Pd0 chelated by a phosphino/bismuthino ligand reacted with dioxygen to form a palladium(II) peroxido complex (see scheme). In this reaction, the bismuthane donor acts as a hemilabile ligand that leaves when O2 enters and comes back, upon O2 elimination. This feature proved to be favorable for the properties of the peroxide as an oxidant.

Publisher URL: http://onlinelibrary.wiley.com/resolve/doi

DOI: 10.1002/chem.201703489

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