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4. In Situ Formation of PBiP Ligands upon Complexation of a Mixed Phosphane/Bismuthane with Group 11 Metal Ions

Author

Materne, Karolin, Hoof, Santina, Frank, Nicolas, Herwig, Christian, and Limberg, Christian

Abstract

The behavior of a xanthene derivative with one bismuthane and one phosphane function, Xan(PPh2)(BiPh2), as a ligand toward group 11 metal cations was investigated. It was found that contact with [Cu(MeCN)4]OTf, AgOTf, [Au(PPh3)OTf], in all three cases leads to a transformation of Xan(PPh2)(BiPh2) into a tridentate PBiP system, where a BiPh unit connects two phosphinoxanthyl moieties. In the resulting compounds, [PhBi(Xan(PPh2))2Cu]OTf, 1, [PhBi(Xan(PPh2))2Ag]OTf, 2, and [PhBi(Xan(PPh2))2AuPPh3]OTf, 3, the metal cations are coordinated tetrahedrally by two phosphane donors, one bismuthane donor and a fourth ligand, corresponding to OTf–in case of 1and 2, or PPh3in the case of 3. DFT calculations in combination with NBO analysis showed that the bismuth atoms in these PBiP ligands act as σ-donors. 3thus corresponds to the first known AuI← BiIIIcomplex.

Published
2024
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5. Bismuthanes as Hemilabile Donors in an O2-Activating Palladium(0) Complex.

Author

Materne, Karolin, Braun ‐ Cula, Beatrice, Herwig, Christian, Frank, Nicolas, and Limberg, Christian

Subjects
*COMPLEX compounds synthesis, *METAL complexes, *BISMUTH compounds, *PALLADIUM compounds, *LIGANDS (Chemistry), *PHOSPHINES
Abstract

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. [ABSTRACT FROM AUTHOR]

Published
2017
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6. Bismuthanes as Hemilabile Donors in an O 2 -Activating Palladium(0) Complex.

Author

Materne K, Braun-Cula B, Herwig C, Frank N, and Limberg C

Abstract

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 O 2 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., (© 2017 Wiley-VCH Verlag GmbH & Co. KGaA, Weinheim.)

Published
2017
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