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Tris(2-pyridyl) Bismuthines: Coordination Chemistry, Reactivity, and Anion-Triggered Pyridyl Coupling

Cite this: Inorg. Chem. 2020, 59, 10, 7103–7116
Publication Date (Web):April 24, 2020
https://doi.org/10.1021/acs.inorgchem.0c00579
Copyright © 2020 American Chemical Society

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    Abstract

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    A series of new tris(2-pyridyl) bismuthine ligands of the type [Bi(2-py′)3] have been prepared, containing a range of substituents at various positions within their pyridyl rings (py′). They can act as intact ligands or, as a result of the low C–Bi bond energy, exhibit noninnocent reactivity in the presence of metal ions. Structural studies of Li+ and Ag+ complexes show that the coordination to metal ions using their pyridyl-N atoms and to anions using the Lewis acidity of their Bi(III) centers can be modified by the presence of substituents within the 2-pyridyl rings, especially at the 6- or 3-positions, which can block the donor-N or Lewis acid Bi sites. Electron withdrawing groups (like CF3 or Br) can also severely reduce their ability to act as ligands to metal ions by reducing the electron donating ability of the pyridyl-N atoms. Noninnocent character is found in the reactions with Cu+ and Cu2+, resulting in the coupling of pyridyl groups to form bipyridines, with the rate of this reaction being dependent on the anion present in the metal salts. This leads to the formation of Bi(III)/Cu(I) complexes containing hypervalent [X2Bi(2-R-py)] (X = Cl, Br) anions. Alternatively, the tris(2-pyridyl) bismuthine ligands can act as 2-pyridyl transfer reagents, transferring 2-py groups to Au(I) and Fe(II).

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    The Supporting Information is available free of charge at https://pubs.acs.org/doi/10.1021/acs.inorgchem.0c00579.

    • NMR spectra, additional X-ray structures, details and information, and HR-MS data (PDF)

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    CCDC 19811151981137 contain the supplementary crystallographic data for this paper. These data can be obtained free of charge via www.ccdc.cam.ac.uk/data_request/cif, or by emailing [email protected], or by contacting The Cambridge Crystallographic Data Centre, 12 Union Road, Cambridge CB2 1EZ, UK; fax: +44 1223 336033.

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