RT info:eu-repo/semantics/article
T1 Tris(2-pyridyl) Bismuthines: Coordination Chemistry, Reactivity, and Anion-Triggered Pyridyl Coupling
A1 García Romero, Álvaro
A1 Plajer, Alex J.
A1 Miguel San José, Daniel
A1 Wright, Dominic Simon
A1 Bond, Andrew D.
A1 Álvarez González, Celedonio Manuel
A1 García Rodríguez, Raúl
AB 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).
PB American Chemical Society
SN 0020-1669
YR 2020
FD 2020
LK http://uvadoc.uva.es/handle/10324/40996
UL http://uvadoc.uva.es/handle/10324/40996
LA eng
NO Inorganic Chemistry, 2020, 59, 10, 7103–7116
NO Producción Científica
DS UVaDOC
RD 15-ene-2025