Tris(2-pyridyl) Bismuthines: Coordination Chemistry, Reactivity, and Anion-Triggered Pyridyl Coupling
| Autor: | García Romero, Álvaro, Plajer, Alex J., Miguel San José, Daniel, Bond, Andrew D., Álvarez González, Celedonio Manuel, Wright, Dominic Simon, García Rodríguez, Raúl, Miguel, Daniel, Wright, Dominic S., García-Rodríguez, Raúl |
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| Rok vydání: | 2020 |
| Předmět: |
Tris
chemistry.chemical_classification 010405 organic chemistry 010402 general chemistry 01 natural sciences Medicinal chemistry 0104 chemical sciences Coordination complex Ion Inorganic Chemistry Bismuthine Coupling (electronics) chemistry.chemical_compound chemistry Reactivity (chemistry) Physical and Theoretical Chemistry |
| Zdroj: | UVaDOC: Repositorio Documental de la Universidad de Valladolid Universidad de Valladolid UVaDOC. Repositorio Documental de la Universidad de Valladolid instname |
| Popis: | Producción Científica 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). Ministerio de Ciencia, Innovación y Universidades (project numbers PGC2018-096880-A-I00, MCIU/AEI/FEDER, UE and PGC2018-099470-B-I00,MCIU/AEI/FEDER, UE) Ministerio de Economía, Industria y Competitividad (Project RYC-2015-19035) |
| Databáze: | OpenAIRE |
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