Abstract
We reviewed the synthesis, structure, and properties of pyridine complexes of AgXO4 (X = Cl, Mn, and Re) compounds with various compositions ([AgPy2] XO4, [AgPy2XO4]·0.5Py, [AgPy4] XO4, and 4 [AgPy2XO4] [AgPy4] XO4). We also clarified the controversial information about the existence and composition of pyridine complexes of silver permanganate, used widely as mild and selective oxidants in organic chemistry. We discussed in detail the available structural and spectroscopic (IR, Raman, and UV) data and thermal behavior, including the existence and consequence of quasi-intramolecular reactions between the reducing ligand and anions containing oxygen.
Highlights
Silver permanganate, perchlorate, and perrhenate (AgXO4, X = Cl, Mn, and Re) are well soluble in pyridine, and various complexes with studied and unknown chemical nature were isolated even in the 19th and the beginning of the 20th century [1,2,3]
Considering the wide use of silver permanganate complexes in organic chemistry, as mild and selective oxidants, and that literature sources contain controversial or incorrect information about these compounds, we discuss the chemistry of pyridine complexes of AgXO4 (X = Cl, Mn, and Re) in detail
(m/z = 28), H2O (m/z = 18), and NO (m/z = 30). They attributed the presence of the pyridine ring oxidation products to the partial oxidation of the pyridine ligands by the permanganate ion
Summary
Perchlorate, and perrhenate (AgXO4, X = Cl, Mn, and Re) are well soluble in pyridine, and various complexes with studied and unknown chemical nature were isolated even in the 19th and the beginning of the 20th century [1,2,3]. Considering the wide use of silver permanganate complexes in organic chemistry, as mild and selective oxidants, and that literature sources contain controversial or incorrect information about these compounds, we discuss the chemistry of pyridine complexes of AgXO4 (X = Cl, Mn, and Re) in detail. We comprehensively summarized their synthesis, composition, structure, and redox properties, including the occurring quasiintramolecular redox reactions between the reducing pyridine ligand and oxidizing XO4− anions and the existence of hydrogen bonds between the acidic C–H and polarized X–O bonds. AgMnO4 AgClO4 AgReO4 AgPy2MnO4 [AgPy2]ClO4 [AgPy2]ReO4 [AgPy2MnO4]·0.5Py [AgPy2ClO4]·0.5Py AgPy2ReO4·0.5Py 4[AgPy2MnO4]·[AgPy4]MnO4 4[AgPy2ClO4]·[AgPy4]ClO4 4AgPy2 ReO4 ·AgPy4 ReO4 [AgPy4]MnO4 [AgPy4]ClO4 [AgPy4]ReO4
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