ChemInform Abstract: Ag5Pb2O6, a Subvalent Oxide,

Abstract

ChemInform Abstract is prepared for the first time as pure compound. Single crystals are obtained by reacting Ag2O and PbO2 under hydrothermal conditions (250-350 rc C, 3-12 d; 0.01-0.05 GPa O2; silver crucible). In its structure (P31m, Z=1) Pb is octahedrally coordinated by O atoms. The octahedra form layers 2 ∞(PbO3) with the same stacking sequence as in bayerite. The resulting silver partial structure exhibits an arrangement of the Ag atoms which is comparable with that in the metal. In accordance with the coordinations of the cations the compound must be formulated as AgI 5PbIV 2OII6-(e-).

Reply to the ‘Comment on “Uncommon structural and bonding properties in Ag16B4O10” by A. Lobato, Miguel Á. Salvadó, and J. Manuel Recio, Chem. Sci., 2021, 12, DOI: 10.1039/D1SC02152D

“…Manifestations of subvalent silver in extended solids can no longer be regarded as exotic singularities since in recent years a sizeable number of oxides displaying such characteristics have been reported. [4][5][6][7][8][9][10][11][12][13][14][15][16] From the empirical point of view there are two particularly noteworthy issues: (1) subvalent silver has been encountered in combination with quite diverse cations, e.g. B, Si, Ge, Pb, Ni, Mn, Os or Pt, apparently without any systematic showing up, which nourishes the expectation that many more such candidates will be accessible; (2) opposite to common presumption, these oxides are strikingly stable in humid air and in particular against oxidising conditions, they even form by solid-state reactions applying elevated oxygen pressure.…”

“…Still, in an early review, 3 the expectation was expressed that these features may enable existence of subvalent species: "The substructures thereby formed have empty s and p conduction bands, which can easily accommodate further electrons on reduction". This assumption has become true, as meanwhile several such subvalent silver oxides have been discovered, [4][5][6][7][8][9][10][11][12][13][14] in addition to previously conrmed Ag 2 F and Ag 3 O. † , 15,16 The most puristic manifestations of bonding interactions between presumably closed shell d 10 species are found in the distorted hcp structures of elemental zinc and cadmium.…”

Synthesis, Characterization, and Electrical Properties of the Series of Oxides Ag5Pb2−xCuxO6 (0.0≤x≤0.5)

“…For instance, there are several copper}lead and silver}lead ternary oxides. There are two known copper}lead oxides, murdochite (Cu PbO ) (8) and Cu PbO (9), and also two silver}lead oxides, the metallic conductor Ag Pb O (10}12) and Ag PbO (10,11,13); the latter is isostructural with Cu PbO , whereas the former has been subject to studies with cation substitutions (In or Bi for Pb) (14) relevant to the present work.…”

High-Pressure Synthesis and Electrochemical Investigation of Ag2Cu2O3

“…Both routes have been widely used in the past. Examples for the former included electrocrystallization of binaries (Ag O , Ag O (1, 2)) as well as precipitation (Ag PbO (3,4)) from an aqueous solution, while, e.g., Ag…”