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Cations in Inorganic Solids

AutorVegas, Ángel
Palabras claveBorides
d¹º-d¹º interactions
Ionic bonding
Rare-earth compounds
Fecha de publicaciónmar-2000
EditorTaylor & Francis
CitaciónCrystallography Reviews, Volume 7, Issue 3 March 2000 , pages 189 - 283
ResumenUntil recently, cations have been considered as small “isolated” entities, occupying the spaces in close-packed arrays of large anions. An inspection however of cation subarrays reveals that some kind of interaction must exist between them, as they reproduce both the topology and the distances of their parent metal structures. Up to now, the existence of clusters has been identified with metal-rich compounds or with compounds in which the metal atoms have unsaturated valences. However, from the results reported here, it can be stated that cations recognize themselves in forming aggregates in such a way that the world of clusters also comes into the field of fully ionic compounds, wherein metal atoms have saturated valences. This kind of interaction has already been observed in silver(I) and gold(I) compounds (and is known as the auriphilic effect or as d10-d10 interactions); but examples are reported here of similar interactions between cations of the alkaline-earth metals. Group 13 elements, lanthanides, Sc, Ti and Y, indicating that this effect is a general feature of inorganic solids. Although some explanations have been reported, the reasons for such interactions remain unclear. This is an open question challenging theoretical chemists. These new ideas are placed in the context of similar ones developed recently, which give to cations a more relevant le in determining crystal structures. Thus, the old ideas of Lebedev regarding the protagonism of “large” cations in the formation of crystal structures is discussed together with the more recent ideas of O'Keeffe and Hyde which describe the crystal structures of oxides as oxygen-stuffed alloys. In many oxides, the cations occupy octahedral or tetrahedral holes in close-packed arrays of anions. It is true that in many other structures, the cations reproduce the topology of the structures of elements or simple alloys, but it is also true that the structure of the parent metal is often preserved in its oxides.
Versión del editorhttp://dx.doi.org/10.1080/08893110008044245
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