Aspects of metal-metal bonding in early-transition-metal dioxides
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A theoretical investigation of metal-metal-bonded clusters and extended networks within dioxide frameworks is presented. In particular, we examine metal-metal bonding and the influence exerted by the oxide "matrix" within hollandites, octahedral layers, and trigonal-prismatic layers. For d2-d2-5 hollandite systems, distortions of zigzag Mo chains are coupled to π interactions with trigonal-planar oxides that stitch the double chains of the structure together. Zigzag chains embedded within Cdl2-like layers are stable for electron counts at which one would expect discrete clusters within a hollandite framework. As in chalcogenides, trigonal-prismatic transition-metal dioxide layers are expected to be most stable for d2 metals. The stability of the trigonal-prismatic layer compounds LiNbO2 and NaNbO2 is understandable as compared with octahedral alternatives and as compared with distorted variants of the trigonal-prismatic structure. © 1985, American Chemical Society. All rights reserved.
author list (cited authors)
Burdett, J. K., & Hughbanks, T.