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Ternary rare earth and actinoid transition metal carbides viewed as carbometalates.pdf
ARTICLE IN PRESS
Journal of Solid State Chemistry 180 (2007) 636–653
/locate/jssc
Ternary rare earth and actinoid transition metal carbides viewed as carbometalates
Enkhtsetseg Dashjava, Guido Kreinera, Walter Schnellea, Frank R. Wagnera, Ru¨ diger Kniepa,?, Wolfgang Jeitschkob
aMax-Planck-Institut fu¨ r Chemische Physik fester Stoffe, No¨thnitzer StraX e 40, D-01187 Dresden, Germany bInstitut fu¨ r Anorganische und Analytische Chemie, Universita¨ t Mu¨ nster, Wilhelm-Klemm-StraX e 8, D-48149 Mu¨ nster, Germany
Received 2 October 2006; received in revised form 8 November 2006; accepted 13 November 2006 Available online 30 November 2006
Abstract
Ternary carbides AxTyCz (A ? rare earth metals and actinoids; T ? transition metals) with monoatomic species C4à as structural entities are classi?ed according to the criteria (i) metal to carbon ratio, (ii) coordination number of the transition metal by carbon atoms, and (iii) the dimensionality of the anionic network [TyCz]nà. Two groups are clearly distinguishable, depending on the metal to carbon ratio. Those where this ratio is equal to or smaller than 2 may be viewed as carbometalates, thus extending the sequence of complex anions from ?uoro-, oxo-, and nitridometalates to carbometalates. The second group, metal-rich carbides with metal to carbon ratios equal to or larger than 4 is better viewed as typical intermetallics (‘‘interstitial carbides’’). The chemical bonding properties have been investigated by analyzing the Crystal Orbital Hamilton Population (COHP). The chemical bonding situation with respect to individual T–C bonds is similar in both classes. The main difference is the larger number of metal–metal bonds in the crystal structures of the metalrich carbides. r 2006 Elsevier Inc. All rights reserved.
Keywords: Carbides; Carbometalates; Rare earth metals; Transition metals; Crystal structure; Chemical bonding
1. Introduction
In the past decades, a large number of investigations were focused on the synthesis, s
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