The Prolific {ZR₆}X₁₂R and {ZR₆}X₁₀ Structure Types with Isolated Endohedrally Stabilized (Z) Rare‐Earth Metal (R) Cluster Halide (X) Complexes

Abstract

Comproportionation reactions of rare-earth metal trihalides, RX 3 , with the respective R metal in the presence of a transition metal Z, preferably from group 8 through 10, yielded single crystals of 31 {ZR 6 }X 12 R and 22 {ZR 6 }X 10 type compounds, in most cases for the first time, especially with R = Tb, Dy, Ho, and Er. These are compared with literature entries. The crystal structures are discussed for the equal-atom pair {IrEr 6 }I 12 Er and {IrEr 6 }I 10 . In both cases,

The Crystal Orbital Hamilton Population (COHP) Method as a Tool to Visualize and Analyze Chemical Bonding in Intermetallic Compounds

“…nickel-group interstitial in agreement with the outcome of the previous MO-theory-based calculations [58]. Furthermore, the bonding within the octahedral [TR6] clusters was shown to be dominated by the heteroatomic T−R interactions besides much lesser R−R bonding [58]. Among the group of rare-earth transition-metal halides composed of cluster oligomers, the crystal structures of a large number of compounds have been identified to contain one particular type of tetramer, [T 4 R 16 ] (Figure 1).…”

“…Furthermore, the bonding within the octahedral [TR 6 ] clusters was shown to be dominated by the heteroatomic T−R interactions besides much lesser R−R bonding [58]. nickel-group interstitial in agreement with the outcome of the previous MO-theory-based calculations [58]. Furthermore, the bonding within the octahedral [TR6] clusters was shown to be dominated by the heteroatomic T−R interactions besides much lesser R−R bonding [58].…”

“…For instance, a closed-shell configuration is expected for the previously identified [CoY 6 ]I 12 Y, for which an application of the electron-counting scheme yields a total of 18 CBEs (=9 + 7·3 − 12); however, the observed ranges of transition-metals being incorporated in the rare-earth clusters indicate certain electronic flexibilities. Chemical-bonding analysis based on the COHP curves of a number of [TR 6 ]X 10 -type compounds demonstrated that the bond energy is optimized for a halide with a nickel-group interstitial in agreement with the outcome of the previous MO-theory-based calculations [58]. Furthermore, the bonding within the octahedral [TR 6 ] clusters was shown to be dominated by the heteroatomic T−R interactions besides much lesser R−R bonding [58].…”

“…Chemical-bonding analysis based on the COHP curves of a number of [TR 6 ]X 10 -type compounds demonstrated that the bond energy is optimized for a halide with a nickel-group interstitial in agreement with the outcome of the previous MO-theory-based calculations [58]. Furthermore, the bonding within the octahedral [TR 6 ] clusters was shown to be dominated by the heteroatomic T−R interactions besides much lesser R−R bonding [58]. nickel-group interstitial in agreement with the outcome of the previous MO-theory-based calculations [58].…”

“…A large number of halides which are composed of isolated rare-earth clusters encapsulating transition-metal atoms has been identified to adopt the [TR 6 ]X 10 and [TR 6 ]X 12 R types of structure (note that the brackets define the components of the clusters) [56][57][58]. In particular, the endohedral transition-metal atoms which can be an element from the manganese-to zinc-groups for the [TR 6 ]X 12 R-type and from the iron-to nickel-groups for the [TR 6 ]X 10 -type are coordinated by octahedra constituted by the rare-earth atoms, while all edges of the octahedral [TR 6 ] clusters are capped by halide ligands.…”