Eight-Coordinate Endohedral Rhenium, Osmium and Iridium Atoms in Rare-Earth Halide Cluster Complexes

Endohedral (interstitial) atoms are essential for almost all of the rare-earth halide cluster complexes. Most of these contain octahedral clusters, some are isolated, but the majority exhibits condensation by common edges to structures of higher dimensionality. Higher coordination numbers of the endohedral atoms are rare. Four examples of extended cluster complexes with eight-coordinate endohedral atoms of sixth-period elements (Re, Os, Ir) are presented. In the quasi-isostructural, non-isotypic halides {ReGd(4)}Br(4) and (OsSc(4))Cl(4), square antiprisms of gadolinium and scandium atoms, respectively, are connected by two common faces to chains, surrounded and loosely connected by halogenido ligands. The Re and Os atoms build a slightly bent chain with only little bonding interactions. Chemical bonding is dominated by endohedral atom-cluster atom and cluster atom-halide interactions. The same is true for the two scandium bromides and {Os(3)Sc(12)}Br(16)Sc, which contain chains of face-sharing square antiprisms and cubes in a ratio of 2:1. Metal metal bonding is attested by short distances between those endohedral Ir and Os atoms, respectively, which center the square antiprisms (283 pm and 290 pm, respectively). Magnetic and conductivity measurements on {Ir(3)Sc(12)}Br(16) reveal paramagnetism and a small-band-gap semiconductor. This is in accord with electronic structure calculations