Oligomeric Rare-Earth-Metal Halide Clusters. Three Structures Built of (Y(16)Z(4))Br(36) Units (Z = Ru, Ir).
Suitable reactions in sealed Nb tubing at 850-950 degrees C gave good yields of a family of oligomeric cluster phases that were characterized by single-crystal X-ray diffraction means. The basic Y(16)Z(4) units ( approximately &fourmacr; symmetry) can be derived from 2+2 condensation of centered Y(6)Br(12)Z-type clusters or as tetracapped truncated tetrahedra Y(16) that are centered by a large tetrahedral Z(4). These are surrounded by 36 bromine atoms which bridge edges or cap faces of the Y(16)Z(4) nuclei and, in part, bridge to metal atoms in other clusters. The principal bonding appears to be Y-Z and Y-Br, with weaker Y-Y (&dmacr; approximately 3.70 Å) and negligible Z-Z interactions. The phase Y(16)Br(20)Ru(4) (P4(2)/nnm, Z = 2; a = 11.662(1) Å, c = 16.992 (2) Å) is isostructural with Y(16)I(20)Ru(4) and with the new Sc(16)Br(20)Z(4) (Z = Fe, Os). Syntheses only in the presence of Ir and ABr-YBr(3) fluxes (A = K-Cs) produce Y(16)Br(24)Ir(4) (Fddd, Z = 8; a = 11.718(3) Å, b = 22.361(7) Å, c = 44.702(2) Å), in which the electron-richer Ir interstitials are compensated by four additional bromine atoms and altered bridging between macroclusters. Larger amounts of YBr(3) yield a third example, Y(20)Br(36)Ir(4) (Y(16)Br(24)Ir(4).4YBr(3), I4(1)a, Z = 4; a = 12.699(1) Å, c = 45.11(1) Å). Here infinite zigzag chains of YBr(6/2) octahedra that share cis edges lie between and bridge to the Y(16)Ir(4) clusters. All of these phases contain 60-electron, closed-shell macroclusters. Y(16)Br(20)Ru(4) and Y(20)Br(36)Ir(4) were found to exhibit temperature-independent (Van Vleck) paramagnetism with values typical of those found for other rare-earth-metal, zirconium, niobium, and tantalum cluster halides.
Steinwand
Sharon J.
SJ
Department of Chemistry, Iowa State University, Ames, Iowa 50011.
Corbett
John D.
JD