| Hydrogen-bridged lanthanide(II)-boron complexes were synthesized and characterized. (CH3CN)xLn[B3H8] 2 was prepared by the metathesis reaction between (NH3) xLnCl2, (Ln = Yb, Eu) and K[B3H8] in liquid NH3 and subsequent displacement of NH3 with CH 3CN. The preliminary structure of (CH3CN)4Yb[B 3H8]2, 1, is interesting since the two [B3H8]− anions have different bonding modes. From NMR spectroscopic studies, the [B3H8] − anion was fluxional even at 213 K. [Yb(CH3CN) 8][B12H12], 2, and (CH3CN) 6Yb[(μ-H)2B11H11], 3, crystallized from the saturated CH3CN solution of (CH3CN) 4Yb[B3H8]2, 1. The oxidized species, [Eu(NH3)6(CH3CN)3][B 3H8]3, 7, was obtained from an CH 3CN solution of (CH3CN)xEu[B3H 8]2, 6. (THF)4Yb[(μ-H)2BC 8H14]2, 8, and [(THF)4K] 2[Eu{lcub}(μ-H)2BC8H14{rcub}4], 10, were synthesized by the metathesis reaction of (THF)xLnCl 2, (Ln = Yb, Eu) with K[H2BC8H14] in THF. 2 and 7 are solvent-separated ion-pairs. 3 is the only structurally characterized metallaborane containing 11 boron atoms. For 3, 8 and 10, the anions are coordinated to the Ln(II) ions through three-center two-electron B-H-Ln bonds. Bridging 6F5)3. Crystal data for 2: monoclinic, Cc, a = 14.2260(10)Å, b = 13.1350(10)Å, c = 16.4780(10)Å, β = 90.000(30)°, Z = 4. Crystal data for 3: monoclinic, P2 1/c, a = 9.5097(10)Å, b = 14.1574(10)Å, c = 22.8192(10)Å, β = 97.321(10)°, Z = 4. Crystal data for 7: hexagonal, P6 3/m, a = b = 14.2797(10)Å, c = 8.8740(10)Å, α = β 90°, γ = 120°, Z = 1. Crystal data for 8: triclinic, P1, a = 9.8616(10)Å, b = 10.2266(10)Å, c = 10.4760(10)Å, α = 69.873(10)°, β = 76.629(10)°, γ = 66.116(10)°, Z = 2. Crystal data for 10: tetragonal, P42/nmc, a = b = 13.4390(19)Å, c = 20.421(4)Å, α = β = γ = 90°, Z = 4.; Cyanide-bridged lanthanide(III)-palladium complexes were prepared and characterized. The metathesis reaction between LnCl3, (Ln = La, Gd) and K2[Pd(CN)4] with a 2 to 3 molar ratio in DMF yielded two different types of one-dimensional arrays: the double-strand Type B array, {lcub}(DMF)10Gd2[Pd(CN)4]3 {rcub}∞, 11, and the zigzag chain Type C array containing “diamond”-shaped metal cores, {lcub}(DMF)12La 2[Pd(CN)4]3{rcub}∞... |
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