Encapsulation of heavy transition metals in iodide clusters. Synthesis, structure, and bonding of the unusual cluster phase yttrium iodide-ruthenium (Y6I10Ru)
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The reaction of Y3Ru with YI3at 800–950 °C in a sealed Ta container affords Y7I12Ru and Y6I10Ru, the yield of the latter increasing with time or temperature. Y7I12Ru is isostructural withsc7C112B on the basis of Guinier powder data (R3, Z = 3, a = 15.4373 (7) Å, c = 10.6126 (6) Å). The new structure type of Y6I10Ru was deduced from its lattice dimensions and symmetry and was refined with single-crystal X-ray diffraction data (PI, Z = 1; a = 9.456 (2) Å, b = 9.643 (2) Å, c = 7.629 (1) Å, a = 97.20 (2)°, β= 105.04 (2)°, γ= 107.79 (2)°; R = 5.2, Rw= 6.7% for 1421 independent reflections, 2θ≤ 55°, Mo Ka radiation). The structure consists of Y6i12clusters centered by Ru and condensed into infinite chains through sharing of inner iodine (I1) atoms with the two adjoining clusters, viz., Y6Ii8Ii-i4/2Ru. The clusters are connected in the other two directions through the more typical Ii_alinkages at metal vertices. The nominal octahedral Y6Ru cluster shows a 0.21-A tetragonal compression, contrary to the usual behavior of ML6units with a tlu4HOMO. Charge-iterative extended Hiickel calculations show that the distortion originates with Y-Y interactions because of a negligible participation of the high-lying Ru 5p orbitals in the HOMO. © 1989, American Chemical Society. All rights reserved.
author list (cited authors)
Hughbanks, T., & Corbett, J. D.