Encapsulation of heavy transition metals in iodide clusters. Synthesis, structure, and bonding of the unusual cluster phase Y sub 6 I sub 10 Ru

Journal Article · Wed Feb 22 00:00:00 EST 1989 · Inorganic Chemistry; (USA)

DOI:https://doi.org/10.1021/ic00303a004· OSTI ID:5040752

Hughbanks, T; Corbett, J D ^[1]

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1. Texas A and M Univ., College Station (USA)

The reaction of Y{sub 3}Ru with YI{sub 3} at 800-950{degree}C in a sealed Ta container affords Y{sub 7}I{sub 12}Ru and Y{sub 6}I{sub 10}Ru, the yield of the latter increasing with time or temperature. Y{sub 7}I{sub 12}Ru is isostructural with Sc{sub 7}Cl{sub 12}B on the basis of Guinier powder data (R{anti 3}, Z = 3, a = 15.4373 (7) {angstrom}, c = 10.6126 (6) {angstrom}). The new structure type of Y{sub 6}I{sub 10}Ru was deduced from its lattice dimensions and symmetry and was refined with single-crystal x-ray diffraction data (P{anti 1}, Z = 1; a = 9.456 (2) {angstrom}, b = 9.643 (2) {angstrom}, c = 7.629 (1) {angstrom}, {alpha} = 97.20 (2){degree}, {beta} = 105.04 (2){degree}, {gamma} = 107.79 (2){degree}; R = 5.2, R{sub w} = 6.7% for 1421 independent reflections, 2{theta} {le} 55{degree}, Mo K{alpha} radiation). The structure consists of Y{sub 6}I{sub 12} clusters centered by Ru and condensed into infinite chains through sharing of inner iodine (I{sup 1}) atoms with the two adjoining clusters, viz., Y{sub 6}I{sup i}{sub 8}I{sup i-i}{sub 4/2}Ru. The clusters are connected in the other two directions through the more typical I{sup i-a} linkages at metal vertices. The nominal octahedral Y{sub 6}Ru cluster shows a 0.21-{angstrom} tetragonal compression, contrary to the usual behavior of ML{sub 6} units with a t{sub 1u}{sup 4} HOMO. Charge-iterative extended Hueckel 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. 20 refs., 4 figs., 3 tabs.

• OSTI ID: 5040752
• Journal Information: Inorganic Chemistry; (USA), Vol. 28:4; ISSN 0020-1669
• Country of Publication: United States
• Language: English

Related Subjects

37 INORGANIC
ORGANIC
PHYSICAL AND ANALYTICAL CHEMISTRY
RUTHENIUM COMPOUNDS
SYNTHESIS
YTTRIUM IODIDES
CRYSTAL STRUCTURE
EXPERIMENTAL DATA
MOLECULAR STRUCTURE
DATA
HALIDES
HALOGEN COMPOUNDS
INFORMATION
IODIDES
IODINE COMPOUNDS
NUMERICAL DATA
REFRACTORY METAL COMPOUNDS
TRANSITION ELEMENT COMPOUNDS
YTTRIUM COMPOUNDS
400201* - Chemical & Physicochemical Properties