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Synthesis and structure of sulfur and selenium capped dihydride triruthenium clusters [Ru-3(CO)(7)(mu-H)(2)(mu-dppm)(mu(3)-E)] (E = S, Se)

Hyder, MI; Begum, N; Sikder, MDH; Hossain, GMG; Hogarth, G; Kabir, SE; Richard, CJ; (2009) Synthesis and structure of sulfur and selenium capped dihydride triruthenium clusters [Ru-3(CO)(7)(mu-H)(2)(mu-dppm)(mu(3)-E)] (E = S, Se). J ORGANOMET CHEM , 694 (2) 304 - 308. 10.1016/j.jorganchem.2008.10.030.

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Abstract

Reaction of [Ru-3(CO)(10)(mu-dppm)] (1) with H2S at 66 degrees C affords high yields of the sulfur-capped dihydride [Ru-3(CO)(7)(mu-H)(2)(mu-dppm)(mu(3)-S)](2), formed by oxidative-addition of both hydrogen-sulfur bonds. Hydrogenation of [Ru-3(CO)(7)(mu-dppm)(mu(3)-CO)(mu(3)-S)] (3) at 110 degrees C also gives 2 in similar yields, while hydrogenation of [Ru-3(CO)(7)(mu-dppm)(mu(3)-CO)(mu(3)-Se)] (4) affords [Ru-3(CO)(7)(mu-H)(2)(mu-dppm)(mu(3)-Se)] (5) in 85% yield. The molecular structures of 2 and 5 reveal that the diphosphine and one hydride simultaneously bridge the same ruthenium-ruthenium edge with the second hydride spanning one of the nonbridged edges. Both 2 and 5 are fluxional at room temperature being attributed to hydride migration between the non-bridged edges. Addition of HBF4 to 2 affords the cationic trihydride [Ru-3(CO)(7)(mu-H)(3)(mu-dppm)(mu(3)-S)][BF4] (6) in which the hydrides are non-fluxional due to the blocking of the free ruthenium-ruthenium edge. (C) 2008 Elsevier B.V. All rights reserved.

Type:Article
Title:Synthesis and structure of sulfur and selenium capped dihydride triruthenium clusters [Ru-3(CO)(7)(mu-H)(2)(mu-dppm)(mu(3)-E)] (E = S, Se)
DOI:10.1016/j.jorganchem.2008.10.030
Keywords:Triuthenium cluster, Dihydride, Sulfide, Selenide, Bridging dppm, Crystal structures, BEARING BRIDGING DPPM, X-RAY STRUCTURES, TRIOSMIUM CLUSTERS, CRYSTAL-STRUCTURES, CARBONYL CLUSTERS, CAPPING SULFIDO, LIGANDS, COMPLEXES, CHEMISTRY, OSMIUM
UCL classification:UCL > School of BEAMS > Faculty of Maths and Physical Sciences > Chemistry

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