Synthesis and crystal structures of urea and thiourea derivatives of diruthenium(II,III) tetraacetate

Cooke, Michael W., Murphy, Christopher A., Cameron, T. Stanley, Beck, Ellen J., Vamvounis, George, and Aquino, Mauel A.S. (2002) Synthesis and crystal structures of urea and thiourea derivatives of diruthenium(II,III) tetraacetate. Polyhedron, 21 (12-13). pp. 1235-1244.

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Diadduct complexes of the mixed-valent form of diruthenium tetraacetate, [Ru-2(mu-O2CCH3)(4)L-2](PF6), with L = urea (1), 1,1,3,3-tetramethylurea (tmu) (2) and 1,1,3,3-tetramethyl-2-thiourea (tmtu) (3) have been synthesized and characterized by elemental analysis, IR and UV-Vis spectroscopy, magnetic susceptibility, cyclic voltammetry and X-ray crystallography. Compound 1 crystallizes as a co-diadduct system from 1-propanol in which both [Ru-2(mu-O2CCH3)(4)(urea)(2)](+) and [Ru-2(mu-O2CCH3)(4)(1-propanol)(2)](+) cations are present in the unit cell. Complex 3 displays a very long Ru-S bond of 2.610(2) Angstrom and is only the second example of a sulfur-donor adduct of a diruthenium tetracarboxylate that has been structurally characterized. Electrochemical measurements on 2 and 3 show them to have reduction potentials of -487 and -541 mV (vs. Fc/Fc(+)), respectively, which is in the range of moderate to strong axial donor adducts despite the long Ru-S bond in 3. Reaction of [Ru-2(mu-O2CCH3)(4)(H2O)(2)](PF6) with thiourea yields a 1:1 complex, [Ru-2(mu-O2CCH3)(4)(thiourea)](PF6), which from solubility and infrared evidence appears to be a polymer in which the thiourea bridges through the sulfur and one of the amine nitrogens.

Item ID: 32744
Item Type: Article (Research - C1)
ISSN: 1873-3719
Keywords: diruthenium carboxylates, urea and thiourea derivatives, crystal structures, infrared spectroscopy
Funders: Natural Sciences and Engineering Research Council of Canada, University Council for Research
Date Deposited: 14 Oct 2015 02:49
FoR Codes: 03 CHEMICAL SCIENCES > 0302 Inorganic Chemistry > 030207 Transition Metal Chemistry @ 100%
SEO Codes: 86 MANUFACTURING > 8616 Computer Hardware and Electronic Equipment > 861604 Integrated Systems @ 100%
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