Axial-site modifications of paddlewheel diruthenium(II, II) complexes supported by hydrogen bonding

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The reactions of paddlewheel-type diruthenium(II, II) complexes, [Ru 2II,II(x-FPhCO2)4(THF)2] (x-FPhCO2- = x-fluorobenzoate with x- = o-, m-, p-), with 2,6-diaminopyridine (dapy) and 7-azaindole (azain) afford axially capped discrete compounds, [Ru2II,II(x-FPhCO2) 4(dapy)2] (x = o-, 1; m-, 2; p-, 3) and [Ru 2II,II(o-FPhCO2)4(azain) 2] (4), respectively. In these compounds, intramolecular hydrogen bonds are observed between NH2 groups for 1-3 or imine NH groups for 4 and oxygen atoms of carboxylate groups. In addition, hydrogen bonds of NH 2···F are also observed for 1 and 4 with an o-positioned F atom on benzoate. This coordination mode, i.e., a dual bonding mode with σ-bonding and hydrogen bonding, should assist ligand coordination to the axial position of the [Ru2] unit. The Ru-N bond distance in 1-4 is shorter than that observed in related compounds reported previously. In a similar fashion, reactions with planar MII dithiobiuret (dtb) complexes, [MII(dtb)2] (MII = PdII and PtII), were carried out. One-dimensional alternating chains, [{Ru2II,II(o-FPhCO2) 4}{MII(dtb)2}] (MII = Pd II, 5; PtII, 6), were obtained, in which the hydrogen-bonding modes of NH2···O and NH 2···F are present, as expected. DFT calculations for the [MII(dtb)2] unit revealed that the LUMO of [MII(dtb)2] lies at -2.159 and -1.781 eV for M = Pd and Pt, respectively, which is much higher than HOMO energy at -4.184 eV calculated for [Ru2II,II(o-FPhCO2)(THF)2], proving that the respective units are essentially electronically isolated in the chains.

Original languageEnglish
Pages (from-to)9908-9914
Number of pages7
JournalInorganic Chemistry
Issue number17
Publication statusPublished - 2013 Sept 2


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