The first report on specific binding mode of diethylmalonate acting as a bridging ligand between ruthenium (II) ions stabilized by intramolecular hydrogen bonds |
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| Authors: | Radhey S Srivastava Frank R Fronczek |
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| Institution: | a Department of Chemistry, University of Louisiana at Lafayette, Lafayette, LA 70504, USA
b Department of Chemistry, Louisiana State University, Baton Rouge, LA 70803, USA |
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| Abstract: | Typically 2,2-diethylmalonate (dem) acts as a chelating ligand and binds to the metal in a η2 (dem-O, O′) mode. However, when cis,fac-RuCl2(TMSO-S)4] is treated with K2(dem), it prefers to bind in an unusual bridging mode (μ-dem-O, O′) with the ruthenium (II) cation containing coordinated water, forming a strong hydrogen bond with the non-coordinated oxygen atoms of the 2,2-diethylmalonate ligand. The reaction products of cis,fac-RuCl2(TMSO-S)4] (1) and cis,fac-RuCl2(DMSO-S)3(DMSO-O)] (2) with dem are the dinuclear species with two bridging dem units, fac-Ru(TMSO-S)3(H2O)(μ2-dem-O, O′)]2 (3) and fac-Ru(DMSO-S)3(H2O)(μ2-dem-O, O′)]2 (4), respectively. The complex 3 was characterized by X-ray crystallography in which water ligands occupy anti positions with respect to each other. The NMR and X-ray study support each other with respect to dinuclear structure of 3 and 4, indicating that the dinuclear structure observed in the solid state is preserved in solution as well. The mononuclear anionic complex with chelating dem unit, K{fac-RuCl(η2-dem-O, O′)(TMSO-S)3} (5), was also isolated from the reaction of 1 and K2(dem) demonstrating that 5 is an intermediate in the formation of 3. |
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| Keywords: | Diethylmalonate TMSO DMSO Dimer Dinuclear Hydrogen bond |
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