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EnglishThe supramol. hydrogen-bonded adducts obtained by treating the cationic bis-amido complex [CoIII(h5-C5H4CONHC5H4N)2]+ with fumaric and maleic acid are investigated and their modes of aggregation in the solid state are explored. It is shown that the bis-amido organometallic complex can be mono- and di-protonated in the reaction with the dicarboxylic acids, leading to the formation of complex, mixed-anion supramol. salts contg. either the dication [CoIII(h5-C5H4CONHC5H4N)(h5-C5H4CONHC5H4NH)]2+, [1H]2+, or the trication [CoIII(h5-C5H4CONHC5H4NH)2]3+, [1H2]3+. The derivs. of the reaction with fumaric acid, namely, [CoIII(h5-C5H4CONHC5H4N)(h5-C5H4CONHC5H4NH)]2+.[PF6]-.1/2[fumarate]2-, [1H]2+.PF6-.1/2[fumarate]2-, and [CoIII(h5-C5H4CONHC5H4NH)2]3+.[PF6]-.[H(fumarate)2]3-.H3O+.H2O, [1H2]3+.[PF6]-.[H(fumarate)2 ]3-.H3O+.H2O, contain either the dianion [fumarate]2- or the hydrogen-bridged supramol. trianion [H(fumarate)2]3-, depending on the amide/acid stoichiometric ratio. In the case of maleic acid, on the other hand, the possibility of intramol. hydrogen-bond formation generates exclusively salts of the hydrogen maleate anions, namely, [CoIII(h5-C5H4CONHC5H4N)(h5-C5H4CONHC5H4NH)]2+.5/2[PF6]-.3/2[Hmaleate]-, 2[1H]2+.5/2[PF6]-.3/2[Hmaleate]-, 2[CoIII(h5-C5H4CONHC5H4NH)2]3+.3[PF6]-.3[Hmaleate]-.2H2O, 2[1H2]3+.3[PF6]-.3[Hmaleate]-.2H2O and [CoIII(h5-C5H4CONHC5H4NH)2]3+.2[PF6]-.[Hmaleate]-.H2O, [1H2]3+.2[PF6]-.[Hmaleate]-.H2O, in which the hydrogen maleate anions act as bridges between the protonated bis-amido organometallic sandwiches.
| Titolo: | Design, preparation and characterization of the adducts of the bis-amido cobalticinium complex [CoIII(h5-C5H4CONHC5H4N) 2][PF6] with fumaric and maleic acids. |
| Autore/i: | BRAGA, DARIO; GIAFFREDA, STEFANO LUCA; POLITO, MARCO; GREPIONI, FABRIZIA |
| Autore/i Unibo: | |
| Anno: | 2005 |
| Rivista: | |
| Digital Object Identifier (DOI): | http://dx.doi.org/10.1002/ejic.200500143 |
| Abstract: | The supramol. hydrogen-bonded adducts obtained by treating the cationic bis-amido complex [CoIII(h5-C5H4CONHC5H4N)2]+ with fumaric and maleic acid are investigated and their modes of aggregation in the solid state are explored. It is shown that the bis-amido organometallic complex can be mono- and di-protonated in the reaction with the dicarboxylic acids, leading to the formation of complex, mixed-anion supramol. salts contg. either the dication [CoIII(h5-C5H4CONHC5H4N)(h5-C5H4CONHC5H4NH)]2+, [1H]2+, or the trication [CoIII(h5-C5H4CONHC5H4NH)2]3+, [1H2]3+. The derivs. of the reaction with fumaric acid, namely, [CoIII(h5-C5H4CONHC5H4N)(h5-C5H4CONHC5H4NH)]2+.[PF6]-.1/2[fumarate]2-, [1H]2+.PF6-.1/2[fumarate]2-, and [CoIII(h5-C5H4CONHC5H4NH)2]3+.[PF6]-.[H(fumarate)2]3-.H3O+.H2O, [1H2]3+.[PF6]-.[H(fumarate)2 ]3-.H3O+.H2O, contain either the dianion [fumarate]2- or the hydrogen-bridged supramol. trianion [H(fumarate)2]3-, depending on the amide/acid stoichiometric ratio. In the case of maleic acid, on the other hand, the possibility of intramol. hydrogen-bond formation generates exclusively salts of the hydrogen maleate anions, namely, [CoIII(h5-C5H4CONHC5H4N)(h5-C5H4CONHC5H4NH)]2+.5/2[PF6]-.3/2[Hmaleate]-, 2[1H]2+.5/2[PF6]-.3/2[Hmaleate]-, 2[CoIII(h5-C5H4CONHC5H4NH)2]3+.3[PF6]-.3[Hmaleate]-.2H2O, 2[1H2]3+.3[PF6]-.3[Hmaleate]-.2H2O and [CoIII(h5-C5H4CONHC5H4NH)2]3+.2[PF6]-.[Hmaleate]-.H2O, [1H2]3+.2[PF6]-.[Hmaleate]-.H2O, in which the hydrogen maleate anions act as bridges between the protonated bis-amido organometallic sandwiches. |
| Data prodotto definitivo in UGOV: | 2005-10-03 14:25:16 |
| Appare nelle tipologie: | 1.01 Articolo in rivista |
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http://hdl.handle.net/11585/9163
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