Options
The mixed-metal carbonyl cluster anion [Ru<sub>3</sub>Ir(CO)<sub>13</sub>]<sup>–</sup> : synthesis, molecular structure, fluxionality, reactivity
Auteur(s)
Haak, Susanne
Ferrand, Vincent
Date de parution
1997
In
Journal of the Chemical Society, Dalton Transactions, 1997//3861-3865
Résumé
The new cluster anion [Ru<sub>3</sub>Ir(CO)<sub>13</sub>]<sup>–</sup><b>1</b> was synthesized in high yield from [Ru<sub>3</sub>(CO)<sub>12</sub>] and [Ir(CO)<sub>4</sub>]<sup>–</sup>. The single-crystal X-ray structure analysis of the bis(triphenylphosphoranylidene)ammonium salt revealed the presence of two isomers, [Ru<sub>3</sub>Ir(CO)<sub>11</sub>(µ-CO)<sub>2</sub>]<sup>–</sup><b>1a</b> and Ru<sub>3</sub>Ir(CO)<sub>9</sub>(µ-CO)<sub>4</sub>]<sup>–</sup><b>1b</b> in the same crystal. Both <b>1a</b> and <b>1b</b> present a tetrahedral Ru<sub>3</sub>Ir framework, differing only by the number of bridging carbonyl ligands. Variable-temperature <sup>13</sup>C NMR spectroscopic studies of <b>1</b> revealed the fluxionality of the carbonyl ligands and the interconversion of both isomers in solution. Protonation of <b>1</b> gave the neutral cluster [HRu<sub>3</sub>Ir(CO)<sub>13</sub>] <b>2</b>, whereas reaction of <b>1</b> with molecular hydrogen yielded the anion [H<sub>2</sub>Ru<sub>3</sub>Ir(CO)<sub>12</sub>]<sup>–</sup><b>3</b>. Either hydrogenation of <b>2</b> or protonation of <b>3</b> gave [H<sub>3</sub>Ru<sub>3</sub>Ir(CO)<sub>12</sub>] <b>4</b>. The tetrahedral structure of the hydrido derivatives was confirmed by a single-crystal X-ray structure analysis of the bis(triphenylphosphoranylidene)ammonium salt of <b>3</b>.
Identifiants
Type de publication
journal article
Dossier(s) à télécharger
