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Cationic arene ruthenium complexes containing chelating 1,10-phenanthroline ligands
Auteur(s)
Date de parution
2005-07-01
In
Journal of Organometallic Chemistry, 2005/690/3202-3211
Résumé
The monocationic chloro complexes containing chelating 1,10-phenanthroline (phen) ligands [(arene)Ru(N∩N)Cl] <sup>+</sup> (<b>1</b>: arene = C<sub>6</sub>H<sub>6</sub>, N∩N = phen; <b>2</b>: arene = C<sub>6</sub>H<sub>6</sub>, N∩N = 5-NO<sub>2</sub>-phen; <b>3</b>: arene = p-MeC<sub>6</sub>H<sub>4</sub>Pr<sup>i</sup>, N∩N = phen; <b>4</b>: arene = p-MeC<sub>6</sub>H<sub>4</sub>Pr<sup>i</sup>, N∩N = 5-NO<sub>2</sub>-phen; <b>5</b>: arene = C<sub>6</sub>Me<sub>6</sub>, N∩N = phen; <b>6</b>: arene = C<sub>6</sub>Me<sub>6</sub>, N∩N = 5-NO<sub>2</sub>-phen; <b>7</b>: arene = C<sub>6</sub>Me<sub>6</sub>, N∩N = 5-NH<sub>2</sub>-phen) have been prepared and characterised as the chloride salts. Hydrolysis of these chloro complexes in aqueous solution gave, upon precipitation of silver chloride, the corresponding dicationic aqua complexes [(arene)Ru(N∩N)(OH<sub>2</sub>)]<sup>2+</sup> (<b>8</b>: arene = C<sub>6</sub>H<sub>6</sub>, N∩N = phen; <b>9</b>: arene = C<sub>6</sub>H<sub>6</sub>, N∩N = 5-NO<sub>2</sub>-phen; <b>10</b>: arene = p-MeC<sub>6</sub>H<sub>4</sub>Pr<sup>i</sup>, N∩N = phen; <b>11</b>: arene = p-MeC<sub>6</sub>H<sub>4</sub>Pri, N∩N = 5-NO<sub>2</sub>-phen; <b>12</b>: arene = C<sub>6</sub>Me<sub>6</sub>, N∩N = phen; <b>13</b>: arene = C<sub>6</sub>Me<sub>6</sub>, N∩N = 5-NO<sub>2</sub>-phen; <b>14</b>: arene = C<sub>6</sub>Me<sub>6</sub>, N∩N = 5-NH<sub>2</sub>-phen), which have been isolated and characterised as the tetrafluoroborate salts. The catalytic potential of the aqua complexes <b>8</b>–<b>14</b> for transfer hydrogenation reactions in aqueous solution has been studied: complexes <b>12</b> and <b>14</b> catalyse the reaction of acetophenone with formic acid to give phenylethanol and carbon dioxide with turnover numbers around 200 (80 °C, 7 h). In the case of <b>12</b>, it was possible to observe the postulated hydrido complex [(C<sub>6</sub>Me<sub>6</sub>)Ru(phen)H]<sup>+</sup> (<b>15</b>) in the reaction with sodium borohydride; <b>15</b> has been characterised as the tetrafluoroborate salt, the isolated product [<b>15</b>]BF<sub>4</sub>, however, being impure. The molecular structures of [(C<sub>6</sub>Me<sub>6</sub>)Ru(phen)Cl]<sup>+</sup> (<b>1</b>) and [(C<sub>6</sub>Me<sub>6</sub>)Ru(phen)(OH<sub>2</sub>)]<sup>2+</sup> (<b>12</b>) have been determined by single-crystal X-ray structure analysis of [<b>1</b>]Cl and [<b>12</b>](BF<sub>4</sub>)<sub>2</sub>.
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journal article
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