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Syntheses and characterization of mono and dinuclear complexes of platinum group metals bearing benzene-linked bis(pyrazolyl)methane ligands
Auteur(s)
Date de parution
2010
In
Journal of Organometallic Chemistry, Elsevier, 2010/695/9/1375–1382
Résumé
Reaction of the benzene-linked bis(pyrazolyl)methane ligands, 1,4-bis{bis(pyrazolyl)-methyl}benzene (L1) and 1,4-bis{bis(3-methylpyrazolyl)methyl}benzene (L2), with pentamethylcyclopentadienyl rhodium and iridium complexes [(η<sup>5</sup>-C<sub>5</sub>Me<sub>5</sub>)M(μ-Cl)Cl]<sub>2</sub> (M = Rh and Ir) in the presence of NH<sub>4</sub>PF<sub>6</sub> results under stoichiometric control in both, mono and dinuclear complexes, [(η<sup>5</sup>-C<sub>5</sub>Me<sub>5</sub>)RhCl(L)]<sup>+</sup> {L = L1 (<b>1</b>); L2 (<b>2</b>)}, [(η<sup>5</sup>-C<sub>5</sub>Me<sub>5</sub>)IrCl(L)]+ {L = L1 (<b>3</b>); L2 (<b>4</b>)} and [{(η<sup>5</sup>-C<sub>5</sub>Me<sub>5</sub>)RhCl}<sub>2</sub>(μ-L)]<sup>2+</sup> {L = L1 (<b>5</b>); L2 (<b>6</b>)}, [{(η<sup>5</sup>-C<sub>5</sub>Me<sub>5</sub>)IrCl}<sub>2</sub>(μ-L)]<sup>2+</sup> {L = L1 (<b>7</b>); L2 (<b>8</b>)}. In contrast, reaction of arene ruthenium complexes [(η<sup>6</sup>arene)Ru(μ-Cl)Cl]<sub>2</sub> (arene = C<sub>6</sub>H<sub>6</sub>, <i>p-<sup>i</sup></i>PrC<sub>6</sub>H<sub>4</sub>Me and C<sub>6</sub>Me<sub>6</sub>) with the same ligands (L1 or L2) gives only the dinuclear complexes [{(η<sup>6</sup>-C<sub>6</sub>H<sub>6</sub>)RuCl}<sub>2</sub>(μ-L)]<sup>2+</sup> {L = L1 (<b>9</b>); L2 (<b>10</b>)}, [{(η<sup>6</sup>-<i>p-<sup>i</sup></i>PrC<sub>6</sub>H<sub>4</sub>Me)RuCl}<sub>2</sub> (μ-L)]<sup>2+</sup> {L = L1 (<b>11</b>); L2 (<b>12</b>)} and [{(η<sup>6</sup>-C<sub>6</sub>Me<sub>6</sub>)RuCl}<sub>2</sub>(μ-L)]<sup>2+</sup> {L = L1 (<b>13</b>); L2 (<b>14</b>)}. All complexes were isolated as their hexafluorophosphate salts. The single-crystal X-ray crystal structure analyses of [<b>7</b>](PF<sub>6</sub>)<sub>2</sub>, [<b>9</b>](PF<sub>6</sub>)<sub>2</sub> and [<b>11</b>](PF<sub>6</sub>)<sub>2</sub> reveal a typical piano-stool geometry around the metal centers with six-membered metallo-cycle in which the 1,4-bis{bis(pyrazolyl)-methyl}benzene acts as a bis-bidentate chelating ligand.
Identifiants
Type de publication
journal article
