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Mono and dinuclear iridium, rhodium and ruthenium complexes containing chelating carboxylato pyrazine ligands: Synthesis, molecular structure and electrochemistry
Auteur(s)
Govindaswamy, Padavattan
Štěpnička, Petr
Ludvík, Jiří
Date de parution
2007
In
Journal of Organometallic Chemistry, Elsevier, 2007/692/8/1661-1671
Résumé
The mononuclear complexes [(η<sup>5</sup>-C<sub>5</sub>Me<sub>5</sub>)IrCl(L<sup>1</sup>)] (<b>1</b>), [(η<sup>5</sup>-C<sub>5</sub>Me<sub>5</sub>)RhCl(L<sup>1</sup>)] (<b>2</b>), [(η<sup>6</sup>-<i>p</i>-Pr<i>i</i>C<sub>6</sub>H<sub>4</sub>Me)RuCl(L<sup>1</sup>)] (<b>3</b>) and [(η<sup>6</sup>-C<sub>6</sub>Me<sub>6</sub>)RuCl(L<sup>1</sup>)] (<b>4</b>) have been synthesised from pyrazine-2-carboxylic acid (HL<sup>1</sup>) and the corresponding complexes [{(η<sup>5</sup>-C<sub>5</sub>Me<sub>5</sub>)IrCl<sub>2</sub>}<sub>2</sub>], [{(η<sup>5</sup>-C<sub>5</sub>Me<sub>5</sub>)RhCl<sub>2</sub>}<sub>2</sub>], [{(η<sup>6</sup>-<i>p</i>-Pr<i><sup>i</sup></i>C<sub>6</sub>H<sub>4</sub>Me)RuCl<sub>2</sub>}<sub>2</sub>], and [{(η<sup>6</sup>-C<sub>6</sub>Me<sub>6</sub>)RuCl<sub>2</sub>}<sub>2</sub>], respectively. The related dinuclear complexes [{(η<sup>5</sup>-C<sub>5</sub>Me<sub>5</sub>)IrCl}<sub>2</sub> (μ-L<sup>2</sup>)] (<b>5</b>), [{(η<sup>5</sup>-C<sub>5</sub>Me<sub>5</sub>)RhCl}<sub>2</sub> (μ-L<sup>2</sup>)] (<b>6</b>), [{(η<sup>6</sup>-<i>p</i>-Pr<i><sup>i</sup></i>C<sub>6</sub>H<sub>4</sub>Me)RuCl}<sub>2</sub> (μ-L<sup>2</sup>)] (<b>7</b>) and [{(η<sup>6</sup>-C<sub>6</sub>Me<sub>6</sub>)RuCl}<sub>2</sub> (μ-L<sup>2</sup>)] (<b>8</b>) have been obtained in a similar manner from pyrazine-2,5-dicarboxylic acid (H<sub>2</sub>L<sub>2</sub>). Compounds isomeric to the latter series, [{(η<sup>5</sup>-C<sub>5</sub>Me<sub>5</sub>)IrCl}<sub>2</sub> (μ-L<sup>3</sup>)] (<b>9</b>), [{(η<sup>5</sup>-C<sub>5</sub>Me<sub>5</sub>)RhCl}<sub>2</sub> (μ-L<sup>3</sup>)] (<b>10</b>), [{(<i>p</i>-Pr<i><sup>i</sup></i>C<sub>6</sub>H<sub>4</sub>Me)RuCl}<sub>2</sub> (μ-L<sup>3</sup>)] (<b>11</b>) and [{(η<sup>6</sup>-C<sub>6</sub>Me<sub>6</sub>)RuCl}<sub>2</sub> (μ-L<sup>3</sup>)] (<b>12</b>), have been prepared by using pyrazine-2,3-dicarboxylic acid (H<sub>2</sub>L<sub>3</sub>) instead of H<sub>2</sub>L<sub>2</sub>. The molecular structures of <b>2</b> and <b>3</b>, determined by X-ray diffraction analysis, show the pyrazine-2-carboxylato moiety to act as an <i>N,O</i>-chelating ligand, while the structure analyses of <b>5–7</b>, confirm that the pyrazine-2,5-dicarboxylato unit bridges two metal centres. The electrochemical behaviour of selected representatives has been studied by voltammetric techniques.
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journal article
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