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Study of novel η<sup>5</sup>-cyclopentadienyl and η<sup>6</sup>-arene platinum group metal complexes containing a N<sub>4</sub>-type ligand and their structural characterization
Auteur(s)
Date de parution
2009
In
Polyhedron, Elsevier, 2009/28/4/844-850
Résumé
The mononuclear η<sup>5</sup>-cyclopentadienyl complexes [(η<sup>5</sup>-C<sub>5</sub>H<sub>5</sub>)Ru(PPh<sub>3</sub>)<sub>2</sub>Cl], [(η</sup>5</sup>-C<sub>5</sub>H<sub>5</sub>)Os(PPh<sub>3</sub>)<sub>2</sub>Br] and pentamethylcyclopentadienyl complex [(η<sup>5</sup>-C<sub>5</sub>Me<sub>5</sub>)Ru(PPh<sub>3</sub>)<sub>2</sub>Cl] react in the presence of 1 eq. of the tetradentate <i>N,N′</i>-chelating ligand 3,5-bis(2-pyridyl)pyrazole (bpp-H) and 1 eq. of NH<sub>4</sub>PF<sub>6</sub> in methanol to afford the mononuclear complexes [(η<sup>5</sup>-C<sub>5</sub>H<sub>5</sub>)Ru(PPh<sub>3</sub>)(bpp-H)]PF<sub>6</sub> ([<b>1</b>]PF<sub>6</sub>), [(η<sup>5</sup>-C<sub>5</sub>H<sub>5</sub>)Os(PPh<sub>3</sub>)(bpp-H)]PF<sub>6</sub> ([<b>2</b>]PF<sub>6</sub>) and [(η<sup>5</sup>-C<sub>5</sub>Me<sub>5</sub>)Ru(PPh<sub>3</sub>)(bpp-H)]PF<sub>6</sub> ([<b>3</b>]PF<sub>6</sub>), respectively. The dinuclear η<sup>5</sup>-pentamethylcyclopentadienyl complexes [(η<sup>5</sup>-C<sub>5</sub>Me<sub>5</sub>)Rh(μ-Cl)Cl]<sub>2</sub> and [(η<sup>5</sup>-C<sub>5</sub>Me<sub>5</sub>)Ir(μ-Cl)Cl]<sub>2</sub> as well as the dinuclear η<sup>6</sup>-arene ruthenium complexes [(η<sup>6</sup>-C<sub>6</sub>H<sub>6</sub>)Ru(μ-Cl)Cl]<sub>2</sub> and [(η<sup>6</sup>-<i>p</i>-<sup>i</sup>PrC<sub>6</sub>H<sub>4</sub>Me)Ru(μ-Cl)Cl]<sub>2</sub> react with 2 eq. of bpp-H in the presence of NH<sub>4</sub>PF<sub>6</sub> or NH<sub>4</sub>BF<sub>4</sub> to afford the corresponding mononuclear complexes [(η<sup>5</sup>-C<sub>5</sub>Me<sub>5</sub>)Rh(bpp-H)Cl]PF<sub>6</sub> ([<b>4</b>]PF<sub>6</sub>), [(η<sup>5</sup>-C<sub>5</sub>Me<sub>5</sub>)Ir(bpp-H)Cl]PF<sub>6</sub> ([<b>5</b>]PF<sub>6</sub>), [(η<sup>6</sup>-C<sub>6</sub>H<sub>6</sub>)Ru(bpp-H)Cl]BF<sub>4</sub> ([<b>6</b>]BF<sub>4</sub>) and [(η<sup>6</sup>-<i>p</i>-<sup>i</sup>PrC<sub>6</sub>H<sub>4</sub>Me)Ru(bpp-H)Cl]BF<sub>4</sub> ([<b>7</b>]BF<sub>4</sub>). However, in the presence of 1 eq. of bpp-H and NH<sub>4</sub>BF<sub>4</sub> the reaction with the same η<sup>6</sup>-arene ruthenium complexes affords the dinuclear salts [(η<sup>6</sup>-C<sub>6</sub>H<sub>6</sub>)<sub>2</sub>Ru<sub>2</sub> (bpp)Cl<sub>2</sub>]BF<sub>4</sub> ([<b>8</b>]BF<sub>4</sub>) and [(η<sup>6</sup>-<i>p</i>-<sup>i</sup>PrC<sub>6</sub>H<sub>4</sub>Me)<sub>2</sub>Ru<sub>2</sub> (bpp)Cl<sub>2</sub>]BF<sub>4</sub> ([<b>9</b>]BF<sub>4</sub>), respectively. These compounds have been characterized by IR, NMR and mass spectrometry, as well as by elemental analysis. The molecular structures of [<b>1</b>]PF<sub>6</sub>, [<b>5</b>]PF<sub>6</sub> and [<b>8</b>]BF<sub>4</sub> have been established by single crystal X-ray diffraction studies and some representative complexes have been studied by UV–vis spectroscopy.
Identifiants
Type de publication
journal article
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