Preparation and Reactivity of Stannyl Complexes of Ruthenium(II) Stabilized by an Indenyl Ligand AlbertinGabriele AntoniuttiStefano CastroJesús LioSebastiano Da 2013 Trichlorostannyl complexes Ru­(SnCl<sub>3</sub>)­(η<sup>5</sup>-C<sub>9</sub>H<sub>7</sub>)­(PPh<sub>3</sub>)­L (<b>1</b>; L = P­(OMe)<sub>3</sub>, P­(OEt)<sub>3</sub>) were prepared by allowing chloro compounds RuCl­(η<sup>5</sup>-C<sub>9</sub>H<sub>7</sub>)­(PPh<sub>3</sub>)­L to react with SnCl<sub>2</sub>·2H<sub>2</sub>O in ethanol. Treatment of compounds <b>1</b> with NaBH<sub>4</sub> in ethanol yielded the tin trihydride derivatives Ru­(SnH<sub>3</sub>)­(η<sup>5</sup>-C<sub>9</sub>H<sub>7</sub>)­(PPh<sub>3</sub>)­L (<b>2</b>). The reaction of trichlorostannyl complexes <b>1</b> with MgBrMe in diethyl ether afforded the chlorodimethylstannyl derivatives Ru­(SnClMe<sub>2</sub>)­(η<sup>5</sup>-C<sub>9</sub>H<sub>7</sub>)­(PPh<sub>3</sub>)­L (<b>3</b>), whereas reaction with Li<sup>+</sup>CCPh<sup>–</sup> in THF yielded the trialkynylstannyl compounds Ru­[Sn­(CCPh)<sub>3</sub>]­(η<sup>5</sup>-C<sub>9</sub>H<sub>7</sub>)­(PPh<sub>3</sub>)­L (<b>4</b>). Treatment of the trihydridostannyl complexes <b>2</b> with the alkyl propiolate HCCCOOR led to the trivinylstannyl derivatives Ru­[Sn­{C­(COOR)CH<sub>2</sub>}<sub>3</sub>]­(η<sup>5</sup>-C<sub>9</sub>H<sub>7</sub>)­(PPh<sub>3</sub>)­L (<b>5</b>,<b> 6</b>; R = Me, Et). However, the reaction of [Ru]–SnH<sub>3</sub> (<b>2</b>) with the propargylic alcohol HCCCPh<sub>2</sub>OH yielded the alkene H<sub>2</sub>CC­(H)­CPh<sub>2</sub>OH and the hydride RuH­(η<sup>5</sup>-C<sub>9</sub>H<sub>7</sub>)­(PPh<sub>3</sub>)­L (<b>7</b>). Treatment of tin trihydride complexes <b>2</b> with H<sub>2</sub>O led to the trihydroxostannyl derivatives Ru­[Sn­(OH)<sub>3</sub>]­(η<sup>5</sup>-C<sub>9</sub>H<sub>7</sub>)­(PPh<sub>3</sub>)­L (<b>8</b>). Protonation of [Ru]–SnH<sub>3</sub> (<b>2</b>) with triflic acid (HOTf) produced the very unstable dihydridostannyl compound Ru­[SnH<sub>2</sub>(OTf)]­(η<sup>5</sup>-C<sub>9</sub>H<sub>7</sub>)­(PPh<sub>3</sub>)­L (<b>9</b>). Stabilization of SnH<sub>2</sub> species was achieved by protonation with HOTf at −30 °C of the cyclopentadienyl compound Ru­(SnH<sub>3</sub>)­(η<sup>5</sup>-C<sub>5</sub>H<sub>5</sub>)­(PPh<sub>3</sub>)­[P­(OMe)<sub>3</sub>], which yielded the complex Ru­[SnH<sub>2</sub>(OTf)]­(η<sup>5</sup>-C<sub>5</sub>H<sub>5</sub>)­(PPh<sub>3</sub>)­[P­(OMe)<sub>3</sub>] (<b>10a</b>). The complexes were characterized by spectroscopy (IR and <sup>1</sup>H, <sup>31</sup>P, <sup>13</sup>C, and <sup>119</sup>Sn NMR data) and by X-ray crystal structure determinations of Ru­[Sn­(CCPh)<sub>3</sub>]­(η<sup>5</sup>-C<sub>9</sub>H<sub>7</sub>)­(PPh<sub>3</sub>)­[P­(OEt)<sub>3</sub>] (<b>4b</b>) and Ru­[Sn­(OH)<sub>3</sub>]­(η<sup>5</sup>-C<sub>9</sub>H<sub>7</sub>)­(PPh<sub>3</sub>)­[P­(OEt)<sub>3</sub>] (<b>8b</b>).