Kuwata, Shigeki Andou, Masahiro Hashizume, Kohjiro Mizobe, Yasushi Hidai, Masanobu Structures and Reactivities of Diruthenium Dithiolene Complexes and Triruthenium Sulfido Clusters Derived from a Hydrosulfido-Bridged Diruthenium Complex The hydrosulfido-bridged diruthenium complex [Cp*RuCl(μ<sub>2</sub>-SH)<sub>2</sub>RuClCp*] (<b>1</b>) reacted with an excess of triethylamine to give the cubane-type tetraruthenium sulfido cluster [(Cp*Ru)<sub>4</sub>(μ<sub>3</sub>-S)<sub>4</sub>] (<b>3</b>). When the reaction was carried out in the presence of alkynes, the dithiolene-bridged diruthenium complexes [(Cp*Ru)<sub>2</sub>(μ<sub>2</sub>-η<sup>2</sup>:η<sup>4</sup>-S<sub>2</sub>C<sub>2</sub>RR‘)] (<b>4</b>) were obtained. The dithiolene ring in <b>4</b> is almost planar. Treatment of <b>4</b> with CO afforded the carbonyl complexes [Cp*Ru(CO)(μ<sub>2</sub>-η<sup>2</sup>:η<sup>4</sup>-S<sub>2</sub>C<sub>2</sub>RR‘)RuCp*] (<b>5</b>) containing a bent dithiolene ring. On the other hand, the reaction of <b>1</b> with an equimolar amount of [RuH<sub>2</sub>(PPh<sub>3</sub>)<sub>4</sub>] resulted in the formation of the triruthenium sulfido cluster [(Cp*Ru)<sub>2</sub>(μ<sub>3</sub>-S)<sub>2</sub>(μ<sub>2</sub>-H)RuCl(PPh<sub>3</sub>)<sub>2</sub>] (<b>6</b>). Cluster <b>6</b> reacted with an excess of NaBH<sub>4</sub> in ethanol to give the dihydrido cluster [(Cp*Ru)<sub>2</sub>(μ<sub>3</sub>-S)<sub>2</sub>(μ<sub>2</sub>-H)RuH(PPh<sub>3</sub>)<sub>2</sub>] (<b>7</b>), which was further converted to the dicarbonyl cluster [(Cp*Ru)<sub>2</sub>(μ<sub>3</sub>-S)<sub>2</sub>Ru(CO)<sub>2</sub>(PPh<sub>3</sub>)] (<b>8</b>) under CO. The detailed structures for [(Cp*Ru)<sub>2</sub>(μ<sub>2</sub>-η<sup>2</sup>:η<sup>4</sup>-S<sub>2</sub>C<sub>2</sub>HBu<sup>t</sup>)] (<b>4a</b>), [Cp*Ru(CO)(μ<sub>2</sub>-η<sup>2</sup>:η<sup>4</sup>-S<sub>2</sub>C<sub>2</sub>HBu<sup>t</sup>)RuCp*] (<b>5a</b>), and <b>6</b>−<b>8</b> have been determined by X-ray crystallography. RR;dithiolene ring;Cp;S 2 C 2 HBu t;CO;SH;cluster;Diruthenium Dithiolene Complexes;Triruthenium Sulfido Clusters Derived 1998-07-03
    https://acs.figshare.com/articles/dataset/Structures_and_Reactivities_of_Diruthenium_Dithiolene_Complexes_and_Triruthenium_Sulfido_Clusters_Derived_from_a_Hydrosulfido-Bridged_Diruthenium_Complex/3782283
10.1021/om980214d.s003