Ruthenium Benzylidene and Vinylidene Complexes in a Sulfur-Rich Coordination Environment

Interaction of Ru(CHPh)(PCy<sub>3</sub>)<sub>2</sub>Cl<sub>2</sub> (Cy = cyclohexyl) with K[N(PPh<sub>2</sub>S)<sub>2</sub>] affords air-stable Ru(CHPh)[N(PPh<sub>2</sub>S)<sub>2</sub>]<sub>2</sub>, <b>1</b>, which has been characterized by X-ray diffraction. The Ru−C<sub>α</sub> and average Ru−S distance for <b>1</b> are 1.88(2) and 2.377 Å, respectively. Reaction of <b>1</b> with CO gives <i>cis</i>-Ru(CO)<sub>2</sub>[N(PPh<sub>2</sub>S)<sub>2</sub>]<sub>2</sub>. Complex <b>1</b> undergoes metathesis with ethyl vinyl ether to give the methoxycarbene complex Ru(CHOEt)[N(PPh<sub>2</sub>S)<sub>2</sub>]<sub>2</sub>, <b>3</b>. Treatment of Ru(CHPh)(PCy<sub>3</sub>)<sub>2</sub>Cl<sub>2</sub> with K[N(PPh<sub>2</sub>Se)<sub>2</sub>] affords Ru(CHPh)[PPh<sub>2</sub>NP(Se)Ph<sub>2</sub>]<sub>2</sub>, <b>4</b>, which has been characterized by X-ray crystallography. The Ru−C, average Ru−P, and average Ru−Se distances are 1.873(8), 2.383, and 2.450 Å, respectively. Reactions of Ru(CHPh)(PCy<sub>3</sub>)<sub>2</sub>Cl<sub>2</sub> with K[P(OR)<sub>2</sub>S<sub>2</sub>] afford <i>cis</i>-Ru(CHPh)(PCy<sub>3</sub>)[P(OR)<sub>2</sub>S<sub>2</sub>]<sub>2</sub> (R = Et (<b>6</b>) and <i>i</i>-Pr (<b>7</b>)). Reaction of Ru(CHPh)(PCy<sub>3</sub>)<sub>2</sub>Cl<sub>2</sub> with 1,4,7-trithiacyclononane ([9]aneS<sub>3</sub>) gives [([9]aneS<sub>3</sub>)Ru(CHPh)(PCy<sub>3</sub>)Cl]Cl, <b>8</b>. Treatment of Ru(CCHPh)(PCy<sub>3</sub>)<sub>2</sub>Cl<sub>2</sub> with K[N(PPh<sub>2</sub>S)<sub>2</sub>] or [9]aneS<sub>3</sub> affords <i>cis</i>-Ru(CCHPh)(PCy<sub>3</sub>)[N(PPh<sub>2</sub>S)<sub>2</sub>]<sub>2</sub> (<b>9</b>) or ([9]aneS<sub>3</sub>)Ru(PCy<sub>3</sub>)Cl<sub>2</sub> (<b>10</b>), respectively. The Ru−C, Ru−P, and average Ru−S distances in <b>9</b> are 1.80(1), 2.420(3), and 2.479 Å, respectively. Complexes <b>1</b> and <b>8</b> are active catalysts for ring-opening metathesis polymerization of norbornene.