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

Interaction of Ru(CHPh)(PCy₃)₂Cl₂ (Cy = cyclohexyl) with K[N(PPh₂S)₂] affords air-stable Ru(CHPh)[N(PPh₂S)₂]₂, 1, which has been characterized by X-ray diffraction. The Ru−C_α and average Ru−S distance for 1 are 1.88(2) and 2.377 Å, respectively. Reaction of 1 with CO gives cis-Ru(CO)₂[N(PPh₂S)₂]₂. Complex 1 undergoes metathesis with ethyl vinyl ether to give the methoxycarbene complex Ru(CHOEt)[N(PPh₂S)₂]₂, 3. Treatment of Ru(CHPh)(PCy₃)₂Cl₂ with K[N(PPh₂Se)₂] affords Ru(CHPh)[PPh₂NP(Se)Ph₂]₂, 4, 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)(PCy₃)₂Cl₂ with K[P(OR)₂S₂] afford cis-Ru(CHPh)(PCy₃)[P(OR)₂S₂]₂ (R = Et (6) and i-Pr (7)). Reaction of Ru(CHPh)(PCy₃)₂Cl₂ with 1,4,7-trithiacyclononane ([9]aneS₃) gives [([9]aneS₃)Ru(CHPh)(PCy₃)Cl]Cl, 8. Treatment of Ru(CCHPh)(PCy₃)₂Cl₂ with K[N(PPh₂S)₂] or [9]aneS₃ affords cis-Ru(CCHPh)(PCy₃)[N(PPh₂S)₂]₂ (9) or ([9]aneS₃)Ru(PCy₃)Cl₂ (10), respectively. The Ru−C, Ru−P, and average Ru−S distances in 9 are 1.80(1), 2.420(3), and 2.479 Å, respectively. Complexes 1 and 8 are active catalysts for ring-opening metathesis polymerization of norbornene.