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−Cα 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.