Ruthenium benzylidene and vinylidene complexes in a sulfur-rich coordination environment

Interaction of Ru(=CHPh)(PCy3)(2)Cl-2 (Cy = cyclohexyl) with K[N(PPh2S)(2)] affords air-stable Ru(=CHPh)[N(PPh2S)(2)](2), 1, which has been characteri zed by X-ray diffraction. The Ru-C-alpha and average Ru-S distance for 1 ar e 1.88(2) and 2.377 Angstrom, 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. Tr eatment of Ru(=CHPh)(PCy3)(2)Cl-2 with K[N(PPh2Se)(2)] affords Ru(=CHPh)[PP h2NP(Se)Ph-2](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, an d 2.450 A, respectively. Reactions of Ru(=CHPh)(PCy3)(2)Cl-2 with K[P(OR)(2 )S-2] afford cis-Ru(=CHPh)(PCy3)[P(OR)(2)S-2](2) (R = Et (6) and i-Pr (7)). Reaction of Ru(=CHPh)(PCy3)(2)Cl-2 with 1,4,7-trithiacyclononane ([9]aneS( 3)) gives [([9]aneS(3))Ru(=CHPh)(PCy3)Cl]Cl, 8. Treatment of Ru(=C=CHPh)(PC y3)(2)Cl-2 with K[N(PPh2S)(2)] or [9]aneS(3) affords cis-Ru(=C=CHPh)(PCy3)[ N(PPh2S)(2)](2) (9) or ([9]aneS(3))Ru(PCy3)Cl-2 (10), respectively. The Ru- C, Ru-P, and average Ru-S distances in 9 are 1.80(1), 2.420(3), and 2.479 A ngstrom, respectively. Complexes 1 and 8 are active catalysts for ring-open ing metathesis polymerization of norbornene.