Oligomerization is kinetically favored in RCM reactions catalyzed by RuCl2(PCy3)(IMes)(CHPh), for a range of unhindered α,ω-dienes leading to large or medium-sized rings, even at dilutions designed to minimize intermolecular reaction. Reversible metathesis (i.e., ethenolysis) is inhibited by rapid volatilization of ethylene. At appropriately high dilutions, however, the RCM products are efficiently liberated by backbiting.

Ruthenium alkylidene complexes containing one aryloxide "pseudohalide" ligand catalyze ring-closing metathesis of diene and ene-yne substrates with exceptionally high efficiency. Chromatographic removal of Ru residues is unexpectedly facile, offering a convenient means of isolating pure organic products in high yields.

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Reaction of RuHCl(PPh3)3 4 with 3‐chloro‐3‐methyl‐1‐butyne effects transformation into RuCl2(PPh3)2(CHCHCMe2) 1c. Starting 4 is available commercially, or via quantitative reaction of RuCl2(PPh3)3 with one equivalent of alkali phenoxides or isopropoxides in refluxing benzene‐2‐propanol. Phosphane exchange between 1c and PCy3 or 1,3‐(CH2PCy2)2C6H4 is rapid at RT, affording RuCl2(PCy3)2(CHCHCMe2) 1b or the novel alkylidene complex RuCl2[1,3‐(CH2PCy2)2C6H4](CHCHCMe2) 7. Much slower exchange occurred on use of RuCl2(PCy3)2(CHPh) (1a) as precursor. Complex 1c is stable indefinitely (months) in the solid state at RT under N2, but dimerizes slowly in solution to give RuCl(PPh3)2(μ‐Cl)3Ru(PPh3)2(CHCHCMe2) 6a. 2,7‐Dimethyl‐octa‐2,4,6‐triene, the formal product of carbene coupling, is observed by 1H NMR. Dimerization does not compete with phosphane exchange. A side‐product arising from use of excess 3‐chloro‐3‐methyl‐1‐butyne in the synthesis of 1c was identified as Ru(IV) carbyne complex RuCl3(PPh3)2(≡CCHCMe2) 5, the structure of which was confirmed by X‐ray crystallography.