The reaction of a mixture of isomers of 4,4,8,8-tetramethyl-tetrahydro-s-indacene (1) with Ru 3 -(CO) 12 afforded cis-{(η 5 -C 5 H 3 ) 2 (CMe 2 ) 2 }Ru 2 (CO) 4 , (2) in 68% yield. Reaction of 2 with Br 2 gave cis-{(η 5 -C 5 H 3 ) 2 (CMe 2 ) 2 }Ru 2 (CO) 4 Br 2 (3) in 88% yield. Reaction of 3 with AgOTf yields cis-[{(η 5 -C 5 H 3 ) 2 (CMe 2 ) 2 }Ru 2 (CO) 4 (μ-Br)][OTf] (4), while reaction of 3 with Me 3 NO and AgOTf yields cis-[{(η 5 -C 5 H 3 ) 2 (CMe 2 ) 2 }Ru 2 (CO) 2 (MeCN) 2 (μ-Br)][OTf] (5). Reaction of 3 under more forcing conditions with AgOTf in MeCN gave cis-[{(η 5 -C 5 H 3 ) 2 (CMe 2 ) 2 }Ru 2 (CO) 2 (MeCN) 4 ][OTf] 2 (6), while a MeCN/C 6 H 6 solvent combination afforded cis-[{(η 5 -C 5 H 3 ) 2 (CMe 2 ) 2 }Ru 2 (η 6 -C 6 H 6 ) 2 ][OTf] 2 (7) in a 64% yield. Removal of the benzene ligands in 7 can be accomplished by first adding Hto the coordinated benzene ligands to afford cis-{(η 5 -C 5 H 3 ) 2 (CMe 2 ) 2 }Ru 2 (η 5 -C 6 H 7 ) 2 (10). Subsequent protonation of 10 in MeCN afforded [cis-{(η 5 -C 5 H 3 ) 2 (CMe 2 ) 2 }Ru 2 (MeCN) 6 ][OTf] 2 (8) in 88% yield. Structural data for 4, 5, 7, and 10 are reported.

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