Thermal treatment of the trinuclear ruthenium complex {μ2-η5:η¹-(C5H4N)(C9H5)}Ru3(CO)9 (1) with 1,5-heptadiene, diallyl sulfide, 1,4-hexadiene, and 1,7-octadiene respectively generated the series of diruthenium products {(C5H4N)(μ2-η5,η¹-C9H5CHCH2CH2R)}Ru2(CO)x (4, R = -CH2CH CHCH3; 6, R = SCH2CH CH2; 7, R = -CH CHCH3; 8, R = -(CH2)3CH CH2) via the insertion of an terminal C C bond into the Ru-C(η¹) bond of 1. When 1 was treated with diallyl ether, the complex {(C5H4N)(μ2-η5,η³-C9H5CCH2CH2OCCHCH3)}Ru2(CO)4 (5) with a five-membered oxygen-containing heterocycle was produced. Reactions of 2-methyl-3-(2-pyridyl)indene or 2,5-dimethyl-3-(2-pyridyl)indene with Ru3(CO)12 gave the cycloruthenated complexes {(C5H4N)(μ2-η5,η¹-RC9H4CH2)}Ru2(CO)5 (9, R = H; 10, R = CH3) with structures similar to those of 4, 7, and 8, via C(sp³)-H activation. The molecular structures of 5-7 and 10 were determined by X-ray diffraction. [ABSTRACT FROM AUTHOR]