Reactions of CpArCHCHArCp [Ar=Ph (1), p-MeOC6H4 (2)] with Ru3(CO)12 in refluxing xylene afforded the unexpected bridgeing C-C cleavage and cyclopentadienyl coupling products: the 2,2'-bisubstituted fulvalene diruthenium complexes (η5:η5-2,2'-ArCH2C5H3C5H3CH2Ar)Ru2(CO)4 [Ar=Ph (5),p-MeOC6H4 (9)] and the partially hydorgented products (η5:η3-ArCH2C5H3C5H6CHAr)Ru2(CO)4 [Ar=Ph(4), p-MeOC6H4 (8)], in addition to the normal bridged bis(cyclopentadienyl) tetracarbonyl diruthenium complexes (ArCHCHAr)[η5-C5H4)Ru(CO)]2(μ-CO)2[Ar=Ph(7),p-MeOC6H4 (10)]. When ligand (tBuC5H4)PhCHCHPh(tBuC5H4) (3) reacted with Ru3(CO)12, the tetrasubstituted fulvalene diruthenium complex (η5:η5-PhCH2tBuC5H2C5H2tBuCH2Ph)Ru2(CO)4 (11) and three normal bridged bis-(cyclopentadienyl) diruthenium complexes (PhCHCHPh)[(η5-tBuC5H3)Ru(CO)]2(μ-CO)2 (12-14) were obtained. The molecular structures of 4, 5, 7-meso, 7-rac, 8, 10-meso, 11, 12, 13, and 14 were determined by X-ray diffraction. The stereochemistry of the reaction was also studied, and the possible mechanism was discussed.