Thermal treatment of the SiH-functionalized cyclopentadienes (RC5H4)SiHMeR‘ [R = H, R‘ = Ph (1),
PhCH2 (2); R = t-Bu, R‘ = Ph (3), PhCH2 (4)] with Ru3(CO)12 gave the cyclic dinuclear metal complexes
trans-[(R‘MeSi)(η5-RC5H3)Ru(CO)2]2 [R = H, R‘ = Ph (7), PhCH2 (8); R = t-Bu, R‘ = Ph (10), PhCH2
(11)] containing two Si−Ru bonds via Si−H activation. A cyclopentenyl complex, [(η2-C5H7)SiMe(CH2Ph)Ru(CO)3]2 (9), bridged by a vinylsilyl ligand was also obtained from the reaction, but reactions of the
SiH-functionalized tetramethylcyclopentadienes (C5Me4H)SiHMeR‘ [R‘ = Ph (5), PhCH2 (6)] with Ru3(CO)12 only gave the cyclic diruthenium complex [(PhMeSi)(η5-C5Me4)]Ru2(CO)6 (12) with one Si−Ru
bond and the desilylation product [(η5-C5Me4H)Ru(CO)]2(μ-CO)2 (13). When 2 and 4 reacted with M(CO)6,
the similar cyclic dinuclear complexes trans-[(PhCH2MeSi)(η5-RC5H3)M(CO)3]2 [R = H, M = W (18);
R = t-Bu, M = Mo (15), W (20)] were obtained, in addition to the desilylation products [(η5-RC5H4)M(CO)3]2 [R = H, M = Mo (14), W (19); R = t-Bu, M = Mo (16), W (21)], but reactions of 6 with
M(CO)6 only gave the desilylation products [(η5-C5Me4H)M(CO)3]2 [M = Mo (17); M = W (22)]. The
molecular structures of 7, 9, 12, 13, 15, 18, and 20 were determined by X-ray diffraction.