Synthesis and structures of the silyl bridged bis(indenyl) diruthenium complexes and a novel indenyl nonanuclear ruthenium cluster Ru9(μ6-C)(CO)14(μ3-η5:η2:η2-C9H7)2

Thermal treatment of C9H7SiMe2C9H7 and C9H7Me2SiOSiMe2C9H7 with Ru3(CO)12 in refluxing xylene gave the corresponding diruthenium complexes (E)[(η5-C9H6)Ru(CO)]2(μ-CO)2 [E = Me2Si (1), Me2SiOSiMe2 (2)]. A desilylation product [(η5-C9H7)Ru(CO)]2(μ-CO)2 (3) was also obtained in the latter case. Similar treatment of C9H7Me2SiSiMe2C9H7 with Ru3(CO)12 gave a novel indenyl nonanuclear ruthenium cluster Ru9(μ6-C)(CO)14(μ3-η5:η2:η2-C9H7)2 (5) with carbon-centered tricapped trigonal prism geometry, in addition to the diruthenium complex (Me2SiSiMe2)[(η5-C9H6)Ru(CO)]2(μ-CO)2 (4) and the desilylation product 3. Complex 4 can undergo a thermal rearrangement to form the product [(Me2Si)(η5-C9H6)Ru(CO)2]2 (6). The molecular structures of 1, 2, 4, 5, and 6 were determined by X-ray diffraction.