| Abstract: | In thermal reactions of the doubly bridged dicyclopentadienes (C5H3R(SiMe2))(C5H3R(GeMe2)) (R=H (1), tBu (5)) with Mo(CO)6, the bridging GeMe2 is cleaved to give the corresponding degermylated products (η5-C5H3R)2(SiMe2)]Mo2(CO)6 (3, rac-7), or both GeMe2 and SiMe2 are cleaved to afford the nonbridged products (η5-C5H4R)Mo(CO)3]2 (2, 6). The reactions also produce germylidyne trimolybdenum clusters (η5-C5H3R)2(SiMe2)](η5-C5H4R)Mo(CO)2]3(μ3-GeMe) (4, rac-/meso-7) containing the Mo3(μ3-GeMe) units. Similarly, reaction of the single GeMe2-bridged dicyclopentadienes (C5H5)2GeMe2 (9) with Mo(CO)6 also results in the degermylated 2, as well as the similar trimolybdenum cluster (η5-C5H5)Mo(CO)2]3(μ3-GeMe) (10). The molecular structures of 4 and trans-5 were determined by X-ray diffraction. |
