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The X-ray analysis of Me 2 Si(C 5 H 3 -3-Me 3 -Si) 2 SmCH(Me 3 Si) 2 (THF) (1) revealed a monomeric structure, while the hydrogenated complex, [Me 2 Si(C 5 H 3 -3-Me 3 Si) 2 SmH(THF)] 2 (2), exhibits binuclear µ-H structure to indicate that Me 2 SiCp′ 2 M f M(µ-Me 2 SiCp′ 2 ) 2 M rearrangement of the η 5 -η 5 ligation occurs during the hydrogenation. The resulting samarocene hydride 2 exhibits high activity as an initiator for the block copolymerization of ethylene with polar monomers such as methyl methacrylate and -caprolactone.

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Hydrozirconation of 1-alkynyl pinacolboronates, 1, with HZrCp2Cl provides gem-borazirconocenes 2. The latter when treated with CuBr gives the homocoupled (1E,3E)-2,3-dibora-1,3-butadienes, 3, in good yield (62−67%). The reaction works even for hindered 2 (R = t-Bu). Structure 3 was assigned on the basis of NMR. Suzuki−Miyaura coupling of 3a (R = n-Bu) with PhI in the presence of CsF leads to the replacement of both boron groups by phenyl and hydrogen to give 6 in 76% yield. Zirconocene-mediated coupling of 1 leads to diastereomeric products:  (1E,3E)-1,3-dibora-1,3-butadienes, 4, in 7−26% isolated yields and (1E,3E)-1,4-dibora-1,3-butadienes, 5, in 17−34% isolated yields. The two isomers can be separated by selective precipitation of 5 from the reaction mixture in pentane (−20 °C) followed by silica gel chromatography to give pure 4. The reaction does not work when R in 1 is the t-Bu group. Assignments of structures for 4 and 5 were done on the basis of 1D and 2D NMR experiments. In addition, a single-crystal X-ray analysis of 5a showed it to be a highly planar and linearly oriented molecule. Suzuki−Miyaura coupling of 4a proceeded to replace the terminal boron group exclusively, while the internal boron group of 4a remained intact.