Abstract
The reactions of zirconocene-alkyne complexes Cp‘2Zr(L)(η2-Me3SiC2SiMe3) {Cp‘2 = (η5-C5H5)2: L = THF, 1; L = pyridine, 2; Cp‘2 = rac-ebthi, 3, [ebthi = 1,2-ethylene-1,1‘-bis(η5-tetrahydroindenyl)]} with 2 equiv (or excess) of bicyclo[2.2.1]hepta-2,5-diene (NBD) in THF at 50 °C result in five-membered zirconacyclopentane complexes Cp2Zr(C14H16) (4) and rac-(ebthi)Zr(C14H16) (5) (C14H16 means two coupled NBDs) in good yields. NMR spectra of complexes 4 and 5 show the C2 symmetry of the molecules, indicating that the two NBD components in the complexes are in exo−trans−exo conformation. An X-ray crystallographic structure determination of 5 confirms that the two NBD fragments are exo−trans−exo linked to form a racemate. Both optical isomers are present in a 1:1 ratio in the crystals. Reactions of 1 and 2 with 1 equiv of NBD have also been investigated, and only zirconacyclopentane complex 4 was isolated from the reactions. The analogous zirconacyclopentane complexes Cp2Zr(C22H20) (6) and rac-(ebthi)Zr(C22H2...
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