Novel synthesis of zirconocene difluoride and alkyl monofluoride complexes

Starting from zirconocene bis(trimethylsilyl)acetylene complexes Cp'Zr-2(L)(eta(2)-btmsa) via the 2-vinylpyridine complexes Cp(')2Zr(2-vipy) a novel synthetic method for zirconocene difluoride and alkyl monofluoride complexes was elaborated. Examples with selected different ligand systems Cp'(2) [Cp-2 = bis(eta(5)-cyclopentadienyl); ebthi := 1,2-ethylene-1,1'-bis(eta(5)-tetrahydroindenyl); (thi)(2) bis(eta(5)-tetrahydroindenyl); Me2Si(eta(5)-C5H4)(2) = dimethylsilylbis(eta(5)-cyclopentadienyl); (i)(2) bis(eta(5)-indenyl); ebi = 1,2-ethylene-1,1'-bis(eta(5)-indenyl); and Me2Si(eta(5)-C9H10)(2) = dimethylsilyl-1,1'-bis(eta(5)-tetrahydroindenyl)] were synthesized. In the series of these investigations new complexes (i)(2)Zr(THF)(eta(2)-btmsa) (1), rac-(ebi)Zr(THF)(eta(2)- btmsa) (2), (thi)(2)Zr(2-vipy) (3), Me2Si(eta(5)-C5H4)(2)Zr(2-vipy) (4), (i)(2)Zr(2-vipy) (5), and rac-(ebthi)Zr(2-Ph-vipy) (6) were prepared as starting materials. Different methods for preparation of the zirconocene difluorides rac-(ebthi)ZrF2 (7), (thi)(2)ZrF2 (8), Me4C2(eta(5)-C5H4)(2)ZrF2 (9), and Me2Si(eta(5)-C9H10)(2)ZrF2 (10) and the monofluorides Cp2Zr(F)(CH2CH2-Py) (11), rac-(ebthi)Zr(F)(CH2CH2-2-py) (12), (thi)(2)Zr(F)(CH2CH2-2-py) (13), Me2Si(eta(5)-C5H4)2Zr(F)(CH2CH2-2-py) (14), and Me2Si(eta(5)-C9H10)(2)ZrF(Me) (15) are reported and compared. The molecular structures of the bis-eta(5)-tetrahydroindenyl complexes 3, 8, and 13 were confirmed by X-ray crystal structure analysis.