First mixed fluoro-chloro group 4 organometallics: Synthesis and spectroscopic and structural characterization of [((C{sub 5}Me{sub 5})ZrF{sub 2}Cl){sub 4}], [((C{sub 5}Me{sub 5})HfF{sub 2}Cl){sub 4}], [(C{sub 5}Me{sub 5}){sub 4}Zr{sub 4}({mu}-F){sub 2}({mu}-F{sub 2}){sub 2}({mu}-Cl){sub 2}Cl{sub 4}], [(C{sub 5}Me{sub 5}){sub 4}Hf{sub 4}({mu}-F){sub 2}{sub 2}({mu}-F{sub 2}){sub 2}({mu}-Cl){sub 2}Cl{sub 4}], [(C{sub 5}Me{sub 4}Et){sub 2}ZrClF], and [(C{sub 5}Me{sub 5}){sub 2}HfClF]
- Universitaet Goettingen (Germany); and others
Tetrameric [(C{sub 5}Me{sub 5})MF{sub 3}{sub 4}] (M = Zr, Hf) react smoothly with Me{sub 3}SiCl in CH{sub 2}Cl{sub 2} at room temperature to give [((C{sub 5}Me{sub 5})ZrF{sub 2}Cl){sub 4}] (1) and [((C{sub 5}Me{sub 5})HfF{sub 2}Cl){sub 4}] (2), respectively in high yield. Treatment of [((C{sub 5}Me{sub 5})MF{sub 3}){sub 4}] (M = Zr, Hf) with Me{sub 2}AlCl in toluene gives mixtures of 1 and [(C{sub 5}Me{sub 5}){sub 4}Zr{sub 4}({mu}-F){sub 2}({mu}-F{sub 2}){sub 2}({mu}-Cl){sub 2}Cl{sub 4}] (3), and 2 and [(C{sub 5}Me{sub 5}){sub 4}Hf{sub 4}({mu}-F){sub 2}({mu}-F{sub 2}){sub 2}({mu}-Cl){sub 2}Cl{sub 4}] (4), respectively, in an approximately 1:1 molar ratio. Metallocene type complexes [(C{sub 5}Me{sub 4}Et){sub 2}ZrCl{sub 2}] and [(C{sub 5}Me{sub 5}){sub 2}HfCl{sub 2}] react with 1 equiv of Me{sub 3}SnF to give [(C{sub 5}Me{sub 4}Et){sub 2}ZrClF] (5) and [(C{sub 5}Me{sub 5}){sub 2}HfClF] (6), respectively. The complexes 1-6 were characterized by spectroscopic methods ({sup 1}H and {sup 19}F NMR and mass spectrometry). The solid state structures of 1, 3, and 5 were determined by single-crystal X-ray diffraction analyses.
- OSTI ID:
- 256486
- Journal Information:
- Inorganic Chemistry, Journal Name: Inorganic Chemistry Journal Issue: 1 Vol. 35; ISSN 0020-1669; ISSN INOCAJ
- Country of Publication:
- United States
- Language:
- English
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