Ring-Opening Reactions of Tetrahydrofuran versus Alkyne Complexation by Group 4 Metallocene Complexes Leading to General Consequences for Synthesis and Reactions of Metallocene Complexes
The reduction of certain group 4 metallocene dichlorides by magnesium or lithium in the presence or absence of Me3SiC2SiMe3 in THF or toluene was investigated, giving in the case of titanium the dinuclear Ti(III) complex [rac-(ebthi)Ti(μ-Cl)]2 (1). For zirconium the 1-oxa-2-zirconacyclohexane 2 was...
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Published in | Organometallics Vol. 26; no. 12; pp. 3000 - 3004 |
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Main Authors | , , , , , , , |
Format | Journal Article |
Language | English |
Published |
WASHINGTON
American Chemical Society
04.06.2007
Amer Chemical Soc |
Subjects | |
Online Access | Get full text |
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Summary: | The reduction of certain group 4 metallocene dichlorides by magnesium or lithium in the presence or absence of Me3SiC2SiMe3 in THF or toluene was investigated, giving in the case of titanium the dinuclear Ti(III) complex [rac-(ebthi)Ti(μ-Cl)]2 (1). For zirconium the 1-oxa-2-zirconacyclohexane 2 was formed by ring-opening reaction of rac-(ebthi)Zr(η2-Me3SiC2SiMe3) with THF. As a byproduct from the synthesis of Cp*2Zr(η2-Me3SiC2SiMe3) starting from Cp*2ZrCl2 another 1-oxa-2-zirconacyclohexane (3) was obtained by ring-opening reaction of THF via the dinuclear complex Cp*2Zr(Cl)-(CH2)4O−Zr(Cl)Cp*2 (4). In the case of hafnium the analogous dinuclear complex Cp*2Hf(Cl)−(CH2)4O−Hf(Cl)Cp*2 (5) and 1-oxa-2-hafnacyclohexane (6) were the main products of the reaction, inhibiting the synthesis of Cp*2Hf(η2-Me3SiC2SiMe3) (7). The tendency for ring opening of THF initiated by metallocenes increases in the series Ti, Zr, Hf, thus leading to consequences for the synthesis of metallocene complexes. |
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Bibliography: | istex:8E10229B37F8BD9CD056E51E6B9F37F7ED2118F4 ark:/67375/TPS-QJGFHRD0-J |
ISSN: | 0276-7333 1520-6041 |
DOI: | 10.1021/om0702173 |