Publikation: ansa-vanadocene complexes : syntheses, structures and ligand exchange reactions
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1997
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Collection of Czechoslovak Chemical Communications. 1997, 62(2), pp. 265-278. ISSN 0010-0765. eISSN 1212-6950. Available under: doi: 10.1135/cccc19970265
Zusammenfassung
Tetramethylethano-bridged vanadocene dichlorides (CH3)4C2(3-R-C5H3)2VCl2 with R = H, Me, t-Bu are obtained by reacting the corresponding ligand MgCl salts with vanadium(III) acetylacetonato compounds, followed by oxidation with PCl3 or AgCl. Smooth ligand exchange reactions of these ansa-vanadocene dichlorides afford acetylacetonato cations and binaphtholate complexes; from these, the dichlorides are regenerated by exposure to MgCl2 in THF solution. Separation of meso and rac isomers (as well as enantiomer separation) is achieved via corresponding binaphtholate complexes; conversion to the vanadium(III) diisonitrile cations (CH3)4C2(3-R-C5H3)2V(CNt-Bu)2+ allows an assessment of diastereoisomer ratios by 1H NMR. Lewis-acidic bistriflate derivatives of these ansa-vanadocene complexes are obtained from the dichlorides by reaction with silver triflate.
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540 Chemie
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ansa-metallocenes, vanadium, acetylacetonato complex, chiral, enantioseparation
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DORER, Birgit, Marc-Heinrich PROSENC, Ursula RIEF, Hans-Herbert BRINTZINGER, 1997. ansa-vanadocene complexes : syntheses, structures and ligand exchange reactions. In: Collection of Czechoslovak Chemical Communications. 1997, 62(2), pp. 265-278. ISSN 0010-0765. eISSN 1212-6950. Available under: doi: 10.1135/cccc19970265BibTex
@article{Dorer1997ansav-23757,
year={1997},
doi={10.1135/cccc19970265},
title={ansa-vanadocene complexes : syntheses, structures and ligand exchange reactions},
number={2},
volume={62},
issn={0010-0765},
journal={Collection of Czechoslovak Chemical Communications},
pages={265--278},
author={Dorer, Birgit and Prosenc, Marc-Heinrich and Rief, Ursula and Brintzinger, Hans-Herbert}
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<dcterms:abstract xml:lang="eng">Tetramethylethano-bridged vanadocene dichlorides (CH<sub>3</sub>)<sub>4</sub>C<sub>2</sub>(3-R-C<sub>5</sub>H<sub>3</sub>)<sub>2</sub>VCl<sub>2</sub> with R = H, Me, t-Bu are obtained by reacting the corresponding ligand MgCl salts with vanadium(III) acetylacetonato compounds, followed by oxidation with PCl<sub>3</sub> or AgCl. Smooth ligand exchange reactions of these ansa-vanadocene dichlorides afford acetylacetonato cations and binaphtholate complexes; from these, the dichlorides are regenerated by exposure to MgCl<sub>2</sub> in THF solution. Separation of meso and rac isomers (as well as enantiomer separation) is achieved via corresponding binaphtholate complexes; conversion to the vanadium(III) diisonitrile cations (CH<sub>3</sub>)<sub>4</sub>C<sub>2</sub>(3-R-C<sub>5</sub>H<sub>3</sub>)<sub>2</sub>V(CNt-Bu)<sub>2</sub><sup>+</sup> allows an assessment of diastereoisomer ratios by <sup>1</sup>H NMR. Lewis-acidic bistriflate derivatives of these ansa-vanadocene complexes are obtained from the dichlorides by reaction with silver triflate.</dcterms:abstract>
<dc:contributor>Dorer, Birgit</dc:contributor>
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