Issue 18, 2005

Chloride-bridged oxovanadium(v) complexes with alkoxyalkoxide ligands. Synthesis, structure, electrochemistry and reactivities

Abstract

A series of mixed alkoxyalkoxo chloro complexes of vanadium(V), [VOCl2(OCH2CH2OR)]2 (R = Me, Et, iPr, Bz), [VOCl2(OCMe2CH2OMe)]2 and [VOCl2(OCH2(cyclo-C4H7O)]2, were synthesised and characterised. The title compounds can be obtained either from VOCl3 and the alkoxyalcohols by HCl elimination or from the corresponding lithium alkoxides and VOCl3 by salt metathesis reaction. X-Ray diffraction studies revealed the title compounds to be dimers with chloride bridging ligands and intramolecular ether coordination. Electrochemical results obtained by cyclic voltammetry indicate irreversible, reductive behaviour. The interactions of the title compounds with oxygen, nitrogen and phosphorus donor ligands were examined. Phosphorus and nitrogen donors lead to reduction products whereas tetrahydrofuran coordinates to the vanadium(V) centre by breaking the chloride bridge. All tetrahydrofuran complexes, [VOCl2(OCH2CH2OR)(thf)] (R = Me, Et, iPr) and [VOCl2(OCMe2CH2OMe)(thf)], have been characterised by single-crystal X-ray diffraction. The solid-state structures of these complexes show that they consist of six-coordinate monomers. Reaction of [VOCl2(OCH2CH2OMe)]2 with Me3SiCH2MgCl gave [VO(CH2SiMe3)3], which has been structurally characterised. The compounds were tested as catalysts for epoxidation and polymerisation reactions. They convert unfunctionalised olefins into the corresponding epoxides with moderate activity. They are good pre-catalysts for the polymerisation of ethene and oligomerise 1-hexene.

Graphical abstract: Chloride-bridged oxovanadium(v) complexes with alkoxyalkoxide ligands. Synthesis, structure, electrochemistry and reactivities

Supplementary files

Article information

Article type
Paper
Submitted
25 Apr 2005
Accepted
30 Jun 2005
First published
29 Jul 2005

Dalton Trans., 2005, 3108-3117

Chloride-bridged oxovanadium(V) complexes with alkoxyalkoxide ligands. Synthesis, structure, electrochemistry and reactivities

E. C. E. Rosenthal, H. Cui, J. Koch, P. Escarpa Gaede, M. Hummert and S. Dechert, Dalton Trans., 2005, 3108 DOI: 10.1039/B505750G

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