Mehrfachbindungen zwischen Hauptgruppenelementen und Übergangsmetallen. LXI. Darstellung und Strukturaufklärung von schwefelund sauerstoffhaltigen Organovanadium(V)-Komplexen

Wolfgang A. Herrmann, Eberhardt Herdtweck, Georg Weichselbaumer

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Oxychlorination of the carbonylvanadium(I) complexes CpV(CO)4 (Cp = C5H5, 1a; C5Me5, 1b; C5H4Me, 1c; C5Me4Et, 1d) provides a general synthetic route to organovanadium(V) compounds of comosition CpVOCl2 (2a-d). Reaction of 2a,b with the sodium salts of phenol, cresol, and thiophenol yields the substitution products (η5-C5H5)VO(OC6H5)2 (3a), (η5-C5Me5)VO(p-OC6H4CH3)2 (3b), (η5-C5Me5)V(O)Cl(p-OC6H4CH3) (3b'), and (η5-C5R5)VO(SC6H5)2 (R = H, 4a; CH3, 4b). 4a crystallizes from diethyl ether/n-hexane solutions as black plates (triclinic space group; distorted tetrahedral coordination geometry). Reaction of 2a,b with glycol in the presence of triethylamine yields the dinuclear complexes [(η5-C5R5)VO]2(μ-O)(μ, η2-OCH2CH2O) (R = H, 5a; CH3, 5b). An X-ray structure analysis reveals that 5b has a seven-membered V2O3C2 core geometry. The 51V NMR spectra provide information on the electronic situation at the central vanadium atoms of complexes 1-5 and related compounds.

Original languageGerman
Pages (from-to)321-332
Number of pages12
JournalJournal of Organometallic Chemistry
Issue number3
StatePublished - 7 May 1989

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