Mehrfachbindungen zwischen Hauptgruppenelementen und Übergangsmetallen. LXII. Alkin-Komplexe der Organorheniumoxide: Redox-Chemie und Nucleophilie der Oxo-Funktion von (η5-Pentamethylcyclopentadienyl)(η2-diphenylethin) oxorhenium(III)

Wolfgang A. Herrmann, Roland A. Fischer, Wolfgang Amslinger, Eberhardt Herdtweck

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Abstract

The novel ReIII oxo alkyne complexes (η5-C5Me5)Re(=O)(η2-RCCR) (3a-c; R = C6H5, CH3, C2H5) are obtained almost quantitiatively by alkaline hydrolysis of the dichloro precursor compounds (η5C5Me5)ReCl22-RCCR) (4a-c). An X-ray diffraction study has revealed that in the phenyl derivative 3a the alkyne group is best described as a two-electron ligand. 17O NMR spectroscopy shows the remarkable electron deficiency of the terminal oxo group. This oxo function however is sufficiently nucleophilic to be converted into the hydroxo psecies [η2-diphenylalkyne)hydroxo(η5-pentamethylcyclopentadienyl)rhenium(III)] tetrafluoroborate (5a) and [(η2-butyne(2))hydroxo(η5-pentamethylcyclopentadienyl)rhenium(III)] tetrafluoroborate (5b) by O-protonation with HBF4. One-electron oxidation of 3a leads to the dinuclear ReIV species [(μ-O)(η5-C5Me5)Re(η2-C6H5CCC6H5)2]2+ without loss of the alkyne ligand. The ReV systems (η5-C5Me5)Re(=O)22-RCCR) (2, generated oxidatively, are not stable as they decompose rapidly by eliminating the alkyne ligand.

Original languageGerman
Pages (from-to)333-343
Number of pages11
JournalJournal of Organometallic Chemistry
Volume362
Issue number3
DOIs
StatePublished - 7 May 1989

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