TY - JOUR
T1 - Mehrfachbindungen zwischen Hauptgruppenelementen und Übergangsmetallen. LXII. Alkin-Komplexe der Organorheniumoxide
T2 - Redox-Chemie und Nucleophilie der Oxo-Funktion von (η5-Pentamethylcyclopentadienyl)(η2-diphenylethin) oxorhenium(III)
AU - Herrmann, Wolfgang A.
AU - Fischer, Roland A.
AU - Amslinger, Wolfgang
AU - Herdtweck, Eberhardt
PY - 1989/5/7
Y1 - 1989/5/7
N2 - 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)ReCl2(η2-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)2(η2-RCCR) (2, generated oxidatively, are not stable as they decompose rapidly by eliminating the alkyne ligand.
AB - 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)ReCl2(η2-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)2(η2-RCCR) (2, generated oxidatively, are not stable as they decompose rapidly by eliminating the alkyne ligand.
UR - http://www.scopus.com/inward/record.url?scp=0000269337&partnerID=8YFLogxK
U2 - 10.1016/0022-328X(89)87255-9
DO - 10.1016/0022-328X(89)87255-9
M3 - Artikel
AN - SCOPUS:0000269337
SN - 0022-328X
VL - 362
SP - 333
EP - 343
JO - Journal of Organometallic Chemistry
JF - Journal of Organometallic Chemistry
IS - 3
ER -