The one-electron oxidation of vanadocene, VCp2, by [FeCp2]+ in toluene affords the 14- electron [VCp2]+ cation, which has been isolated as an unsolvated species for the first time. Vanadium hexacarbonyl reacts with VCp2 to give the í-isocarbonyl derivative Cp2V(í-OC)V- (CO)5 as a transient species, which has been characterized in solution by IR analysis. By reaction of VCp2 with V(13CO)6 followed by treatment with 12CO, the ionic dicarbonyl derivative [VCp2(12CO)2][V(13CO)6] is formed, thus showing that during the formation of the ionic compound no redistribution of the carbonyl ligands between the two metal centers occurs. Bis(cyclopentadienyl)vanadium(II) and Co2(CO)8 give Cp2VCo(CO)4, which slowly decomposes in solution even at low temperature to give [VCp2(CO)2][Co(CO)4], which was identified by conventional methods, including single-crystal X-ray diffraction. The reactivity of the unsolvated [VCp2]+ cation as well as that of the heterobimetallic compound containing vanadium and cobalt with several Lewis bases is reported.
Oxidation products of vanadocene and of its permethylated analogue, including the isolation and the reactivity of the unsolvated VCp2+ cation
CALDERAZZO, FAUSTO;PAMPALONI, GUIDO;
1999-01-01
Abstract
The one-electron oxidation of vanadocene, VCp2, by [FeCp2]+ in toluene affords the 14- electron [VCp2]+ cation, which has been isolated as an unsolvated species for the first time. Vanadium hexacarbonyl reacts with VCp2 to give the í-isocarbonyl derivative Cp2V(í-OC)V- (CO)5 as a transient species, which has been characterized in solution by IR analysis. By reaction of VCp2 with V(13CO)6 followed by treatment with 12CO, the ionic dicarbonyl derivative [VCp2(12CO)2][V(13CO)6] is formed, thus showing that during the formation of the ionic compound no redistribution of the carbonyl ligands between the two metal centers occurs. Bis(cyclopentadienyl)vanadium(II) and Co2(CO)8 give Cp2VCo(CO)4, which slowly decomposes in solution even at low temperature to give [VCp2(CO)2][Co(CO)4], which was identified by conventional methods, including single-crystal X-ray diffraction. The reactivity of the unsolvated [VCp2]+ cation as well as that of the heterobimetallic compound containing vanadium and cobalt with several Lewis bases is reported.I documenti in IRIS sono protetti da copyright e tutti i diritti sono riservati, salvo diversa indicazione.
