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Organovanadium chemistry
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Organovanadium chemistry
Organovanadium chemistry is the chemistry of organometallic compounds containing a carbon (C) to vanadium (V) chemical bond. Organovanadium compounds find only minor use as reagents in organic synthesis but are significant for polymer chemistry as catalysts.
Oxidation states for vanadium are +2, +3, +4 and +5. Low valency vanadium is usually stabilized with carbonyl ligands. Oxo derivatives are relatively common, unlike the organic complexes of neighboring elements.
Vanadium carbonyl can be prepared by reductive carbonylation of vanadium salts:
The salt can be oxidized to the 17e binary carbonyl V(CO)6.
Conversely, reduction gives the V(CO)3−
5 anion. The rubidium and cesium salts are stable at room temperature, but not the sodium salt. Soft electrophiles attack the anion to give heptacoordinate and octacoordinate cluster complexes.
Vanadocene dichloride, the first organovanadium complexes to be reported, is prepared from sodium cyclopentadienyl and vanadium tetrachloride:
Reduction of this compound gives the parent vanadocene (Cp2V):
Vanadocene is the lightest transition metal metallocene that is isolable at room temperature. Vanadocene reacts with high pressures of carbon monoxide to give CpV(CO)4. Photolysis of the tetracarbonyl gives Cp2V2(CO)5. Several analogous indenyl complexes are known.
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Organovanadium chemistry
Organovanadium chemistry is the chemistry of organometallic compounds containing a carbon (C) to vanadium (V) chemical bond. Organovanadium compounds find only minor use as reagents in organic synthesis but are significant for polymer chemistry as catalysts.
Oxidation states for vanadium are +2, +3, +4 and +5. Low valency vanadium is usually stabilized with carbonyl ligands. Oxo derivatives are relatively common, unlike the organic complexes of neighboring elements.
Vanadium carbonyl can be prepared by reductive carbonylation of vanadium salts:
The salt can be oxidized to the 17e binary carbonyl V(CO)6.
Conversely, reduction gives the V(CO)3−
5 anion. The rubidium and cesium salts are stable at room temperature, but not the sodium salt. Soft electrophiles attack the anion to give heptacoordinate and octacoordinate cluster complexes.
Vanadocene dichloride, the first organovanadium complexes to be reported, is prepared from sodium cyclopentadienyl and vanadium tetrachloride:
Reduction of this compound gives the parent vanadocene (Cp2V):
Vanadocene is the lightest transition metal metallocene that is isolable at room temperature. Vanadocene reacts with high pressures of carbon monoxide to give CpV(CO)4. Photolysis of the tetracarbonyl gives Cp2V2(CO)5. Several analogous indenyl complexes are known.