Vanadocene, bis(η5-cyclopentadienyl) vanadium, is the organometallic compound with the formula V(C5H5)2, commonly abbreviated Cp2V. It is a violet crystalline, paramagnetic solid. Vanadocene has relatively limited practical use, but it has been extensively studied.
V(C5H5)2 is a metallocene, a class of organometallic compounds that typically have a metal ion sandwiched between two cyclopentadienyl rings. In the solid state, the molecule has D5d symmetry. The vanadium(II) center resides equidistant between the center of the two cyclopentadienyl rings at a crystallographic center of inversion. The average V-C bond distance is 226 pm.[1] The Cp rings of vanadocene are dynamically disordered at temperatures above 170 K and are only fully ordered at 108 K.
Vanadocene was first prepared in 1954 by Birmingham, Fischer, and Wilkinson via a reduction of vanadocene dichloride with aluminum hydride, after which vanadocene was sublimed in vacuum at 100 ˚C.[2] A modern synthesis of vanadocene that allows production in higher quantities requires treating [V<sub>2</sub>Cl<sub>3</sub>(THF)<sub>6</sub>]2[Zn<sub>2</sub>Cl<sub>6</sub>] with cyclopentadienylsodium.[3]
2 [V<sub>2</sub>Cl<sub>3</sub>(THF)<sub>6</sub>]2[Zn<sub>2</sub>Cl<sub>6</sub>] + 8 NaCp + THF → 4 Cp2V
Vanadocene is a reactive molecule. As it only has 15 valence electrons available, it readily reacts with many ligands. With alkynes, for example, it reacts to yield the corresponding vanadium-cyclopropene complexes.[4]
One reaction involves carbon monoxide, leading to an ionic vanadocene derivative when performed in inert atmosphere:
Cp2V + V(CO)6 → [Cp<sub>2</sub>V(CO)<sub>2</sub>][V(CO)<sub>6</sub>]Vanadocene is readily oxidized to the monocation when treated with a ferrocenium salt in toluene.[5]
VCp2 + [FeCp<sub>2</sub>]BR4 → [VCp<sub>2</sub>]BR4 + FeCp2 (R = Ph or 4-C6H4F)These monocations are extremely air-sensitive and have a redox potential of -1.10 V.
Vanadocene reacts with high pressures of carbon monoxide to give CpV(CO)4.[6]