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Vanadocene

Vanadocene, bis(η<sup>5</sup>-cyclopentadienyl) vanadium, is the organometallic compound with the formula V(C<sub>5</sub>H<sub>5</sub>)<sub>2</sub>, commonly abbreviated Cp<sub>2</sub>V. It is a violet crystalline, paramagnetic solid. Vanadocene has relatively limited practical use, but it has been extensively studied.

Structure and bonding

V(C<sub>5</sub>H<sub>5</sub>)<sub>2</sub> 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 D<sub>5d</sub> 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. The Cp rings of vanadocene are dynamically disordered at temperatures above 170 K and are only fully ordered at 108 K.

Preparation

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. 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>]<sub>2</sub>[Zn<sub>2</sub>Cl<sub>6</sub>] with cyclopentadienylsodium.

2 [V<sub>2</sub>Cl<sub>3</sub>(THF)<sub>6</sub>]<sub>2</sub>[Zn<sub>2</sub>Cl<sub>6</sub>] + 8 NaCp + THF → 4 Cp<sub>2</sub>V

Properties

With only 15 valence electrons, vanadocene is highly reactive. For example, it adds alkynes to yield the corresponding vanadium-cyclopropene complexes.

Likewise, high carbon monoxide pressures give CpV(CO)<sub>4</sub>. That piano-stool complex can rearrange to an ionic, mixed-valence, vanadium hexacarbonyl derivative:

Cp<sub>2</sub>V + V(CO)<sub>6</sub> → [Cp<sub>2</sub>V(CO)<sub>2</sub>]<sup>+</sup>[V(CO)<sub>6</sub>]<sup>&minus;</sup>

Vanadocene is extremely air-sensitive, and either 12% (by mass) hydrochloric acid or ferrocenium in toluene will easily oxidize an electron from the complex:

VCp<sub>2</sub> + [FeCp<sub>2</sub>]BR<sub>4</sub> → [VCp<sub>2</sub>]BR<sub>4</sub> + FeCp<sub>2</sub> (R = Ph or 4-C<sub>6</sub>H<sub>4</sub>F)

The monocations themselves oxidize in air, having a redox potential of -1.10&nbsp;V.

Related compounds

References