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Tantalum(III) chloride

Tantalum(III) chloride or tantalum trichloride is a non-stoichiometric chemical compound with a range of composition from TaCl<sub>2.9</sub> to TaCl<sub>3.1</sub> Anionic and neutral clusters containing Ta(III) chloride include [Ta<sub>6</sub>Cl<sub>18</sub>]<sup>4−</sup> and [Ta<sub>6</sub>Cl<sub>14</sub>](H<sub>2</sub>O)<sub>4</sub>.

Formation

Tantalum(III) chloride is formed by reducing tantalum(V) chloride with tantalum metal. this is done by heating tantalum(III) chloride to 305&nbsp;°C, passing the vapour over tantalum foil at 600°, and condensing the trichloride at 365&nbsp;°C. If the condensing region is kept at too high a temperature, then TaCl<sub>2.5</sub> deposits instead.

The trichloride can also be prepared by thermal decomposition of TaCl<sub>4</sub>, with removal of volatile TaCl<sub>5</sub>. TaCl<sub>5</sub> can be vapourised leaving behind TaCl<sub>3</sub>.

"Salt-free reduction" of a toluene solution of TaCl<sub>5</sub> with 1,4-disilyl-cyclohexadiene in the presence of ethylene produces a complex of TaCl<sub>3</sub>:

Properties

Above 500&nbsp;°C, TaCl<sub>3</sub> disproportionates further releasing TaCl<sub>5</sub>. TaCl<sub>3</sub> is insoluble in room temperature water, or dilute acid, but dissolves in boiling water. A blue-green solution is formed.

Complexes

Tantalum(III) chloride can form complexes with some ligands as a monomer or dimer.

Complexes include Ta(=C-CMe<sub>3</sub>)(PMe<sub>3</sub>)<sub>2</sub>Cl<sub>3</sub>, [TaCl<sub>3</sub>(P(CH<sub>2</sub>C<sub>6</sub>H<sub>5</sub>)<sub>3</sub>THF]<sub>2</sub>μ-N<sub>2</sub> and [TaCl<sub>3</sub>THF<sub>2</sub>]<sub>2</sub>μ-N<sub>2</sub> (dinitrogen complexes).

As a dimer, complexes include Ta<sub>2</sub>Cl<sub>6</sub>(SC<sub>4</sub>H<sub>8</sub>)<sub>3</sub> (SC<sub>4</sub>H<sub>8</sub>=tetrahydrothiophene). Ta<sub>2</sub>Cl<sub>6</sub>(SMe<sub>2</sub>)<sub>3</sub>, Ta<sub>2</sub>Cl<sub>6</sub>(thiane)<sub>3</sub> and Ta<sub>2</sub>Cl<sub>6</sub>(thiolane)<sub>3</sub> have a double bond between the two tantalum atoms, and two bridging chlorides, and a bridging ligand.

References