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Bis(cyclooctadiene)nickel(0)

Bis(cyclooctadiene)nickel(0) is the organonickel compound with the formula Ni(C<sub>8</sub>H<sub>12</sub>)<sub>2</sub>, also written Ni(cod)<sub>2</sub>. It is a diamagnetic coordination complex featuring tetrahedral nickel(0) bound to the alkene groups in two 1,5-cyclooctadiene ligands. This highly air-sensitive yellow solid is a common source of Ni(0) in chemical synthesis.

Preparation and properties

The complex is prepared by reduction of anhydrous nickel(II) acetylacetonate in the presence of the diolefin:

Ni(acac)<sub>2</sub> + 2 cod + 2 AlEt<sub>3</sub> → Ni(cod)<sub>2</sub> + 2 acacAlEt<sub>2</sub> + C<sub>2</sub>H<sub>6</sub> + C<sub>2</sub>H<sub>4</sub>

Ni(cod)<sub>2</sub> is moderately soluble in several organic solvents.

If exposed to air, the solid oxidizes in a few minutes to nickel(II) oxide. As a result, this compound is generally handled in a glovebox.

Reactions

The reactivity of Ni(cod)<sub>2</sub> has been extensively examined. One or both 1,5-cyclooctadiene ligands are readily displaced by phosphines, phosphites, bipyridine, and isocyanides.

Oxidation gives the highly reactive monocation, which can be isolated when using weakly coordinating anions:

Of its many catalytic reactions, Ni(cod)<sub>2</sub> in the presence of phosphine ligands catalyzes the demethoxylation of anisoles by hydrosilanes:

References