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Chloro(cyclopentadienyl)bis(triphenylphosphine)ruthenium

Chloro(cyclopentadienyl)bis(triphenylphosphine)ruthenium is the organoruthenium half-sandwich compound with formula RuCl(PPh<sub>3</sub>)<sub>2</sub>(C<sub>5</sub>H<sub>5</sub>). It as an air-stable orange crystalline solid that is used in a variety of organometallic synthetic and catalytic transformations. The compound has idealized C<sub>s</sub> symmetry. It is soluble in chloroform, dichloromethane, and acetone.

Preparation

Chloro(cyclopentadienyl)bis(triphenylphosphine)ruthenium was first reported in 1969 when it was prepared by reacting dichlorotris(triphenylphosphine)ruthenium(II) with cyclopentadiene.

RuCl<sub>2</sub>(PPh<sub>3</sub>)<sub>3</sub> + C<sub>5</sub>H<sub>6</sub> → RuCl(PPh<sub>3</sub>)<sub>3</sub>(C<sub>5</sub>H<sub>5</sub>) + HCl

It is prepared by heating a mixture of ruthenium(III) chloride, triphenylphosphine, and cyclopentadiene in ethanol.

Reactions

Chloro(cyclopentadienyl)bis(triphenylphosphine)ruthenium(II) undergoes a variety of reactions often by involving substitution of the chloride. With phenylacetylene it gives the phenyl vinylidene complex:

(C<sub>5</sub>H<sub>5</sub>)(PPh<sub>3</sub>)<sub>2</sub>RuCl + HC<sub>2</sub>Ph + NH<sub>4</sub>[PF<sub>6</sub>] → [Ru(C:CHPh)(PPh<sub>3</sub>)<sub>2</sub>(C<sub>5</sub>H<sub>5</sub>)][PF<sub>6</sub>] + NH<sub>4</sub>Cl

Displacement of one PPh<sub>3</sub> by carbon monoxide affords a chiral compound.

(C<sub>5</sub>H<sub>5</sub>)(PPh<sub>3</sub>)<sub>2</sub>RuCl + CO → (C<sub>5</sub>H<sub>5</sub>)(PPh<sub>3</sub>)(CO)RuCl + PPh<sub>3</sub>

The compound can also be converted into the hydride:

(C<sub>5</sub>H<sub>5</sub>)(PPh<sub>3</sub>)<sub>2</sub>RuCl + NaOMe → (C<sub>5</sub>H<sub>5</sub>)(PPh<sub>3</sub>)<sub>2</sub>RuH + NaCl + CH<sub>2</sub>O

A related complex is tris(acetonitrile)cyclopentadienylruthenium hexafluorophosphate, which has three labile MeCN ligands.

Applications

Chloro(cyclopentadienyl)bis(triphenylphosphine)ruthenium(II) serves as a catalyst for a variety of specialized reactions. For example, in the presence of NH<sub>4</sub>PF<sub>6</sub> it catalyzes the isomerisation of allylic alcohols to the corresponding saturated carbonyls.

References