Английская Википедия:Chloro(cyclopentadienyl)bis(triphenylphosphine)ruthenium

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Chloro(cyclopentadienyl)bis(triphenylphosphine)ruthenium is the organoruthenium half-sandwich compound with formula RuCl(PPh₃)₂(C₅H₅). 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_s 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.

RuCl₂(PPh₃)₃ + C₅H₆ → RuCl(PPh₃)₃(C₅H₅) + 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:

(C₅H₅)(PPh₃)₂RuCl + HC₂Ph + NH₄[PF₆] → [Ru(C:CHPh)(PPh₃)₂(C₅H₅)][PF₆] + NH₄Cl

Displacement of one PPh₃ by carbon monoxide affords a chiral compound.

(C₅H₅)(PPh₃)₂RuCl + CO → (C₅H₅)(PPh₃)(CO)RuCl + PPh₃

The compound can also be converted into the hydride:

(C₅H₅)(PPh₃)₂RuCl + NaOMe → (C₅H₅)(PPh₃)₂RuH + NaCl + CH₂O

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 NH₄PF₆ it catalyzes the isomerisation of allylic alcohols to the corresponding saturated carbonyls.