Chloro(cyclopentadienyl)bis(triphenylphosphine)ruthenium explained

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 Cs 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.[1]

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.[2]

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[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>] + NH4Cl

Displacement of one PPh3 by carbon monoxide affords a chiral compound.[3]

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

The compound can also be converted into the hydride:[4]

(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.[5]

Notes and References

  1. Gilbert JD, Wilkinson, G . New Complexes of Ruthenium(II) with Triphenylphosphine and other Ligands . . 10.1039/J19690001749 . 1969 . 1749.
  2. Bruce, M. I.; Hamiester, C., Swincer, A. G., Wallis, R. C. "Some η5-Cyclopentadienylruthenium(II) Complexes Containing Triphenylphosphine" Inorganic Syntheses 1982, volume 21, pp 78-82.
  3. Blackmore T, Bruce MI,((Stone, F. G. A.)). 1971 . Some New η-Cyclopentadienyltuthenium Complexes . J. Chem. Soc. A . 2376–2382 . 10.1039/J19710002376.
  4. Wilczewski, T. . Bochenska, M. . Biernat, J. . amp . 1981 . Cyclobentadienyl-Ruthenium Complexes . . 10.1016/S0022-328X(00)84619-7 . 215 . 87–96.
  5. Murahashi, Shun-Ichi. "Ruthenium in Organic Synthesis" (2006) Wiley-VCH: Weinheim.