Chloro(cyclopentadienyl)bis(triphenylphosphine)ruthenium

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.

CpRuCl(PPh₃)₂

Identifiers
CAS Number	32993-05-8
3D model (JSmol)	Interactive image
ChemSpider	34560989
ECHA InfoCard	100.154.457
PubChem CID	78076231
InChI InChI=1S/2C18H15P.C5H5.ClH.Ru/c2*1-4-10-16(11-5-1)19(17-12-6-2-7-13-17)18-14-8-3-9-15-18;1-2-4-5-3-1;;/h2*1-15H;1-3H,4H2;1H;/q;;-1;;+2/p-1 Key: WGQMSPWAXIDKEY-UHFFFAOYSA-M InChI=1/2C18H15P.C5H5.ClH.Ru/c2*1-4-10-16(11-5-1)19(17-12-6-2-7-13-17)18-14-8-3-9-15-18;1-2-4-5-3-1;;/h2*1-15H;1-3H,4H2;1H;/q;;-1;;+2/p-1 Key: WGQMSPWAXIDKEY-REWHXWOFAY
SMILES c1ccc(cc1)P(c2ccccc2)c3ccccc3.c1ccc(cc1)P(c2ccccc2)c3ccccc3.c1ccc[cH-1]1.[Cl-].[Ru+2]
Properties
Chemical formula	C41H35ClP2Ru
Molar mass	726.19 g/mol
Appearance	Orange solid
Melting point	135 °C (275 °F; 408 K)
Solubility in water	Insoluble
Hazards
GHS pictograms
GHS Signal word	Warning
GHS hazard statements	H302, H312, H315, H319, H332, H335
GHS precautionary statements	P261, P264, P270, P271, P280, P301+312, P302+352, P304+312, P304+340, P305+351+338, P312, P321, P322, P330, P332+313, P337+313, P362, P363, P403+233, P405, P501
Except where otherwise noted, data are given for materials in their standard state (at 25 °C [77 °F], 100 kPa).
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Infobox references

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[PF₆] → [Ru(C:CHPh)(PPh₃)₂(C₅H₅)][PF₆] + 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]

References

1. Gilbert JD, Wilkinson, G (1969). "New Complexes of Ruthenium(II) with Triphenylphosphine and other Ligands". J. Chem. Soc.: 1749. doi:10.1039/J19690001749.
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. doi:10.1002/9780470132524
3. Blackmore T, Bruce MI, Stone, F. G. A. (1971). "Some New η-Cyclopentadienyltuthenium Complexes". J. Chem. Soc. A: 2376–2382. doi:10.1039/J19710002376.
4. Wilczewski, T.; Bochenska, M. & Biernat, J. (1981). "Cyclobentadienyl-Ruthenium Complexes". J. Organomet. Chem. 215: 87. doi:10.1016/S0022-328X(00)84619-7.
5. Murahashi, Shun-Ichi. "Ruthenium in Organic Synthesis" (2006) Wiley-VCH: Weinheim. ISBN 978-3-527-30692-3