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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 Cs symmetry. It is soluble in chloroform, dichloromethane, and acetone.

CpRuCl(PPh3)2
Identifiers
3D model (JSmol)
ChemSpider
ECHA InfoCard 100.154.457 Edit this at Wikidata
  • 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 ☒N
    Key: WGQMSPWAXIDKEY-UHFFFAOYSA-M ☒N
  • 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
  • c1ccc(cc1)P(c2ccccc2)c3ccccc3.c1ccc(cc1)P(c2ccccc2)c3ccccc3.c1ccc[cH-1]1.[Cl-].[Ru 2]
Properties
C41H35ClP2Ru
Molar mass 726.19 g/mol
Appearance Orange solid
Melting point 135 °C (275 °F; 408 K)
Insoluble
Hazards
GHS labelling:
GHS07: Exclamation mark
Warning
H302, H312, H315, H319, H332, H335
P261, P264, P270, P271, P280, P301 P312, P302 P352, P304 P312, P304 P340, P305 P351 P338, P312, P321, P322, P330, P332 P313, P337 P313, P362, P363, P403 P233, 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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Preparation

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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

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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

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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

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  1. ^ Gilbert JD, Wilkinson, G (1969). "New Complexes of Ruthenium(II) with Triphenylphosphine and other Ligands". J. Chem. Soc.: 1749. doi:10.1039/J19695001749.
  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/J19710002376.2376-2382&rft.date=1971&rft_id=info:doi/10.1039/J19710002376&rft.aulast=Blackmore&rft.aufirst=T&rft.au=Bruce, MI&rft.au=Stone, F. G. A.&rfr_id=info:sid/en.wikipedia.org:Chloro(cyclopentadienyl)bis(triphenylphosphine)ruthenium" class="Z3988">
  4. ^ Wilczewski, T.; Bochenska, M. & Biernat, J. (1981). "Cyclobentadienyl-Ruthenium Complexes". J. Organomet. Chem. 215: 87–96. doi:10.1016/S0022-328X(00)84619-7.87-96&rft.date=1981&rft_id=info:doi/10.1016/S0022-328X(00)84619-7&rft.au=Wilczewski, T.&rft.au=Bochenska, M.&rft.au=Biernat, J.&rfr_id=info:sid/en.wikipedia.org:Chloro(cyclopentadienyl)bis(triphenylphosphine)ruthenium" class="Z3988">
  5. ^ Murahashi, Shun-Ichi. "Ruthenium in Organic Synthesis" (2006) Wiley-VCH: Weinheim. ISBN 978-3-527-30692-3
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