Chloro(cyclopentadienyl)bis(triphenylphosphine)ruthenium

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/c21-4-10-16(11-5-1)19(17-12-6-2-7-13-17)18-14-8-3-9-15-18;1-2-4-5-3-1;;/h21-15H;1-3H,4H2;1H;/q;;-1;;+2/p-1 Key: WGQMSPWAXIDKEY-UHFFFAOYSA-M ; InChI=1/2C18H15P.C5H5.ClH.Ru/c21-4-10-16(11-5-1)19(17-12-6-2-7-13-17)18-14-8-3-9-15-18;1-2-4-5-3-1;;/h21-15H;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 labelling:
Pictograms
Signal word	Warning
Hazard statements	H302, H312, H315, H319, H332, H335
Precautionary statements	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). verify (what is ?) Infobox references

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.^[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

^ Gilbert JD, Wilkinson, G (1969). "New Complexes of Ruthenium(II) with Triphenylphosphine and other Ligands". J. Chem. Soc.: 1749. doi:10.1039/J19690001749.
^ 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
^ Blackmore T, Bruce MI, Stone, F. G. A. (1971). "Some New η-Cyclopentadienyltuthenium Complexes". J. Chem. Soc. A: 2376–2382. doi:10.1039/J19710002376.
^ Wilczewski, T.; Bochenska, M. & Biernat, J. (1981). "Cyclobentadienyl-Ruthenium Complexes". J. Organomet. Chem. 215: 87–96. doi:10.1016/S0022-328X(00)84619-7.
^ Murahashi, Shun-Ichi. "Ruthenium in Organic Synthesis" (2006) Wiley-VCH: Weinheim. ISBN 978-3-527-30692-3

[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: 87–96. 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

[1]

[2]

[3]

[4]

[5]

Chloro(cyclopentadienyl)bis(triphenylphosphine)ruthenium

Preparation

Reactions

Applications

References

Portal di Ensiklopedia Dunia