Dichlorotris(triphenylphosphine)ruthenium(II)

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Dichlorotris(triphenylphosphine)ruthenium(II)
Names
IUPAC name Dichlorotris(triphenylphosphine)ruthenium(II)
Other names Ruthenium tris(triphenylphosphine) dichloride; Tris(triphenylphosphine)dichlororuthenium; Tris(triphenylphosphine)ruthenium dichloride;Tris(triphenylphosphine)ruthenium(II) dichloride
Identifiers
CAS Number
3D model (JSmol)
ChemSpider
ECHA InfoCard 100.035.957
EC Number
  • 239-569-7
PubChem CID
CompTox Dashboard (EPA)
InChI
  • InChI=1S/3C18H15P.2ClH.Ru/c3*1-4-10-16(11-5-1)19(17-12-6-2-7-13-17)18-14-8-3-9-15-18;;;/h3*1-15H;2*1H;/q;;;;;+2/p-2 checkYKey: WIWBLJMBLGWSIN-UHFFFAOYSA-L checkY
  • InChI=1/3C18H15P.2ClH.Ru/c3*1-4-10-16(11-5-1)19(17-12-6-2-7-13-17)18-14-8-3-9-15-18;;;/h3*1-15H;2*1H;/q;;;;;+2/p-2Key: WIWBLJMBLGWSIN-NUQVWONBAX
SMILES
  • ...c3c(P(c1ccccc1)c2ccccc2)cccc3.c1ccccc1P(c2ccccc2)c3ccccc3.c1ccccc1P(c2ccccc2)c3ccccc3
Properties
Chemical formula C54H45Cl2P3Ru
Molar mass 958.83 g/mol
Appearance Black Crystals or Red-Brown
Density 1.43 g cm−3
Melting point 133 °C; 271 °F; 406 K
Structure
Crystal structure Monoclinic
Space group C2h5-P21/c
Lattice constant a = 18.01 Å, b = 20.22 Å, c = 12.36 Åα = 90°, β = 90.5°, γ = 90°
Coordination geometry Octahedral
Hazards
GHS labelling:
Pictograms GHS07: Exclamation mark
Signal word Warning
Hazard statements H302, H312, H332
Precautionary statements P261, P264, P270, P271, P280, P301+P312, P302+P352, P304+P312, P304+P340, P312, P322, P330, P363, P501
Except where otherwise noted, data are given for materials in their standard state (at 25 °C , 100 kPa). checkY verify (what is checkY☒N ?) Infobox references

Dichlorotris(triphenylphosphine)ruthenium(II) is a coordination complex of ruthenium. It is a chocolate brown solid that is soluble in organic solvents such as benzene. The compound is used as a precursor to other complexes including those used in homogeneous catalysis.

Synthesis and basic properties

RuCl2(PPh3)3 is the product of the reaction of ruthenium trichloride trihydrate with a methanolic solution of triphenylphosphine.

2 RuCl3(H2O)3 + 7 PPh3 → 2 RuCl2(PPh3)3 + 2 HCl + 5 H2O + OPPh3

The coordination sphere of RuCl2(PPh3)3 can be viewed as either five-coordinate or octahedral. One coordination site is occupied by one of the hydrogen atoms of a phenyl group. This Ru---H agostic interaction is long (2.59 Å) and weak. The low symmetry of the compound is reflected by the differing lengths of the Ru-P bonds: 2.374, 2.412, and 2.230 Å. The Ru-Cl bond lengths are both 2.387 Å.

Reactions

In the presence of excess of triphenylphosphine, RuCl2(PPh3)3 binds a fourth phosphine to give black RuCl2(PPh3)4. The triphenylphosphine ligands in both the tris(phosphine) and tetrakis(phosphine) complexes are readily substituted by other ligands. The tetrakis(phosphine) complex is a precursor to the Grubbs catalysts.

Dichlorotris(triphenylphosphine)ruthenium(II) reacts with hydrogen in the presence of base to give the purple-colored monohydride HRuCl(PPh3)3.

RuCl2(PPh3)3 + H2 + NEt3 → HRuCl(PPh3)3 + Cl

Dichlorotris(triphenylphosphine)ruthenium(II) reacts with carbon monoxide to produce the all trans isomer of dichloro(dicarbonyl)bis(triphenylphosphine)ruthenium(II).

RuCl2(PPh3)3 + 2 CO → trans,trans,trans-RuCl2(CO)2(PPh3)2 + PPh3

This kinetic product isomerizes to the cis adduct during recrystallization. trans-RuCl2(dppe)2 forms upon treating RuCl2(PPh3)3 with dppe.

RuCl2(PPh3)3 + 2 dppe → RuCl2(dppe)2 + 3 PPh3

RuCl2(PPh3)3 catalyzes the decomposition of formic acid into carbon dioxide and hydrogen gas in the presence of an amine. Since carbon dioxide can be trapped and hydrogenated on an industrial scale, formic acid represents a potential storage and transportation medium.

Use in organic synthesis

RuCl2(PPh3)3 facilitates oxidations, reductions, cross-couplings, cyclizations, and isomerization. It is used in the Kharasch addition of chlorocarbons to alkenes.

Dichlorotris(triphenylphosphine)ruthenium(II) serves as a precatalyst for the hydrogenation of alkenes, nitro compounds, ketones, carboxylic acids, and imines. On the other hand, it catalyzes the oxidation of alkanes to tertiary alcohols, amides to t-butyldioxyamides, and tertiary amines to α-(t-butyldioxyamides) using tert-butyl hydroperoxide. Using other peroxides, oxygen, and acetone, the catalyst can oxidize alcohols to aldehydes or ketones. Using dichlorotris(triphenylphosphine)ruthenium(II) the N-alkylation of amines with alcohols is also possible (see "borrowing hydrogen").

RuCl2(PPh3)3 efficiently catalyzes carbon-carbon bond formation from cross couplings of alcohols through C-H activation of sp3 carbon atoms in the presence of a Lewis acid.

References

  1. ^ Stephenson, T. A.; Wilkinson, G. "New Complexes of Ruthenium (II) and (III) with Triphenylphosphine, Triphenylarsine, Trichlorostannate, Pyridine, and other Ligands", J. Inorg. Nucl. Chem., 1966, 28, 945-956. doi:10.1016/0022-1902(66)80191-4
  2. ^ P. S. Hallman, T. A. Stephenson, G. Wilkinson "Tetrakis(Triphenylphosphine)Dichloro-Ruthenium(II) and Tris(Triphenylphosphine)-Dichlororuthenium(II)" Inorganic Syntheses, 1970 volume 12 doi:10.1002/9780470132432.ch40
  3. ^ Sabo-Etienne, S.; Gellier, M., "Ruthenium: Inorganic and Coordination Chemistry", Encyclopedia of Inorganic Chemistry, 2006, John Wiley & Sons Sabo-Etienne, Sylviane; Grellier, Mary (2006). "Ruthenium: Inorganic & Coordination Chemistry Based in part on the article Ruthenium: Inorganic & Coordination Chemistry by Bruno Chaudret & Sylviane Sabo-Etienne which appeared in the Encyclopedia of Inorganic Chemistry, First Edition". Encyclopedia of Inorganic Chemistry. doi:10.1002/0470862106.ia208. ISBN 0470860782.
  4. ^ La Placa, Sam J.; Ibers, James A. (1965). "A Five-Coordinated d6 Complex: Structure of Dichlorotris(triphenylphosphine)ruthenium (II)". Inorganic Chemistry. 4 (6): 778–783. doi:10.1021/ic50028a002.
  5. ^ Georgios C. Vougioukalakis, Robert H. Grubbs "Ruthenium-Based Heterocyclic Carbene-Coordinated Olefin Metathesis Catalysts" Chem. Rev., 2010, volume 110, pp 1746–1787 Vougioukalakis, Georgios C.; Grubbs, Robert H. (2010). "Ruthenium-Based Heterocyclic Carbene-Coordinated Olefin Metathesis Catalysts". Chemical Reviews. 110 (3): 1746–1787. doi:10.1021/cr9002424. PMID 20000700.
  6. ^ Schunn, R. A.; Wonchoba, E. R. (1972). "Chlorohydridotris(triphenylphosphine)ruthenium(II)". Inorganic Syntheses. Vol. 13. p. 131. doi:10.1002/9780470132449.ch26. ISBN 9780470132449.
  7. ^ Loges, B.; Boddien, A.; Junge, H.; Beller, M., "Controlled Generation of Hydrogen from Formic Acid Amine Adducs at Room Temperature and Application in H2/O2 Fuel Cells", Angew. Chem. Int. Ed., 2008, 47, 3962-3965 Loges, Björn; Boddien, Albert; Junge, Henrik; Beller, Matthias (2008). "Controlled Generation of Hydrogen from Formic Acid Amine Adducts at Room Temperature and Application in H2/O2Fuel Cells". Angewandte Chemie International Edition. 47 (21): 3962–3965. doi:10.1002/anie.200705972. PMID 18457345.
  8. ^ a b Plummer, J. S.; Shun-Ichi, M.; Changjia, Z. "Dichlorotris(triphenylphosphine)ruthenium(II)", e-EROS Encyclopedia of Reagents for Organic Synthesis, 2010, John Wiley doi:10.1002/047084289X.rd137.pub2
  9. ^ Shu-Yu, Z.; Yong-Qiang, T.; Chun-An, F.; Yi-Jun, J.; Lei, S.; Ke, C.; En, Z.; "Cross-Coupling Reactions between alcohols through sp3 C-H Activation Catalyzed by a Ruthenium/Lewis Acid System" Chem. Eur. J., 2008, 14, 10201-10205 Zhang, Shu-Yu; Tu, Yong-Qiang; Fan, Chun-An; Jiang, Yi-Jun; Shi, Lei; Cao, Ke; Zhang, En (2008). "Cross-Coupling Reaction between Alcohols through sp3CH Activation Catalyzed by a Ruthenium/Lewis Acid System". Chemistry - A European Journal. 14 (33): 10201–10205. doi:10.1002/chem.200801317. PMID 18844197.
Ruthenium compounds
Ru(0)
Ru(I)
Ru(II)
Ru(II,III)
Ru(III)
Ru(IV)
Ru(V)
Ru(VI)
Ru(VII)
Ru(VIII)