Dichlorotris(triphenylphosphine)ruthenium(II)

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Dichlorotris(triphenylphosphine)­ruthenium(II)
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
3D model (
JSmol
)
ChemSpider
ECHA InfoCard
 100.035.957 Edit this at Wikidata
EC Number
  • 239-569-7
  • 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 checkY
    Key: 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-2
    Key: WIWBLJMBLGWSIN-NUQVWONBAX
  • [Ru+2].[Cl-].[Cl-].c3c(P(c1ccccc1)c2ccccc2)cccc3.c1ccccc1P(c2ccccc2)c3ccccc3.c1ccccc1P(c2ccccc2)c3ccccc3
Properties
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
Monoclinic
C2h5-P21/c
a = 18.01 Å, b = 20.22 Å, c = 12.36 Å
α = 90°, β = 90.5°, γ = 90°
Octahedral
Hazards
GHS labelling:
GHS07: Exclamation mark
Warning
H302, H312, H332
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 [77 °F], 100 kPa).
checkY verify (what is checkY☒N ?)

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.[1][2]

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.[3] 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.[4] 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.[5]

Dichlorotris(triphenylphosphine)ruthenium(II) reacts with hydrogen in the presence of base to give the purple-colored monohydride HRuCl(PPh3)3.[6]

RuCl2(PPh3)3 + H2 + NEt3 → HRuCl(PPh3)3 + [HNEt3]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

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.[7] 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.[8]

Dichlorotris(triphenylphosphine)ruthenium(II) serves as a precatalyst for the

borrowing hydrogen").[8]

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.[9]

References

  1. doi:10.1016/0022-1902(66)80191-4
  2. doi:10.1002/9780470132432.ch40
  3. ISBN 0470860782
    .
  4. doi:10.1021/ic50028a002
    .
  5. PMID 20000700
    .
  6. ISBN 9780470132449
    .
  7. PMID 18457345
    .
  8. ^
    doi:10.1002/047084289X.rd137.pub2
  9. PMID 18844197
    .
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