Bis(triphenylphosphine)rhodium carbonyl chloride

Last updated
Bis(triphenylphosphine)rhodium carbonyl chloride
RhCl(CO)(PPh3)2.svg
Names
Other names
Bis(triphenylphosphine)rhodium(I) carbonyl chloride
Identifiers
3D model (JSmol)
EC Number
  • 237-712-8
PubChem CID
UNII
  • InChI=1S/2C18H15P.CO.ClH.Rh/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;;/h2*1-15H;;1H;/p-1
    Key: RMJBMLFXJWHQJH-UHFFFAOYSA-M
  • [C-]#[O+].C1=CC=C(C=C1)P(C2=CC=CC=C2)C3=CC=CC=C3.C1=CC=C(C=C1)P(C2=CC=CC=C2)C3=CC=CC=C3.[Cl-].[Rh]
Properties
RhCl(CO)[P(C6H5)3]2
Molar mass 690.94
Appearanceyellow solid
Hazards
GHS labelling:
GHS-pictogram-exclam.svg
Warning
H302, H312, H315, H319, H332
P261, P264, P270, P271, P273, 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).

Bis(triphenylphosphine)rhodium carbonyl chloride is the organorhodium complex with the formula [RhCl(CO)(PPh3)2]. This complex of rhodium(I) is a bright yellow, air-stable solid. It is the Rh analogue of Vaska's complex, the corresponding iridium complex. With regards to its structure, the complex is square planar with mutually trans triphenylphosphine (PPh3) ligands. The complex is a versatile homogeneous catalyst. [1]

Synthesis and reactions

Bis(triphenylphosphine)rhodium carbonyl chloride was originally prepared by treating Rh2Cl2(CO)4 with triphenylphosphine. [2] However, it is typically produced by the carbonylation of Wilkinson's catalyst: [3]

RhCl[P(C6H5)3]3 + CO → RhCl(CO)[P(C6H5)3]2 + P(C6H5)3

In homogeneous catalysis, this conversion is typically an undesirable side-reaction since [RhCl(CO)(PPh3)2] is a poor hydrogenation catalyst.

Bis(triphenylphosphine)rhodium carbonyl chloride is the precursor to tris(triphenylphosphine)rhodium carbonyl hydride, an important catalyst for hydroformylation.

RhCl(CO)[P(C6H5)3]2 + NaBH4 + P(C6H5)3 → RhH(CO)[P(C6H5)3]3 + NaCl + BH3

References

  1. Kikukawa, Kiyoshi; Westcott, Stephen A.; Croatt, Mitchell P.; Williams, Travis J.; Wender, Paul A.; Li, Yiming; Jiang, Xuefeng (2015). "Carbonyl(chloro)bis(triphenylphosphine)rhodium(I)". e-EROS Encyclopedia of Reagents for Organic Synthesis. pp. 1–22. doi:10.1002/047084289X.rc021.pub3. ISBN   978-0-470-84289-8.
  2. Vallarino, L. (1957). "Carbonyl Complexes of Rhodium. I. Complexes with Triarylphosphines, Triarylarsines, and Triarylstibines". Journal of the Chemical Society: 2287–92. doi:10.1039/jr9570002287.
  3. D. Evans; J. A. Osborn; G. Wilkinson (2007). "Trans -Carbonylchlorobis(Triphenyl-Phosphine)Rhodium and Related Complexes". trans-Carbonylchlorobis(Triphenylphosphine)Rhodium and Related Complexes. Inorganic Syntheses. Vol. 28. pp. 79–80. doi:10.1002/9780470132593.ch18. ISBN   978-0-470-13259-3.