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

Related Research Articles

<span class="mw-page-title-main">Wilkinson's catalyst</span> Chemical compound

Wilkinson's catalyst (chlorido­tris(triphenylphosphine)­rhodium(I)) is a coordination complex of rhodium with the formula [RhCl(PPh3)], where 'Ph' denotes a phenyl group. It is a red-brown colored solid that is soluble in hydrocarbon solvents such as benzene, and more so in tetrahydrofuran or chlorinated solvents such as dichloromethane. The compound is widely used as a catalyst for hydrogenation of alkenes. It is named after chemist and Nobel laureate Sir Geoffrey Wilkinson, who first popularized its use.

<span class="mw-page-title-main">Vaska's complex</span> Chemical compound

Vaska's complex is the trivial name for the chemical compound trans-carbonylchlorobis(triphenylphosphine)iridium(I), which has the formula IrCl(CO)[P(C6H5)3]2. This square planar diamagnetic organometallic complex consists of a central iridium atom bound to two mutually trans triphenylphosphine ligands, carbon monoxide and a chloride ion. The complex was first reported by J. W. DiLuzio and Lauri Vaska in 1961. Vaska's complex can undergo oxidative addition and is notable for its ability to bind to O2 reversibly. It is a bright yellow crystalline solid.

<span class="mw-page-title-main">Triphenylphosphine</span> Chemical compound

Triphenylphosphine (IUPAC name: triphenylphosphane) is a common organophosphorus compound with the formula P(C6H5)3 and often abbreviated to PPh3 or Ph3P. It is versatile compound that is widely used as a reagent in organic synthesis and as a ligand for transition metal complexes, including ones that serve as catalysts in organometallic chemistry. PPh3 exists as relatively air stable, colorless crystals at room temperature. It dissolves in non-polar organic solvents such as benzene and diethyl ether.

<span class="mw-page-title-main">Rhodium(III) chloride</span> Chemical compound

Rhodium(III) chloride refers to inorganic compounds with the formula RhCl3(H2O)n, where n varies from 0 to 3. These are diamagnetic red-brown solids. The soluble trihydrated (n = 3) salt is the usual compound of commerce. It is widely used to prepare compounds used in homogeneous catalysis.

Martin Arthur Bennett FRS is an Australian inorganic chemist. He gained recognition for studies on the co-ordination chemistry of tertiary phosphines, olefins, and acetylenes, and the relationship of their behaviour to homogeneous catalysis.

<span class="mw-page-title-main">Organoiridium chemistry</span> Chemistry of organometallic compounds containing an iridium-carbon bond

Organoiridium chemistry is the chemistry of organometallic compounds containing an iridium-carbon chemical bond. Organoiridium compounds are relevant to many important processes including olefin hydrogenation and the industrial synthesis of acetic acid. They are also of great academic interest because of the diversity of the reactions and their relevance to the synthesis of fine chemicals.

<span class="mw-page-title-main">Chloro(cyclopentadienyl)bis(triphenylphosphine)ruthenium</span> Chemical compound

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.

<span class="mw-page-title-main">Dimethylphenylphosphine</span> Chemical compound

Dimethylphenylphosphine is an organophosphorus compound with a formula P(C6H5)(CH3)2. The phosphorus is connected to a phenyl group and two methyl groups, making it the simplest aromatic alkylphosphine. It is colorless air sensitive liquid. It is a member of series (CH3)3-n(C6H5)2P that also includes n = 0, n = 2, and n = 3 that are often employed as ligands in metal phosphine complexes.

<span class="mw-page-title-main">Bis(triphenylphosphine)palladium chloride</span> Chemical compound

Bis(triphenylphosphine)palladium chloride is a coordination compound of palladium containing two triphenylphosphine and two chloride ligands. It is a yellow solid that is soluble in some organic solvents. It is used for palladium-catalyzed coupling reactions, e.g. the Sonogashira–Hagihara reaction. The complex is square planar. Many analogous complexes are known with different phosphine ligands.

<span class="mw-page-title-main">Organorhodium chemistry</span> Field of study

Organorhodium chemistry is the chemistry of organometallic compounds containing a rhodium-carbon chemical bond, and the study of rhodium and rhodium compounds as catalysts in organic reactions.

In chemistry, metal-catalysed hydroboration is a reaction used in organic synthesis. It is one of several examples of homogeneous catalysis.

<span class="mw-page-title-main">Metal-phosphine complex</span>

A metal-phosphine complex is a coordination complex containing one or more phosphine ligands. Almost always, the phosphine is an organophosphine of the type R3P (R = alkyl, aryl). Metal phosphine complexes are useful in homogeneous catalysis. Prominent examples of metal phosphine complexes include Wilkinson's catalyst (Rh(PPh3)3Cl), Grubbs' catalyst, and tetrakis(triphenylphosphine)palladium(0).

<span class="mw-page-title-main">Tris(triphenylphosphine)rhodium carbonyl hydride</span> Chemical compound

Carbonyl hydrido tris(triphenylphosphine)rhodium(I) [Carbonyl(hydrido)tris(triphenylphosphane)rhodium(I)] is an organorhodium compound with the formula [RhH(CO)(PPh3)3] (Ph = C6H5). It is a yellow, benzene-soluble solid, which is used industrially for hydroformylation.

<span class="mw-page-title-main">Bis(triphenylphosphine)platinum chloride</span> Chemical compound

Bis(triphenylphosphine)platinum chloride is a metal phosphine complex with the formula PtCl2[P(C6H5)3]2. Cis- and trans isomers are known. The cis isomer is a white crystalline powder, while the trans isomer is yellow. Both isomers are square planar about the central platinum atom. The cis isomer is used primarily as a reagent for the synthesis of other platinum compounds.

<span class="mw-page-title-main">Dichlorobis(triphenylphosphine)nickel(II)</span> Chemical compound

Dichlorobis(triphenylphosphine)nickel(II) refers to a pair of metal phosphine complexes with the formula NiCl2[P(C6H5)3]2. The compound exists as two isomers, a paramagnetic dark blue solid and a diamagnetic red solid. These complexes function as catalysts for organic synthesis.

<span class="mw-page-title-main">Rhodium carbonyl chloride</span> Chemical compound

Rhodium carbonyl chloride is an organorhodium compound with the formula Rh2Cl2(CO)4. It is a red-brown volatile solid that is soluble in nonpolar organic solvents. It is a precursor to other rhodium carbonyl complexes, some of which are useful in homogeneous catalysis.

The Tsuji–Wilkinson decarbonylation reaction is a method for the decarbonylation of aldehydes and some acyl chlorides. The reaction name recognizes Jirō Tsuji, whose team first reported the use of Wilkinson's catalyst (RhCl(PPh3)3) for these reactions:

<span class="mw-page-title-main">Dicarbonyl(acetylacetonato)rhodium(I)</span> Chemical compound

Dicarbonyl(acetylacetonato)rhodium(I) is an organorhodium compound with the formula Rh(O2C5H7)(CO)2. The compound consists of two CO ligands and an acetylacetonate. It is a dark green solid that dissolves in acetone and benzene, giving yellow solutions. The compound is used as a precursor to homogeneous catalysts.

<span class="mw-page-title-main">Hydridotetrakis(triphenylphosphine)rhodium(I)</span> Chemical compound

Hydridotetrakis(triphenylphosphine)rhodium(I) is the coordination complex with the formula HRh[P(C6H5)3]4. It consists of a Rh(I) center complexed to four triphenylphosphine (PPh3) ligands and one hydride. The molecule has idealized C3v symmetry. The compound is a homogeneous catalyst for hydrogenation and related reactions. It is a yellow solid that dissolves in aromatic solvents.

<span class="mw-page-title-main">(Triphenylphosphine)iron tetracarbonyl</span> Chemical compound

(Triphenylphosphine)iron tetracarbonyl is a coordination complex with the formula Fe(CO)4(PPh3) (Ph = C6H5). An off-white solid, this complex is derived from iron pentacarbonyl by replacement of one carbonyl ligand by triphenylphosphine (PPh3).

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.