Wilkinson's catalyst: Difference between revisions

{{short description|Chemical compound}}

{{Use dmy dates|date=June 2023}}

| Verifiedfields = changed

| Watchedfields = changed

| verifiedrevid = 434240157

| ImageSize =

| ImageSize3 =

| ImageName3 = Wilkinson's

| IUPACName = (''SP''-4)-chlorido­tris(triphenylphosphene)­rhodium

| OtherNames = Rhodium(I) tris(triphenylphosphene) chloride,<br />Wilkinson's catalyst,<br />Tris(triphenylphosphene)&shy;rhodium(I) chloride

|Section1={{Chembox Identifiers

| CASNo_Ref = {{cascite|correct|CAS}}

| UNII_Ref = {{fdacite|correct|FDA}}

| UNII = 0FV534BKEV

| PubChem = 84599

| StdInChI=1S/3C18H15P.ClH.Rh/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;1H;/p-1

| StdInChIKey = QBERHIJABFXGRZ-UHFFFAOYSA-M

| SMILES = Cl[Rh-3]([P+](c0ccccc0)(c0ccccc0)c0ccccc0)([P+](c0ccccc0)(c0ccccc0)c0ccccc0)[P+](c0ccccc0)(c0ccccc0)c0ccccc0

|Section2={{Chembox Properties

| SolubleOther = 20 g/L (CHCl₃, CH₂Cl₂), 2 g/L ([[benzene]], [[toluene]])<ref name=IS/>

| MeltingPtC = 245 to 250

| MeltingPt_notes =

|Section3={{Chembox Structure

| Coordination = square planar ''d''⁸ (diamagnetic; ''sp''²''d''-hybridized)

|Section7={{Chembox Hazards

| ExternalSDS =

| Hazards_ref=<ref>{{cite web |title=Chlorotris(triphenylphosphine)rhodium(I) |url=https://pubchem.ncbi.nlm.nih.gov/compound/84599#section=Safety-and-Hazards |website=pubchem.ncbi.nlm.nih.gov |language=en}}</ref>

| GHSPictograms = {{GHS07}}

| GHSSignalWord = Warning

| HPhrases = {{H-phrases|302|317|413}}

| PPhrases = {{P-phrases|261|264|270|272|273|280|301+312|302+352|330|333+313|363|501}}

|Section8={{Chembox Related

| OtherCompounds = [[triphenylphosphene]]<br />[[tetrakis(triphenylphosphene)palladium(0)|Pd(PPh₃)₄]]<br />[[Vaska's complex|IrCl(CO)[P(C₆H₅)₃]₂]]

'''Wilkinson's catalyst''' ('''chlorido&shy;tris(triphenylphosphine)&shy;rhodium(I)''') is a [[coordination complex]] of [[rhodium]] with the formula [RhCl(P(C6H5)₃], 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 [[alkene]]s. It is named after chemist and Nobel laureate Sir [[Geoffrey Wilkinson]], who first popularized its use.

Historically, Wilkinson's catalyst has been a paradigm in catalytic studies leading to several advances in the field such as the implementation of some of the first heteronuclear magnetic resonance studies for its structural elucidation in solution (³¹P),<ref>{{Cite journal|last1=Meakin|first1=P.|last2=Jesson|first2=J. P.|last3=Tolman|first3=C. A.|date=1 May 1972|title=Nature of chlorotris(triphenylphosphene)rhodium in solution and its reaction with hydrogen|journal=Journal of the American Chemical Society|volume=94|issue=9|pages=3240–3242|doi=10.1021/ja00764a061|issn=0002-7863}}</ref> [[Parahydrogen|parahydrogen-induced polarization spectroscopy]] to determine the nature of transient reactive species,<ref>{{Cite journal|last1=Duckett|first1=Simon B.|last2=Newell|first2=Connie L.|last3=Eisenberg|first3=Richard|title=Observation of New Intermediates in Hydrogenation Catalyzed by Wilkinson's Catalyst, RhCl(PPh3)3, Using Parahydrogen-Induced Polarization|journal=Journal of the American Chemical Society|volume=116|issue=23|pages=10548–10556|doi=10.1021/ja00102a023|year=1994}}</ref> or one of the first detailed kinetic investigation by Halpern to elucidate the mechanism.<ref>{{Cite journal|last=Halpern|first=Jack|date=1 January 1981|title=Mechanistic aspects of homogeneous catalytic hydrogenation and related processes|journal=Inorganica Chimica Acta|volume=50|pages=11–19|doi=10.1016/S0020-1693(00)83716-0}}</ref> Furthermore, the catalytic and organometallic studies on Wilkinson's catalyst also played a significant role on the subsequent development of cationic Rh- and Ru-based asymmetric hydrogenation transfer catalysts which set the foundations for modern asymmetric catalysis.<ref>{{Cite book|title=Organotransition metal chemistry- From bonding to Catalysis|last=Hartwig|first=John F.|publisher=University Science Books|year=2010|isbn=978-1-891389-53-5}}</ref>

According to single crystal X-ray diffraction the compound adopts a slightly distorted square planar structure.<ref>{{cite journal | last1 = Bennett | first1 = Michael J. | last2 = Donaldson | first2 = Peter B. | year = 1977 | title = Crystal and molecular structure of the orange and red allotropes of chlorotris(triphenylphosphine)rhodium(I) | journal = Inorganic Chemistry | volume = 16 | issue = 3| pages = 655–660 | doi = 10.1021/ic50169a033}}</ref>

In analyzing the bonding, it is a complex of Rh(I), a ''d''⁸ [[transition metal]] ion. From the perspective of the [[18-electron rule]], the four ligands each provides two electrons, for a total of 16-electrons. As such the compound is [[coordinatively unsaturated]], i.e. susceptible to binding substrates (alkenes and H₂). In contrast, IrCl(PPh₃)₃ undergoes cyclometallation to give HIrCl(PPh₃)₂(PPh₂C₆H₄), a coordinatively saturated Ir(III) complex that is not catalytically active.<ref>{{cite journal|doi=10.1021/ja01053a016|title=Chlorotris(triphenylphosphine)iridium(I) and Related Complexes. Oxidative Addition Reactions and Hydrogen Abstraction from the Coordinated Ligand|journal=Journal of the American Chemical Society|volume=91|issue=25|pages=6983–6994|year=1969|last1=Bennett|first1=M. A.|last2=Milner|first2=D. L.}}</ref>

== Synthesis ==

Wilkinson's catalyst is usually obtained by treating [[rhodium(III) chloride|rhodium(III) chloride hydrate]] with an excess of [[triphenylphosphine]] in refluxing ethanol.<ref name="Bennett">{{cite journal|last1=Bennett|first1= M. A.|last2= Longstaff|first2= P. A.|title= Complexes of Rhodium(I) with Triphenylphosphine. |journal=Chem. Ind. (London) |date=1965|volume=1965 |page=846}}</ref><ref name="Osborn">{{cite journal|last1=Osborn |first1=J. A. |last2=Jardine|first2=F. H. |last3=Young |first3=J. F. |author4=Geoffrey Wilkinson | title=The Preparation and Properties of Tris(triphenylphosphine)halogenorhodium(I) and Some Reactions Thereof Including Catalytic Homogeneous Hydrogenation of Olefins and Acetylenes and Their Derivatives| journal= [[Journal of the Chemical Society A]] | year = 1966|volume=1966 | pages = 1711–1732 | doi = 10.1039/J19660001711|author4-link=Geoffrey Wilkinson }}</ref><ref name=IS>{{cite book|chapter=Tris(triphenylphosphine)halorhodium(I) |first1= J. A. |last1=Osborn |first2=G. |last2=Wilkinson |title= Inorganic Syntheses |year= 1967 |volume=10 |page=67|doi=10.1002/9780470132418.ch12|isbn= 9780470132418 }}</ref> Triphenylphosphine serves as both a [[ligand]] and a two-electron reducing agent that oxidizes itself from oxidation state (III) to (V). In the synthesis, three equivalents of triphenylphosphine become ligands in the product, while the fourth reduces rhodium(III) to rhodium(I).

:RhCl₃(H₂O)₃ + 4 PPh₃ → RhCl(PPh₃)₃ + OPPh₃ + 2 HCl + 2 H₂O

Wilkinson's catalyst is best known for [[homogeneous catalyst|catalyzing]] the [[hydrogenation]] of olefins with molecular hydrogen.<ref>{{cite journal | author1 = Arthur Birch |first2= D. H. |last2=Williamson | journal = [[Organic Reactions]] | year = 1976 | volume = 24 | pages = 1 |title = Homogeneous Hydrogenation Catalysts in Organic Synthesis|author1-link= Arthur Birch (organic chemist) }}</ref><ref>{{cite book|first=B. R.|last= James |title=Homogeneous Hydrogenation |publisher=John Wiley & Sons |location=New York, NY|date=1973}}</ref> The mechanism of this reaction involves the initial dissociation of one or two triphenylphosphine ligands to give 14- or 12-electron complexes, respectively, followed by [[oxidative addition]] of H₂ to the metal. Subsequent π-complexation of alkene, migratory insertion (intramolecular hydride transfer or olefin insertion), and [[reductive elimination]] complete the formation of the [[alkane]] product, e.g.:<ref>{{cite web|url=https://www.ch.imperial.ac.uk/rzepa/blog/?p=26709|first=Henry|last=Rzepa|author-link=Henry Rzepa|website=Chemistry with a Twist|title=A mechanistic exploration of the Wilkinson hydrogenation catalyst. Part 1: Model templates|date=21 Jan 2024}}</ref>

[[File:WilkinsonCycleJMBrown.png|520px|center]]

In terms of their rates of hydrogenation, the degree of substitution on the olefin substrate is the key factor, since the rate-limiting step in the mechanism is the insertion into the olefin which is limited by the severe steric hindrance around the metal center. In practice, terminal and disubstituted alkenes are good substrates, but more hindered alkenes are slower to hydrogenate. The hydrogenation of alkynes is troublesome to control since alkynes tend to be reduced to alkanes, via intermediacy of the cis-alkene.<ref name=Burgess>Kevin Burgess, [[Wilfred van der Donk]], Chul-Ho Jun, Young Jun Park, "Chlorotris(triphenylphosphine)-rhodium(I)" Encyclopedia of Reagents for Organic Synthesis 2005 John Wiley & Sons. {{doi|10.1002/047084289X.rc162s.pub2}}</ref> Ethylene reacts with Wilkinson's catalyst to give RhCl(C₂H₄)(PPh₃)₂, but it is not a substrate for hydrogenation.<ref name=Osborn/>

===Related catalytic processes===

Wilkinson's catalyst also catalyzes many other hydrofunctionalization reactions including [[hydroacylation]], [[hydroboration]], and [[hydrosilylation]] of alkenes.<ref name=Burgess/> Hydroborations have been studied with [[catecholborane]] and [[pinacolborane]].<ref>{{cite journal | first1 = D. A. |last1=Evans |first2=G. C. |last2=Fu |first3=A. H. |last3=Hoveyda | title = Rhodium(I)-catalyzed hydroboration of olefins. The documentation of regio- and stereochemical control in cyclic and acyclic systems | year = 1988 | journal = [[J. Am. Chem. Soc.]] | volume = 110 | issue = 20 | pages = 6917–6918 | doi=10.1021/ja00228a068}}</ref> It is also active for the hydrosilylation of alkenes.<ref>{{cite journal | first1 = I. |last1=Ojima |first2=T. |last2=Kogure | journal = [[Tetrahedron Lett.]] | year = 1972 | volume = 13 | issue = 49 | pages = 5035–5038 | doi = 10.1016/S0040-4039(01)85162-5 | title = Selective reduction of α,β-unsaturated terpene carbonyl compounds using hydrosilane-rhodium(I) complex combinations}}</ref>

In the presence of strong base and hydrogen, Wilkinson's catalyst forms reactive Rh(I) species with superior catalytic activities on the hydrogenation of internal alkynes and functionalized tri-substituted alkenes.<ref>{{Cite journal|last1=Perea Buceta|first1=Jesus E.|last2=Fernández|first2=Israel|last3=Heikkinen|first3=Sami|last4=Axenov|first4=Kirill|last5=King|first5=Alistair W. T.|last6=Niemi|first6=Teemu|last7=Nieger|first7=Martin|last8=Leskelä|first8=Markku|last9=Repo|first9=Timo|date=23 November 2015|orig-year=2015|title=Diverting Hydrogenations with Wilkinson's Catalyst towards Highly Reactive Rhodium(I) Species|journal=Angewandte Chemie International Edition|language=en|volume=54|issue=48|pages=14321–14325|doi=10.1002/anie.201506216|pmid=26437764|issn=1521-3773}}</ref>

==Reactions==

RhCl(PPh₃)₃ reacts with [[carbon monoxide]] to give [[bis(triphenylphosphine)rhodium carbonyl chloride]], ''trans''-RhCl(CO)(PPh₃)₂. The same complex arises from the decarbonylation of [[aldehyde]]s:

Upon stirring in benzene solution, RhCl(PPh₃)₃ converts to the poorly soluble red-colored [[dimer (chemistry)|dimer]] [RhCl(PPh₃)₂]₂. This conversion further demonstrates the lability of the triphenylphosphine ligands.

In the presence of base, H₂, and additional triphenylphosphine, Wilkinson's complex converts to [[hydridotetrakis(triphenylphosphine)rhodium(I)]], HRh(PPh₃)₄. This 18e complex is also an active hydrogenation catalyst.<ref>Eduardo Peña-Cabrera "Hydridotetrakis(triphenylphosphine)rhodium" Encyclopedia of Reagents for Organic Synthesis, 2001, John Wiley & Sons. {{doi|10.1002/047084289X.rh030m}}</ref>

==See also==

*[[Rhodium-catalyzed hydrogenation]]

{{reflist|30em}}

{{Rhodium compounds}}

[[Category:Rhodium(I) compounds]]

[[Category:Triphenylphosphine complexes]]

[[Category:Coordination complexes]]

[[Category:Hydrogenation catalysts]]