Wilkinson's Catalyst Mechanism and Uses

2/1/2016
WILKINSON'SCATALYST|HYDROGENATION|MECHANISM|ADICHEMISTRY
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ORGANOMETALLICCHEMISTRY
WILKINSON'SCATALYST
RhCl(PPh 3)3Chlorotris(triphenylphosphine)rhodium(I),isknownasWilkinsons
catalyst.Itisusedasahomogeneoushydrogenationcatalyst.Itisasquareplanar
16electroncomplex.TheoxidationstateofRhodiuminitis+1.
Preparation:
*ItcanbepreparedbyreactingRhCl3.3H2OwithexcessPPh 3inEtOH.
Uses:
Itisusedintheselectivehydrogenationofalkenesandalkyneswithoutaffecting
thefunctionalgroupslike:C=O,CN,NO2,Aryl,CO2Retc.
http://www.adichemistry.com/inorganic/organometallic/catalysis/wilkinson/wilkinsonscatalyst.html
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MECHANISMOFHYDROGENATIONCATALYTICCYCLE
Indeed,Wilkinson'scatalystisaprecatalystthatisconvertedtoanactiveform
bylosingonetriphenylphosphineligandbeforeenteringthecatalyticcycle.Usually,
thesolventmoleculefillsthevacantsite.
Initially, the catalyst activates the molecular dihydrogen by oxidative addition

mechanismtogivea18valenceelectrondihydridocomplex.Theoxidationstateof
Rh is increased to +3. Thus formed dihydrido complex binds to the olefin in the
nextstepwiththeconcomitantlossofsolventorPPh 3ligand.Sincetheactivation
ofdihydrogenoccursbeforeadditionofolefin,thispathisreferredtoasdihydride
path.
Nowoneofthehydrogenundergoesmigratoryinsertionatthedoublebond.This
isaslowstepi.e.,RateDeterminingStep(RDS).
Immediatelyandfinally,thealkaneisreleasedrapidlybyanirreversiblereductive
elimination step that completes the catalytic cycle. The oxidation state of Rh is
decreasedto+1andthecatalystisregenerated.
However, other paths and intermediates are also possible under the given
reactionconditions(seebelow).
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Abovemechanismissupportedbyfollowingobservations.
* The rate of reaction decreases when excess of PPh 3 is added indicating the
initialdissociationofoneofthePPh 3ligandbeforedihydrogenactivation.
* It is observed that strong acids like ethylene act as poisons by binding

stronglywiththeelectronrichRhmetalcenterandinhibithydrogenation.
Though ethylene cannot be hydrogenated in presence of Wilkinson's catalyst

under normal conditions, hydrogen transfer can be achieved with preformed
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dihydridocomplex.
The rates of hydrogenations decrease with increase in the alkyl group

substitution on double bond mirroring their relative binding affinities to the metal
center.Itisalsopartlyduetostericfactors.
Therefore,forasuccessfulhydrogenation,oxidativeadditionofdihydrogenprior
tothebindingofolefiniscrucial.
*ThereisminimalscramblingofH/Dintheproduct,whenanequimolarmixture
ofH2andD2areused.
This indicates the formation of dihydrido complex that transfers both of its
hydridoligandstotheolefinandthatthefinalreductiveeliminationstepisveryfast
andirreversible.
SELECTIVEHYDROGENATIONBYWILKINSON'SCATALYST
Wilkinson'scatalystcanbeusedtoachieveselectivehydrogenations.
* Less substituted and sterically less hindered double bonds are selectively
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hydrogenated.
* Exocyclic double bonds are selectively hydrogenated over endocyclic double

bonds.
*Cisalkenesarereducedrapidlythantransalkenes.
*Isolateddoublebondsarerapidlyhydrogenatedoverconjugateddienes.
* Terminal alkynes are hydrogenated more rapidly than terminal alkenes. The
selectivitycanbeenhancedbyusingacidicalcoholiccosolvents.
* Functional groups like C=O, C=N, NO2, Aryl, CO2R etc., are unaffected. The
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compatibility of Wilkinson's catalyst with polar multiple bonds indicates the metal
hydridebondisprimarilycovalentincharacter.
Note: But sterically unhindered aldehyde groups are susceptible to

decarbonylation,alsorenderingthecatalystineffective.
* Unsaturated substrates containing polar functionality are hydrogenated more

rapidly.Itmaybeduetoeasycoordinationofolefintothecatalystthatisassisted
bypolarfunctionalgroup.
STEREOCHEMISTRYOFWILKINSON'SHYDROGENATION
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STEREOCHEMISTRYOFWILKINSON'SHYDROGENATION
Hydrogenations catalyzed by Wilkinson's catalyst involve stereospecific syn
hydrometallation of the multiple bond followed by stereospecific reductive
elimination. Hence the hydrogenation of olefins or alkynes result in syn addition
products.
E.g. Hydrogenation of Maleic acid or Fumaric acid with D2 in presence of

Wilkinson'scatalystisdiastereoselective.HydrogenationofMaleicacidwithD2give
mesocompoundexclusively.
Whereas,withfumaricacid,aracemicmixtureisformed.
HenceWilkinson'shydrogenationisbothstereospecificaswellasstereoselective.
It is stereospecific in the sense that one stereo isomer gives only one stereo
isomerasexclusiveproduct.Itisduetostereospecificnatureofthemechanism.
However it is also stereoselective since only one diastereomer is formed

selectivelyasmajorproduct.Thisisalsopartlyduetoothermechanismsoperating
underreactionconditions.
Itisobservedthathydrogenationofalkynesgivecisalkenesasmajorproducts.
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ThediastereoselectivityofWilkinson'shydrogenationisevidentintheformation
ofendoproductasmajoronewiththefollowingbicyclicsystem.Thecatalystbinds
tothedoublebondfromtheleasthinderedexofaceofthebicyclicsystemthatis
followedbysynadditionoftwohydrogenatoms.
DECARBONYLATIONWITHWILKINSON'SCATALYST
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DECARBONYLATIONWITHWILKINSON'SCATALYST
SinceRh(II)isalowvalentandcoordinatelyunsaturatedmetalandcanbindto
COstrongly,theWilkinson'scatalystcanbeusedtobringaboutdecarbonylationof
aldehydesthroughoxidativeadditionroute.
Mechanism:
The process is noncatalytic, since the catalyst cannot be regenerated. The

complex, chlorocarbonylbis(triphenylphosphine) rhodium, formed during the
reaction is quite stable and it is not possible to dissociate CO ligand at mild
temperatures. Hence stoichiometric amounts of the complex is required to carry
outthisconversion.
However, it is possible to make decarbonylation reaction catalytic with

Wilkinson'scatalystbyemployingDiPhenylPhosphorylAzide(DPPA),whichremoves
CO ligand from chlorocarbonylbis(triphenylphosphine) rhodium to regenerate the
activeformofcatalyst.
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Author:AdityavardhanVutturiGoogle+profile
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Wilkinson's Catalyst Mechanism and Uses

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Initially, the catalyst activates the molecular dihydrogen by oxidative addition

* It is observed that strong acids like ethylene act as poisons by binding

Though ethylene cannot be hydrogenated in presence of Wilkinson's catalyst

The rates of hydrogenations decrease with increase in the alkyl group

* Exocyclic double bonds are selectively hydrogenated over endocyclic double

Note: But sterically unhindered aldehyde groups are susceptible to

* Unsaturated substrates containing polar functionality are hydrogenated more

E.g. Hydrogenation of Maleic acid or Fumaric acid with D2 in presence of

However it is also stereoselective since only one diastereomer is formed

The process is noncatalytic, since the catalyst cannot be regenerated. The

However, it is possible to make decarbonylation reaction catalytic with

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