Homogeneous catalysis using supercritical fluids: Recent trends and systems studied

J. of Supercritical Fluids 38 (2006) 211–231

Homogeneous catalysis using supercritical fluids: Recent trends and systems studied Philip G. Jessop ∗ Department of Chemistry, Queen’s University, 90 Bader Lane, Kingston, Ont., Canada K7L 3N6 Received 18 August 2005; received in revised form 21 November 2005; accepted 21 November 2005 In memory of Aydin Akgerman.

Abstract Homogeneous catalysis in supercritical fluids has changed, since the mid-1990s, from a new and essentially unexplored field into a mature field with a considerable body of information. Most of the reported studies have taken place since the last comprehensive reviews in 1999. This review presents comprehensive tables of the systems which have been studied in supercritical fluids, along with a brief description of the recent trends in the area. © 2006 Elsevier B.V. All rights reserved. Keywords: Homogeneous catalysis; Supercritical fluids; Catalyst recycling; Asymmetric synthesis

1. Introduction to homogeneous catalysis in supercritical fluids Although supercritical fluids (SCFs) [1] have been known since 1822 [2,3] and homogeneous catalysis in SCFs has been known since Ipatiev’s experiments in 1913 [4], intensive research on homogeneous catalysis in SCFs by multiple research groups did not begin until the mid-1990s [5]. Growth of the field thereafter was extremely rapid. Reviews of the topic in 1999 were already hard-pressed to include every published reaction [6,7], and since then no review has attempted the feat. The

Abbreviations: acac, acetylacetonate; BArF, tetrakis(3,5-bis(trifluorome-

thyl)phenyl)borate; Bcat, ; Cl8 tpfpp, 2,3,7,8,12,13,17,18octachloro-5,10,15,20-tetrakis(pentafluorophenyl)porphyrin; cod, 1,5-cyclooctadiene; dabco, 1,4-diazabicyclo[2.2.2]octane; dba, (E,E)-dibenzylideneacetone; dcpe, 1,2-bis(dicyclohexylphosphino)ethane; DMAP, 4-dimethylaminopyridine; hfacac, 1,1,1,5,5,5-hexafluoroacetylacetonate; iPr, isopropyl; Karstedt’s catalyst, platinum–divinyltetramethyldisiloxane complex; MAO, methyl alumoxane; Rf , perfluoroalkyl, usually (CF2 )5 CF3 ; salen, ethylenebis(salicylimine) or derivatives thereof; sc, supercritical; SCF, supercritical fluid; tBu, tert-butyl; tpfpp, 5,10,15,20-tetrakis(pentafluorophenyl)porphyrin; tpp, 5,10,15,20-tetraphenylporphyrin ∗ Tel.: +1 613 533 3212; fax: +1 613 533 6669. E-mail address: [email protected]. 0896-8446/$ – see front matter © 2006 Elsevier B.V. All rights reserved. doi:10.1016/j.supflu.2005.11.025

present review will include a brief outline of the advantages of using SCFs, the current trends in the field, and tables of all of the reactions that have been studied so far [8]. Supercritical fluids, which are pure compounds or mixtures heated and pressurized beyond their critical points [9], have many advantages as solvents for homogeneous catalysis. A few of these advantages are true for all SCF solvents and essentially all reactions: mass transfer is very rapid, the solvent is completely miscible with gaseous reactants, and the solvent is easy to remove from the product. Some advantages are specific to supercritical CO2 (scCO2 ); it is nontoxic, nonflammable, nonhalogenated, nonpolluting [10], and does not cause cancer or other long-term health problems. Finally, some advantages are specific to certain combinations of SCFs and reactions. Polar SCFs such as fluoroform have variable dielectric constants, allowing reactions to be tuned [11,12]. Supercritical CO2 can act as both a solvent and an in situ protecting group [13,14]. Quite commonly, SCFs serve as both reactant and solvent; the homogeneously catalyzed polymerization of supercritical ethene is an industrialized example [3]. As a result of the advantages of SCFs, some but by no means all reactions have improved rates or selectivities when performed in SCFs rather than liquid solvents. Improved rates have been observed especially in reactions involving reagent gases [15–19]. Improvements or changes in reaction selectivity are harder to predict but have been observed in a number

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P.G. Jessop / J. of Supercritical Fluids 38 (2006) 211–231

Table 1 Homogeneously catalyzed reactions in supercritical or liquid CO2 a Catalystb

Reference

Sc(OTf)3

[42,43]

CF3 C6 H4 SO3 H

[113]

Ti(OPr)4 /BINOL

[114]

PdCl2 (PPh3 )2

[115]

Alkylation

CF3 (CF2 )7 SO3 H

[116]

Baylis–Hillman

Dabco

[117]

Carbonation

[NEt4 ]Br

[118]

Carbonation

[PMe(C2 H4 Rf)3 ]I

[66]

Carbonation

ReBr(CO)5

[119]

Carbonation

LiBr

[120]

Carbonation

Al(salen)(OR)

[121]

Type

Substrate

Product

Aldol

Aldol

Cyclohexanone

Aldol (Mukaiyama)

Alkoxycarbonylation

AllylBr, CO, EtOH

AllylCO2 Et

Carbonation

CO2 /MeOH

(MeO)2 CO

Bu2 Sn(OMe)2

[122]

Carbonation

CO2 /EtOH

(EtO)2 CO

Zn(L26 )OH

[123]

Carbonation

CO2 /MeC(OMe)3

(MeO)2 CO

Bu2 Sn(OMe)2

[124]

Carbonation

CO2 /Me2 C(OMe)2

(MeO)2 CO

Bu2 Sn(OMe)2

[125]

FeClL24

[126]

Carbonation

P.G. Jessop / J. of Supercritical Fluids 38 (2006) 211–231

213

Table 1 (Continued ) Type

Substrate

Product

Carbonation

Catalystb

Reference

DBU

[127,128]

Carbonylation

RNH2 /CO/ROH

PdCl2 , CuCl2

[129]

Carbonylation

RNH2 /CO

PdCl2 , CuCl2

[130]

Carbonylation

CH4 /CO/hν

CH3 CHO

RhCl(PMe3 )3

[104]

Carbonylation

C2 H6 /CO/hν

EtCHO

RhCl(CO)(PMe3 )2

[103]

PdCl2 , CuCl2

[131]

RhCl(CO)(PMe3 )2

[132,133]

Carbonylation

PdCl2 [P(OEt)3 ]2

[109,18]

Cascade

[Rh(cod)(EtDuPHOS)]+ OTf−

[134]

Carbonylation

Carbonylation

Benzene

PhCHO

Copolymerization

Polyether/polycarbonate

ZnO/HO2 CCH CHCO2 C2 H4 Rf

[135,136]

Copolymerization

Polyether/polycarbonate

CrCl(tpfpp)

[137]

Al(acac)3

[138]

Pd(O2 CF3 )2 /P(2-furyl)3

[39]

Pd(OAc)2 /Pt Bu2 (C6 H4 -2-Ph)

[139]

RuCl2 (PMe3 )(C6 H6 )

[140]

[NBu4 ]Br

[141]

Copolymerization

Coupling

2PhI

Ph–Ph

Coupling

Coupling

PhCCH/CO2 /HNR2

Coupling

R2 NH/RX/CO2

R2 NC(O)OR

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P.G. Jessop / J. of Supercritical Fluids 38 (2006) 211–231

Table 1 (Continued ) Type

Substrate

Cyclization

EtC CEt/CO2

Product

Cyclization

Catalystb

Reference

Ni(cod)2 /PMe3

[142,143]

CpCo(cod)

[143]

Cyclization

RC CR

PdCl2 /CuCl2

[144,130]

Cyclization

RC CR (R = CH2 Cl)

PdCl2 /CuCl2

[130]

Cyclization

RC CH

CpCo(CO)2

[145,146]

Cyclization

ArNCO

CpCo(Me)2 (PPh3 )

[30]

HN(O2 SCF3 )2

[147]

Rh2 (TBSP)4f

[12]

RhCl(PMe3 )3

[104]

Diels–Alder

AlCl3

[148]

Diels–Alder

Sc(O3 SCF3 )3

[24]

Diels–Alder

Sc(O3 SC8 F17 )3

[149]

Diels–Alder

Yb(ClO4 )3 or Sc(OTf)3 + i Pr-pybox

[150,151]

C 6 R3 H3

Cyclocondensation

Cyclopropanation

Styrene

Dehydrogenation

Cyclooctane/hν

Cyclooctene

P.G. Jessop / J. of Supercritical Fluids 38 (2006) 211–231

215

Table 1 (Continued ) Catalystb

Reference

Diels–Alder (aza)

Sc(O3 SC8 F17 )3

[149]

Diels–Alder (aza)

LiO3 SC8 F17

[152]

Dihydroxylation

Mo(CO)6

[153,154]

Epoxidation

Mo(CO)6

[155]

Epoxidation

Mo(CO)6

[143]

Epoxidation

(Me3 SiC5 H4 )MoO2 Cl

[57]

Epoxidation

VO(OiPr)3 or Ti(OiPr)4 and tartrate

[153,156]

Epoxidation

V(O)L3

[157]

Type

Substrate

Product

Esterification

RCO2 H/R OH

RCO2 R

CF3 C6 H4 SO3 H

[158,159,113]

Esterification

Ac2 O + ROH

ROAc

Yb{N(Rf )2 }3

[60]

Etherification

PdCl2 , CuCl2

[23,130]

Etherification

PdCl2 (MeCN)2

[130]

Friedel–Crafts

Ph3 COH/PhOMe

Ph3 CC6 H4 OMe

CF3 CO2 H

[160]

Glaser coupling

PhC CH

PhCCCCPh

PdCl2 and/or CuCl2

[144,130]

Heck

PhI/styrene

Pd(OAc)2 /PPh(C6 F5 )2

[161,70]

Heck

Pd(OAc)2 /L22

[162]

Heck

Pd(OAc)2 /L15

[163]

Heck

Pd(O2 CF3 )2 /L4

[38,37]

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P.G. Jessop / J. of Supercritical Fluids 38 (2006) 211–231

Table 1 (Continued ) Catalystb

Reference

Heck

Pd(OAc)2 /Pt Bu3

[34]

Heck

PdCl2 (L6 )2

[56]

Hydroaminomethylation

Rh(cod)(hfacac)/L18

[14]

Hydroboration

Rh(coe)2 (hfacac)/2L21

[164]

Type

Substrate

Product

Hydroformylation

CH2 CH2

RCHO

Rh(acac)(CO)2 /L17

[165]

Hydroformylation

CH2 CH2

RCHO

Ru3 (CO)12

[166]

Hydroformylation

CH2 CH2

RCHO

RhH(CO)L3 15

[167]

Hydroformylation

Propene

RCHO

Co2 (CO)8

[28,168,169]

Hydroformylation

Propene

RCHO

Co2 (CO)6 (L17 )2

[170]

Hydroformylation

1-Alkene

RCHO

Rh2 (OAc)4 /3PEt3

[33,35]

Hydroformylation

1-Alkene

RCHO

Rh(acac)(CO)2 /PPh2 (C6 F5 )

[171]

Hydroformylation

1-Alkene

RCHO

Rh(acac)(CO)2 /PEt3

[172]

Hydroformylation

1-Alkene

RCHO

Rh(acac)(CO)2 /10L16

[48]

Hydroformylation

1-Alkene

RCHO

Rh(acac)(CO)2 /10L20

[173]

Hydroformylation

1-Alkene

RCHO

[Rh(cod)(hfacac)] + PR3

[45,59]

Hydroformylation

1-Alkene

RCHO

RhClL3 17 or RhH(CO)L3 17

[174–178]

Hydroformylation

1-Alkene

RCHO

RhH(CO)L3 15

[179]

Hydroformylation

1-Alkene

RCHO

[RhCl(cod)]2 /L23

[54]

Hydroformylation

Diene

Dialdehyde

[Rh(acac)(CO)2 ]/4L15

[180,181]

Rh(acac)(CO)2 /10L16

[182,19]

Hydroformylation

P.G. Jessop / J. of Supercritical Fluids 38 (2006) 211–231

217

Table 1 (Continued ) Catalystb

Reference

Hydroformylation

Rh(acac)(CO)2 /8L25

[51,182]

Hydroformylation

Rh(acac)(L13 )

[183]

Hydroformylation

[Rh(cod)(EtDuPHOS)]+ BArF−

[184]

Hydroformylation

Rh(acac)(L13 ) or Rh(acac)(CO)2 /L14

[185,186]

Hydroformylation

RhCl(L23 )3

[55]

Hydroformylation

Rh(acac)(CO)2 /BINAPHOS

[187]

Type

Substrate

Product

Hydrogenation

Isoprene

Isopentenes

Rh(hfacac)(P–P)

[188]

Hydrogenation

1-Octene

Octane

RhCl(L23 )3

[53,52]

Hydrogenation

PhCH CHCHO

PhCH CHCH2 OH

RuCl3 /[(C6 F5 )2 PCH2 ]2 or PPh(C6 F5 )2

[189,190]

Hydrogenation

[Rh(cod)(EtDuPHOS]+ BArF−

[21]

Hydrogenation

[RuCl2 (C6 H6 )]2 /L9

[191]

Hydrogenation

Ru(OAc)2 (H8 BINAP)

[41]

Hydrogenation

Ru(OAc)2 (L7 )

[192]

Hydrogenation

Ru(OAc)2 (tolBINAP)

[95]

Hydrogenation

Ru(OAc)2 (MeOBIPHEP)

[147]

Hydrogenation

[Rh(cod)(L10 )]BArF

[193]

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P.G. Jessop / J. of Supercritical Fluids 38 (2006) 211–231

Table 1 (Continued ) Catalystb

Reference

Hydrogenation

[Rh(cod)2 ]BF4 /L11

[194]

Hydrogenation

RuCl2 (L8 )

[195]

Hydrogenation

RuCl2 (MeOBIPHEP)

[147]

Hydrogenation

[RuCl2 (C6 H6 )]2 /L9

[191]

Hydrogenation

[Ir(cod)L12 ]BArF

[17]

Type

Substrate

Product

Hydrogenation

Nitrile-butadiene rubber

Hydrogenated rubber

OsHCl(O2 )(CO)(PCy3 )2

[106]

Hydrogenation

CO2

HCO2 H

RuH2 (PMe3 )4

[15,16]

Hydrogenation

CO2 /NHR2

HC(O)NR2

RuCl2 (PMe3 )4

[196,16]

Hydrogenation

CO2 /NH2 Ph

HC(O)NHPh

RuCl2 (PMe3 )4

[197]

Hydrogenation

CO2 /NHR2

HC(O)NR2

RuCl2 (dppe)2

[198–200]

Hydrosilation

CO2 /HSiR3

HCO2 SiR3

RuH2 (PMe3 )4

[155]

Hydrosilation

Me(RO)2 SiH/H2 C CHRf

Me(RO)2 Si-CH2 CH2 Rf

Karstedt catalyst

[108]

[NiCl(allyl)]2 L1

[201]

Hydrovinylation

Isomerization

n-Hexane

Isomers

AlBr3

[20]

Isomerization

1-Hexene

2-Hexene

Fe3 (CO)12

[6]

Mannich

Yb(OTf)3

[42,43]

Mannich

LiO3 SC8 F17

[152]

Neber

dihydroquinidine

[202]

RuCl2 (CHCHCPh2 )(PCy3 )2

[13,25]

Olefin metathesis (RCM)

␣,␻-Dienes

Cycloalkene

P.G. Jessop / J. of Supercritical Fluids 38 (2006) 211–231

219

Table 1 (Continued ) Type

Substrate

Product

Catalystb

Reference

Oxidation

Cyclohexane

Cyclohexanone

FeCl(tpfpp)

[22]

Oxidation

Cyclohexane

Cyclohexanol

FeCl(tpp)

[203]

Oxidation

Cyclohexene

FeCl(tpfpp)

[204,205]

Oxidation

1-Alkene

PdCl2 , CuCl2

[130,206,207]

Oxidation

MnCl(salen)

[208]

Oxidation

Rh(dcpe)(hfacac)

[209]

Oxidation

PdCl(NO2 )(MeCN)2 , CuCl2

[210,130]

Oxidation

CuCl/phenanthroline

[211]

2-Alkanone

Oxidation

PhCH2 OH

PhCHO

(dppe)PtS2 {Ru(N)Me2 }2

[212]

Oxidation

PPh3 /O2

OPPh3

(Me3 SiC5 H4 )MoO2 Cl

[57]

Co2 (CO)8

[213]

Pauson–Khand

Polymerization

H2 C CH2

Pd(Me)(MeCN)(L2 )

[214]

Polymerization

PhC CH

Rh(nbd)(acac)/L18

[215–217]

Polymerization

Co(tpfpp)

[218]

Polymerization

EtAlCl2

[219]

Polymerization

Sn(O2 CCHEtBu)2

[220]

Polymerization

SnBu2 (OMe)2

[221]

220

P.G. Jessop / J. of Supercritical Fluids 38 (2006) 211–231

Table 1 (Continued ) Catalystb

Reference

Polymerization

DMAP

[222]

Polymerization

BF3 ·THF

[219]

Type

Substrate

Product

Polymerization

CH2 CH2

Polyethylene

[PdMe(MeCN)L2 ]+

[223,224]

Polymerization (ROMP)

Norbornene

Polynorbornene

[Ru(H2 O)6 ](OTs)2

[225,226]

Polymerization (ROMP)

Norbornene

Polynorbornene

Ru( CHPh)Cl2 (PCy3 )2

[25,227]

Polymerization

Isobutylene

Polymer

Polymerization

Isobutylene

Polymer

TiCl4 /BCl3

[229]

Polymerization

Dicarboxylic acid dichloride/diol

Polyester

Pyridine or NEt3

[230]

Reduction

CO2

CO

[Re(bpy)(CO)(P(OR)3 )]+ BArF−

[231]

Reduction

Cu(hfa)2

Cu

Pd(hfa)2

[232]

C8 F17 SO3 H or Sn(OTf)2

[233,234]

PhC CPh

PdCl2 L2 22 , CuI

[162]

Styrene

Pd(dba)2 /L15

[163]

Ar–Ph Ar–Ar Ar–Ph Ph–Ph Ph–Ph

PdCl2 (L6 )2 PdCl2 (L19 )2 PdCl2 (L6 )2 Pd(OAc)2 /Pt Bu3 PdCl2 L2 22

[56] [65] [56] [34] [162]

Ring-opening

Sonogashira

PhI/PhC CH

Stille

Stille Stille Suzuki Suzuki Suzuki

ArI/PhSnBu3 ArBr/Ar SnBu3 ArI/PhB(OH)2 PhI/PhB(OH)2 PhI/PhB(OH)2

[228]

a In at least some of the reactions presented in this table, the substrates, products or catalysts are incompletely soluble in the supercritical phase. Some of these may also have been performed at conditions below the mixture critical point. In papers in which more than one substrate or ligand was described, a single typical substrate and a typical ligand are shown in the table. b Numbered ligands are defined in the Schemes and in the list below. Ligand abbreviations are defined in Scheme 1 and in the list of abbreviations: L15 = P(C6 H3 -3,5-(CF3 )2 )3 ; L16 = P(C6 H4 -4-C6 F13 )3 ; L17 = P(C6 H4 -4-CF3 )3 ; L18 = P(C6 H4 -4-CH2 CH2 C6 F13 )3 ; L19 = P(C6 H4 -3-C8 F17 )3 ;

L20 = PPh2 (C6 H4 -4-CO2 Me); L21 = PCy2 (CH2 CH2 C6 F13 ); L22 = PPh(CH2 CH2 C6 F13 )2 ; L23 =

L25 =

; L26 =

.

; L24 =

;

P.G. Jessop / J. of Supercritical Fluids 38 (2006) 211–231

221

Table 2 Homogeneously catalyzed reactions in supercritical water Type

Substrate

Product

Catalyst

Reference

Cyclotrimerization

RC≡CH

C 6 H3 R3

CpCo(CO)2

[235]

NaOH

[236]

NaOH NiO or NaOH ZrO2 or NaOH H2 SO4

[237] [238] [239] [240–243]

Co(OAc)2 or MnCl2

[244,245]

NaOD

[246]

Pd(OAc)2

[247]

NaOH BF3 or Ni(BF4 )2 MnBr2 Mn2+ , Cu2+ Fe3+ , Cu2+ , etc.

[248] [249] [250] [251,252] [253]

Decarboxylation Dehydrogenation Dehydrogenation Dehydrogenation Dehydration

Refuse-derived fuel Polystyrene Lignin Alcohol

H2 H2 H2 Alkene

Dehydration Deuterationa

C6 H6

Heck

PhI/styrene

Hydrogenation Hydrolysis Oxidation Oxidative degradation Oxidative degradation

Coal extracts PhOPh C6 H4 Me2 ArOH ArNH2

a

C6 D6

Hydrogenated extracts PhOH C6 H4 (CO2 H)2 CO2 , H2 O, etc. CO2 , H2 O, etc.

In scD2 O.

of systems [20–23]. Other reactions have been found to have pressure-tunable selectivity [24,11,12,25]. The number of homogeneously catalyzed reactions that have been studied has increased enormously over the past decade. Before 1994, the only examples that had been studied were ethylene polymerization, olefin hydroformylation, Diels–Alder, isomerizations, degradative oxidation, and hydrogenation of coal extracts. Since then, one could be forgiven for thinking that almost every kind of reaction imaginable has been studied in at least one SCF (Tables 1–3). However, there are still many important reaction types that have not yet been tested in SCFs: carbonylation of alcohols or alkyl halides [26], carbonylation of nitroarenes to isocyanates, hydrocyanation of olefins, hydrogenation of CO, hydrogenation of arenes [27], chlorination of alkenes, reactions involving very strong bases (e.g. Grignards), and key enantioselective reactions such as isomerization and dihydroxylation. Some of these reactions have been avoided for good reasons. Hydrocyanations and the preparation of isocyanates involve solutions of toxic species in SCFs, a situation that can only be safely handled in very specialized facilities. Because the pressure of SCFs rises rapidly with increasing temperature, exothermic reactions such as the chlorination of alkenes would present a significant explosion risk if performed in SCFs; the industrial polymerization of scC2 H4 proves that this problem can, with appropriate engineering, be overcome. Finally, a lack of inertness of the SCFs is inhibiting study of reactions involving very strong bases. Fluoroform and CO2 are too acidic, but C2 H6 should be inert. Testing these missing reactions in SCFs may or may not be a useful exercise; whether they might have improved performance in supercritical fluids is not clear. The rates of the hydrocyanations and hydrogenations may improve if they are first order in the reagent gases.

Solvent effects on enantioselectivity are very difficult to predict. One can expect that these questions will be addressed in future studies. 2. Development of CO2 -soluble catalysts Homogeneous catalysts are notoriously insoluble in supercritical CO2 and similarly nonpolar SCFs such as ethane and fluoroform. Inorganic salts such as PdCl2 , organometallic complexes containing aromatic ligands, and charged catalysts of any type have very poor solubility in scCO2 . However, neutral catalysts or catalyst precursors that are either volatile (such as HCl or AlCl3 ) or contain CO2 -philic ligands have appreciable solubility. The types of ligands that are known to be sufficiently CO2 -philic or at least sufficiently nonpolar to be soluble or usable in scCO2 include carbonyl ligands [28–30], highly fluorinated ligands (such as highly fluorinated carboxylates or diketonates) [31,32], trialkylphosphines [15,16,33–35], and trialkylphosphites [36]. Ligands that tend not to make CO2 -soluble complexes are aromatic ligands such as the ubiquitous triphenylphosphine and chiral ligands such as those in Scheme 1, although strategies to make these soluble have been developed. There are four basic strategies: (a) switch to more soluble phosphines such as trialkylphosphines, despite their greater basicity, (b) switch to the more soluble but not particularly basic tri(2-furyl)phosphine (Scheme 2) [37–40], (c) add cosolvents or surfactants [41–43] to increase the solubility of the complex, and (d) add CO2 -philic substituents to the meta or para positions of the aromatic rings. For example, adding either fluorine atoms [44] or fluorinated chains [45] dramatically increases the solubility of the ligand. In order to avoid the electron-withdrawing effect of these sub-

222

P.G. Jessop / J. of Supercritical Fluids 38 (2006) 211–231

Table 3 Homogeneously catalyzed reactions in other SCFs or compressed gases Type

SCF

Substrate

Alkylation

CHF3

PhCHO/ZnEt2

Alkylation

CHF3

Carbonylation

C 2 H6

C2 H6 /hν

Carbonylation

C 3 H8

C3 H8

Copolymerization Copolymerization Copolymerization

C 2 H4 C 2 H4 C 2 H4

C2 H4 /1-alkene C2 H4 /diene C2 H4 /vinyl acetate

Cyclopropanation

CHF3

Styrene

Esterification

CH2 F2

RCO2 H/MeOH

Hydrogenation

CHF3

Oxidation

C 3 H8

C3 H8

Pauson–Khand

C 2 H4

RC CR, CO

Polymerization Polymerization Polymerization Polymerization Polymerization

C 2 H4 C 2 H4 C 2 H4 C 2 H4 C 2 H4

C2 H4 C2 H4 C2 H4 C2 H4 C2 H4

Polymerization

NH3

Transesterification

MeOH

RCO2 Et

stituents, one can insert one, two or three methylene spacers between the aromatic ring and the perfluoroalkyl chain. This is done not only for phosphine ligands [45] but also for phosphite [46] and cyclopentadienyl [47] ligands as well. In some cases the spacer was not added because the electron-withdrawing effect of the fluorous tail was beneficial to catalysis [48]. A range of fluorinated chiral phosphine ligands is shown in Scheme 3 while nonchiral ligands are listed as a footnote to Table 1. Attachment of a highly fluorinated polymer instead of a small fluoroalkyl chain is also quite effective [49–55]. Nonfluorinated substituents which enhance the solubility of triarlyphosphines are extremely rare (Scheme 2): a peracetylated sugar group is known to be somewhat effective [40]. A silicone polymer enhances the solubility of an alkyldiarylphosphine [56]. Addition of trimethylsilyl groups to cyclopentadienyl ligands has been shown to increase the solubility of complexes in CO2 [57].

Product

Catalyst

Reference

An aminoalcohol

[254,255]

CF3 (CF2 )7 SO3 H

[116]

RhCl(CO)(PMe3 )2

[103]

RhCl(CO)(PMe3 )2

[132]

Metallocenes/MAO Metallocenes/MAO t-Butylperpivalate/AlEt3

[256,257] [258,259] [260]

Rh2 (TBSP)4

[11,12]

CF3 C6 H4 SO3 H

[113]

Ru(OAc)2 (H8 BINAP)

[261,262]

FeCl(Cl8 tpfpp)

[263]

Co2 (CO)8

[264]

Oligomers Polyethylene Polyethylene Polyethylene Polyethylene

AlCl3 Metallocenes/MAO A Nd metallocene A zirconocene/MAO t-Butylperpivalate/AlEt3

[4] [265–269] [270] [271] [272]

[HGaNH]n

NH3

[273]

RCO2 Me

BF3

[274]

EtCHO

Copolymer Copolymer Copolymer

RCO2 Me

n,i-PrOH

Finally, it should be noted that even cationic catalyst precursors can be used in scCO2 if the anion is carefully chosen so as to optimize the solubility. Anions that are preferred are those that are large and highly fluorinated such as “BArF” (tetrakis(3,5bis(trifluoromethyl)phenyl)borate) [21]. Use of perfluoroalkanoate anions is also effective [58], but they have a higher tendency to coordinate to the metal centre and may actually have been coordinated in the example published. 3. Recycling of homogeneous catalysts using supercritical fluids The creativity of SCF researchers has resulted in the development of a wide variety of ways in which homogeneous catalysts can be recovered after a reaction and then reused.

P.G. Jessop / J. of Supercritical Fluids 38 (2006) 211–231

223

Scheme 1. Some nonfluorinated ligands that have been tested in scCO2 .

(a) By lowering the pressure to precipitate the catalyst from the SCF (CESS method) [59,17]. (b) By cooling the SCF until the catalyst precipitates [60]. (c) By using catalysts that are essentially insoluble in the SCF [61] (especially if the reaction is performed in the absence of CO2 but the separation is performed with scCO2 ) [62]. (d) By using a membrane which will allow the SCF and the products to pass through but not the catalyst molecules [63,64].

(e) By releasing the scCO2 entirely and extracting the fluorinated catalyst from the organic product using a fluorous solvent [65]. (f) By auto-separation of a product which is insoluble in the SCF [66]. (g) By dissolution of the catalyst in a liquid that is immiscible with the SCF (i.e. biphasic catalysis) [67]. While the reaction could take place in either the liquid or the SCF,

Scheme 2. Nonfluorinated CO2 -soluble aromatic phosphines [40,56].

224

P.G. Jessop / J. of Supercritical Fluids 38 (2006) 211–231

Scheme 3. Fluorinated chiral ligands that have been tested in scCO2 . Rf = (CF2 )5 CF3 .

the product and the catalyst partition preferentially into the SCF and the liquid phases, respectively. The liquid can be water [68–70], ionic liquid [71–77], a liquid polymer [78], or ethylene glycol [70]. Emulsification of the biphasic system during catalysis can help reaction rates [69]. (h) By using an inverted biphasic system in which the catalyst preferentially partitions into a SCF while the product preferentially partitions into a liquid that is immiscible with the SCF [79–82]. (i) By attaching the catalyst to a solid polymer or other solid support [83–88]. 4. New trends New areas of research in the field include many variations on the theme; new phases in which to perform reactions, other

types of catalysis not previously evaluated in SCFs, and the development of new materials by catalysis in SCFs. New phases which have been tested as media for homogeneous catalysis include expanded liquids and induced melts. Expanded liquids are organic liquids into which large quantities of gas have been dissolved. As a result, the volume of the liquid phase increases greatly [89] (sometimes well over 10fold) and other physical properties change as well, including viscosity, surface tension, diffusion rates, solubility of reagent gases, solubility of catalysts and substrates, density, polarity, and melting point. Rate constants and equilibrium constants for reactions dissolved in the organic liquid also change as a result of the expansion of the liquid. The gas is typically CO2 but could be any gas relatively near its critical temperature. While most organic liquids undergo this expansion when exposed to CO2 (over 30 bar), a few such as diols, triols, liquid polymers and

P.G. Jessop / J. of Supercritical Fluids 38 (2006) 211–231

ionic liquids do not expand significantly. Nevertheless, the physical properties of the liquid polymers and ionic liquids do change with increasing CO2 pressure. Compared to supercritical fluids, expanded liquids have many of the same advantages (high diffusion rates for example) without the cost of the higher pressure required by pure SCFs. Homogeneously catalyzed reactions in expanded liquids [90–94] and even expanded ionic liquids [95] have been reported. CO2 dissolved into an alcohol in this way can act as a catalyst precursor for acid-catalyzed reactions [96–98]. Induced melts are liquids or softened-solid phases prepared by the addition of CO2 pressure over an organic solid. The pressure of CO2 (or any other gas near its critical pressure) causes the melting point of the solid to decrease such that it melts or at least softens. Solventless reactions of solids, which are typically very slow for obvious mass-transfer reasons, can be accelerated by the addition of pressurized CO2 in this manner, without the pressure being high enough for the CO2 to act as a compressed gas solvent [99]. The principal disadvantage of this technique is that the melting point depression is usually limited to a 20 or 30 K drop, although for some compounds the melting point depression can be significantly greater. Classes of homogeneous catalysis that have received less attention in SCF studies include phase transfer catalysis, photocatalysis, and electrocatalysis. Early efforts in phase transfer catalysis were reviewed in 1999 [100] and there have been more examples since [101,102]. There have been very few examples of photocatalysis [103,104]. Homogeneous electrocatalysis in SCFs seems to be entirely unexplored. Modification of polymeric materials by homogeneous catalysis in SCFs has also been reported. In the case of an insoluble polymer, the SCF can serve to swell the polymer and transport the SCF-soluble catalyst into the swollen or porous solid polymer [105,106]. This technique had been used earlier with free-radical initiated polymerization in scCO2 inside a polymer [107]. Homogeneous catalysis for the modification of SCFsoluble polymers is also possible [108]. 5. Conclusions Researchers have evaluated a large number of homogeneously catalyzed reactions in supercritical fluids during the past dozen years. In contrast, the tables include only seven entries published before 1993. Of the 154 systems studied in scCO2 , fully 42 concern hydrogenation and hydroformylation, two reactions which have been constantly emphasised over this time period. Although some major reaction types have not yet been evaluated in SCFs, researchers have quite reasonably moved towards development of related methods, including many new protocols for catalyst recycling or immobilization. References [1] P.G. Jessop, W. Leitner, Chemical Synthesis using Supercritical Fluids, VCH/Wiley, Weinheim, 1999. [2] C.C. de LaTour, sur les effets qu’on obtient par l’application simultan´ee de la chaleur et de la compression a` certains liquides, Ann. Chim. Phys. 21 (1822) 127–132, 178–182.

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