Lab of Inorganic Chemistry Department of Chemistry, University of Ioannina, 45110 Ioannina, GREECE...

ADVANCED CATALYSIS: BIOMIMETIC OXIDATION CATALYSIS

Lab of Inorganic ChemistryDepartment of Chemistry,

University of Ioannina, 45110 Ioannina,

GREECE

Maria Louloudi

Oxidation of hydrocarbons

R1 C C R4R2 R3

oxidantcatalyst

R1 C C R4R2 R3

O

oxidantcatalyst R1

H2C C

HR2

OH

R1

H2C

H2C R2

oxidantcatalyst R1

H2C C R2

O

R1

H2C

H2C R2

?

OH

C-(CH3)3

C-(CH3)3 O2

C-(CH3)3

C-(CH3)3

OH

HO

C-(CH3)3

C-(CH3)3

O

OO2

catalyst catalyst

3,5-di-t-butylcatechol

DTBP2,4-di-t-butylphenol

DTBC3,5-di-t-butylquinone

DTBQ

? Phenol oxidation

DEMAND: EFFICIENT CATALYSTS FOR SELECTIVE OXIDATION OF HYDROCARBONS UNDER MILD CONDITIONS

Fine chemistry&

Industry

alkane oxidation (i.e., CH4 CH3OH,

steroid hydroxylation)

olefin oxidation

Oxidation-degradation of environmental pollutant (i.e., chlorophenol degradation)

New oxidation catalysts

ENERGY SAVING STRATEGIES

Catalytic reactions

Environmental friendly oxidants

Biomimetic Systems

Heterogeneous Catalysts

TYPES OF CATALYSTS - ENZYMES

• The “Gold Standard” of catalysts

• Highly specific

• Highly selective

• Highly efficient

• Catalyze very difficult reactions– N2 NH3

– CO2 + H2O C6H12O6

• Works better in a cell than in a 100000 l reactor

MANGANESE CATALASE

2 H2O2 2 H2O + O2

ÊáôáëÜóç

Core of the active site in Lactobacillus plantarum catalase.

Proposed mechanism of H2O2

decomposition by manganese catalase

Wu, A. J.; Penner-Hahn, J. E.; Pecoraro, V. L., Chem. Rev. 2004, 104, 903-938

MANGANESE CATALASE MIMICS

Structures of some of the ligands used for manganese catalase mimics

MANGANESE SUPEROXIDE DISMUTASE (MN-SOD)

The active center of Manganese Superoxide Dismutase

Superoxide dismutation mechanism for mononuclear Mn-SOD under physiological

conditions

Holm, R. H.; Kennepohl, P.; Solomon, E. I., Chem. Rev. 1996, 96, 2239-2314

MANGANESE SOD MIMICS

Structures of some of the ligands used in the synthesis of Mn complexes and manganesecomplexes for modeling of MnSOD

P-450

Active site of P-450 (X = H2O or OH–)Generally accepted mechanism of

Catalytic cycle of P-450

Mansuy, D.; Battioni, P., in Bioinorganic catalysis, Reedijk, J.; Bouwman, E. Ed; Second Edition, Marcel Deker, New York, 1999; pp 323-354

METHANE MONOOXYGENASE (MMO)CH4 + O2 + NADH + H+ CH3OH + H2O + NAD+

Active site structures of MMOox and MMOred

Wallar, B. J.; Lipscomb, J. D., Chem. Rev. 1996, 96, 2625-2657

Generally accepted mechanism of Catalytic cycle of MMO

BLEOMYCIN

Schematic representation of the structure of a part of iron bleomycin

Bleomycin is an effective antitumor drug. Its antitumor activity is believed to arisefrom its ability to activate O2 and to cleave DNA oxidatively in a double strand fashion.

The active intermediate is a low-spin FeIII–OOH species.

Que, L., Jr., in Bioinorganic Catalysis, Reedijk, J. Ed; First Edition, Marcel Dekker; Inc, New York, 1993; p 347

CATECHOL OXIDASE

B.Krebs et al Nat.Struct.Biol. 5 (1998) 1084B.Krebs et al J.Biol.Inorg.Chem. 4 (1999) 56J.Reedijk et al Chem.Soc.Rev. 35 (2006) 814

Active site structure

Generally accepted mechanism of Catechol oxidase

TYROSINASEO

OCu2+

Cu2+

NNN

N

O O

O

OCu2+

Cu2+

NNN

N

OHHO

2H+

O

OCu2+

Cu2+

NNN

N

O H+

Cu+Cu+

NNN

NO

OCu2+

Cu2+

NNN

N

O O

OH

Cu2+Cu2+

NNN

N

OOH++ H2O

monophenolase cycle

OHHO

2H+

3H+

OO

+ H2O

oxy-D

oxy-T

oxymet

O2

diphenolase cycle

deoxymet-D

OH

TYROSINASE MIMICS

Manganese, Iron and Copper in Biomimetic Oxidation Catalysis

MANGANESE, IRON AND COPPER IN BIOMIMETIC OXIDATION CATALYSIS

OXIDANTS

Molecular oxygen Ο2

Hydrogen peroxideΗ2Ο2

Η2Ο2

1. Mild oxidant

2. Cheap

3. Easily available

4. Environmental friendly (Η2Ο the only side

product)

5.High content of active oxygen (47%)

Metal–oxygen species

Mechanisms of Metal-catalyzed Oxidations: General Considerations

Heterolytic oxygen transfer

Peroxometal versus oxometal pathways

early transition metals (Mo, W, Re, V, Ti, Zr)

later transition metals (Ru,Os) and particularly first row elements (Cr, Mn, Fe)

MΝ(SALEN) CATALYSTS

The epoxidation reaction:

Structure of a typical Mn(salen) complex

Jacobsen’s Mn(salen) catalysts

Zhang, W.; Loebach, J. L.; Wilson, S. R.; Jacobsen, E. N., J. Am. Chem. Soc. 1990, 112, 2801-2803Zhang, W.; Jacobsen, E. N., J. Org. Chem. 1991, 56, 2296-2298

Jacobsen, E. N.; Zhang, W.; Muci, A. R.; Ecker, J. R.; Deng, L., J. Am. Chem. Soc. 1991, 113, 7063-7064

Berkessel’s imidazole tethered Mn(salen) complex

Berkessel, A.; Frauenkron, M.; Schwenkreis, T.; Steinmetz, A., J. Mol. Catal. A-Chem. 1997, 117, 339-346

Jacobsen’s PyO tethered Mn(salen) complex

Finney, N. S.; Pospisil, P. J.; Chang, S.; Palucki, M.; Konsler, R. G.; Hansen, K. B.; Jacobsen, E. N., Angew. Chem.-Int. Edit. Engl. 1997, 36, 1720-1723

Katsuki’s conformationally fixed Mn(salen) complex

Ito, Y. N.; Katsuki, T., Tetrahedron Lett. 1998, 39, 4325-4328

Mn-porphyrins

[Mn(Cl8tdcpp)]+, a “third generation” porphyrin complex

Meunier, B., Chem. Rev. 1992, 92, 1411-1456

Manganese-Me3tacn Complexes and Derivatives

Schematic structure of dinuclear manganese complexes that can be formed with the ligand Me3tacn ligand under different synthetic conditions

de Boer, J. W.; Brinksma, J.; Browne, W. R.; Meetsma, A.; Alsters, P. L.; Hage, R.; Feringa, B. L., J.Am. Chem. Soc. 2005, 127, 7990-7991

Other Mn Complexes

Schematic drawing of the ligands tptn and R,R-mcp

Brinksma, J.; Hage, R.; Kerschner, J.; Feringa, B. L., Chem. Commun. 2000, 537-538Murphy, A.; Dubois, G.; Stack, T. D. P., J. Am. Chem. Soc. 2003, 125, 5250-5251

Lane, B. S.; Vogt, M.; DeRose, V. J.; Burgess, K., J. Am. Chem. Soc. 2002, 124, 11946-11954

Formation of the peroxycarbonate complex (A) by the direct reaction ofperoxymonocarbonate and (B) by the reaction of a peroxy complex with hydrogencarbonate

Manganese Catalysts Containing Phenol-oxazoline Ligands

Hoogenraad, M.; Kooijman, H.; Spek, A. L.; Bouwman, E.; Haasnoot, J. G.; Reedijk, J., Eur. J. Inorg.Chem. 2002, 2897-2903

Manganese Catalysts Containing Acetylacetone-based Schiff Base Ligands

NNH

N

F3C

O

F3C

CF3

CF3

O

N N N N

CH3

CH3

O

H3C

H3C

O

OH

Ag. Stamatis, P. Doutsi, Ch. Vartzouma, K.C. Christoforidis, Y. Deligiannakis, M. Louloudi, J. Mol. Catal. A 297 (2009), 44Ch. Vartzouma, E. Evaggellou, Y. Sanakis, N. Hadjiliadis, M. Louloudi, J. Mol. Catal. A 263 (2007), 77

M. Louloudi, K. Mitopoulou, E. Evaggelou, Y. Deligiannakis, N. Hadjiliadis, J. Mol. Catal. A 198 (2003), 231

IRON COMPLEXES

Kim, C.; Dong, Y. H.; Que, L., J. Am. Chem. Soc. 1997, 119, 3635-3636Chen, K.; Costas, M.; Kim, J. H.; Tipton, A. K.; Que, L., J. Am. Chem. Soc. 2002, 124, 3026-3035

Ryu, J. Y.; Kim, J.; Costas, M.; Chen, K.; Nam, W.; Que, L., Chem. Commun. 2002, 1288-1289

Wada, A.; Ogo, S.; Nagatomo, S.; Kitagawa, T.; Watanabe, Y.; Jitsukawa, K.; Masuda, H., Inorg. Chem. 2002, 41, 616-618

Roelfes, G.; Lubben, M.; Leppard, S. W.; Schudde, E. P.; Hermant, R. M.; Hage, R.; Wilkinson, E. C.;Que, L.; Feringa, B. L., J. Mol.Catal. A-Chem. 1997, 117, 223-227.

Roelfes, G.; Lubben, M.; Hage, R.; Que, L.; Feringa, B. L., Chem. Eur. J. 2000, 6, 2152-2159

COPPER COMPLEXES

Oxidation of 3,5-di-t-butylcatechol (DTBC) to 3,5-di-t-butylquinone (DTBQ) with Ο2

D.Zois, Ch. Vartzouma, Y. Deligiannakis, N. Hadjiliadis, L. Casella, E. Monzani, M. Louloudi, J. Mol. Catal. A 261 (2007), 306-317E. Monzani, L. Quinti, A. Perotti, L. Casella, M. Gullotti, L. Randaccio,S. Geremia, G. Nardin, P. Faleschini, G. Tabbi, Inorg. Chem. 37

(1998) 553–562M. Gullotti, L. Santagostini, R. Pagliarin, A. Granata, L. Casella, J. Mol.Catal.: A Chem. 235 (2005) 271–284

(DTBC) oxidation to (DTBQ) with 71% yield

Catalytic cycle for the oxidation of DTBC by the dinuclear copper(II) complexes with O2

(DTBC) to (DTBQ) with 62% yield

M. Louloudi, K. Mitopoulou, E. Evaggelou, Y. Deligiannakis, N. Hadjiliadis, J. Mol. Catal. A 198 (2003) 231–240

HETEROGENEOUS vs HOMOGENEOUSCATALYSIS

ADVANTAGES: Easy recovery of the catalyst** Catalyst protection by the support

* Other benefits from the support: reactivity & selectivity

* No metal leaching --- environmental friendly procedure

* Catalyst reuse

DISADVANTAGES: * Reduced reactivity of the active catalyst centres

* H2O2 dismutation by the support

Examples of Different Inorganic Supports

ΤΑCN complex on silica surface

“Salen” catalyst into clay layers

“Salen” catalyst into MCM-41

Catalyst immobilized into zeolite

Schematic representation of supported metal complexes : heterogeneous catalysts

HETEROGENEOUSCATALYSTS

support

carbon chain

biomimetic ligand

M

metal ion

labile ligands

HYBDID ORGANIC-INORGANIC MATERIALS

silica gel

Si

O

O

Si

O

Si

O

L

OH

SiO2

L: ligand

Si

O

O

Si

O

Si

O

L

OH

SiO2M

Biomimetic complex

support

carbon chain

biomimetic ligand

M

metal ion

labile ligands

Synthetic strategy

The Active Catalyst

Si

O

O

Si

O

Si

O

L

OH

SiO2M

The same coordination environment & immobilization by covalent bond

MLn L'MLn-1 L'=L

MLn... MLn

encapsulation

Immobilization on a membrane

Rj + Pj / διαλύτης 2

MLn* / διαλύτης 1

Supported homogeneous catalysts

Silica modification via sol-gel procedure

MLn L'MLn-1 L'=L

The same coordination environment & immobilization by covalent bond

Possible evolution of a simple Q-type center during sol-gel reaction: 15 different species can be detected

Hydrolysis and condensation reactions are pH-dependant.

Development and condensation of silicon-centeres during the gel formation are also pH-dependent

HYBDID ORGANIC-INORGANIC MATERIALS

silica gel

Si

O

O

Si

O

Si

O

L

OH

SiO2

L: ligand

Si

O

O

Si

O

Si

O

L

OH

SiO2M

Biomimetic complex

The Active Catalyst

Synthetic strategy

Synthetic procedures of supported metal complexes used as heterogeneous catalysts

Preparation of an organically modified mesoporous silica via sol-gel methodology

Synthesis of silicon-precursors

1. Hydrosililation

2. Nucleophilic abstraction of halogens

3. Grignard-reactions

Synthesis of silicon-precursors

4. Condensation reactions

Synthetic procedures of supported metal complexes used as heterogeneous catalysts

Surface area versus loading of the active centers of the heterogeneous catalyst

MANGANESE, IRON AND COPPER IN HETEROGENEOUS BIOMIMETIC OXIDATION CATALYSIS

OXIDANTS

Molecular oxygen Ο2

Hydrogen peroxideΗ2Ο2

HETEROGENEOUS vs HOMOGENEOUSCATALYSIS

ADVANTAGES: Easy recovery of the catalyst** Catalyst protection by the support

* Other benefits from the support: reactivity & selectivity

* No metal leaching --- environmental friendly procedure

* Catalyst reuse

DISADVANTAGES: * Reduced reactivity of the active catalyst centres

* H2O2 dismutation by the support

Heterogeneous biomimetic oxidation catalysts

D.E.De Vos, S.Wildeman, B.F.Sels, P.J.Grobet, P.A.Jacobs, Angew. Chem. Int. Ed. Engl., 38, 1999, 980

Manganese-Me3tacn Catalysts

A.R.Silva, K.Wilson, J.H.Clark, C.Freire, Micr. Mesop. Mater., 2006, 128

Mn(salen) catalysts

Ch.Vartzouma, El.Evaggellou, Y.Sanakis, N.Hadjiliadis, M. Louloudi. Journal of Molecular Catalysis A: Chemical 263, 2007, 77

OOOH

SiO

N

N

N

N

CH3

R O

CH3

R O

R=CH3, G-AR=CF3, G-B

Ag.Stamatis, D.Giasafaki, M. Louloudi. Journal of Molecular Catalysis A: Chemical 2009, in press

Mn-Heterogeneous catalysts with Acetylacetone-based Schiff Bases

K.J.Ciuffi, H.C.Sacco, J.C.Biazzotto, E.A.Vidoto, O.R.Nascimento, O.A.Serra, Y.Iamamoto, J.Non-Cryst. Solids, 273, 2000, 100

Mn-porphyrins

E.R. Milaeva, O.A.lGerasimova, A.L. Maximov, E.A. Ivanova, E.A. Karachanov, N. Hadjiliadis, M. Louloudi, Catalysis Communications 8 (2007), 2069

A.Serafimidou, Ag.Stamatis, M.Louloudi. Cat. Comm. 9,2008, 35

D.Zois, Ch.Vartzouma, Y.Deligiannakis, N.Hadjiliadis,L.Casella, E. Monzani, M.Louloudi. Journal of Molecular Catalysis A: Chemical 261, 2007, 306

Mn-Heterogeneous catalysts with Imidazole-based biomimetic ligands

Heterogeneous Copper catalysts

M. Louloudi, K. Mitopoulou, E. Evaggelou, Y. Deligiannakis, N. Hadjiliadis, J. Mol. Catal. A 198 (2003), 231D.Zois, Ch. Vartzouma, Y. Deligiannakis, N. Hadjiliadis, L. Casella, E. Monzani, M. Louloudi, J. Mol. Catal. A 261 (2007),

306-317


C-(CH3)3

OH

C-(CH3)3

C-(CH3)3

O

C-(CH3)3

DTBC

OH O

O2

καταλύτης

DTBQ

0

10

20

30

40

50

60

70

80

90

100

% o

xidat

ion

DTBQ formation DTBC conversion

DTBQ2L

A

DTBQ2L

A.SiO

2

DTBQB

DTBQB.SiO

2

Table 2.

catalyst DTBQ formation (%) (TON)a

24h 48h

DTBC conversion (%) (TON)b

24h 48h Cu2(LA) 60.0

(400) 70.6 (471)

68.6 (457)

79.0 (527)

Cu2(LA).SiO2 69.0 (460)

92.6 (617)

90.0 (600)

96.0 (640)

Cu(LB) 23.0 (153)

37.1 (247)

24.5 (163)

38.2 (255)

Cu(LB).SiO2 49.7 (331)

78.1 (521)

61.4 (409)

88.7 (591)

aTON : moles of DTBQ formed per mole of catalyst bTON : moles of DTBC converted per mole of catalyst

Conditions: [3,5-di-t-butylcatechol]:[catalyst]:[base] = 200:0.3:3 ή 200:0.3:30


Tetrahedron 2006,62,9911-9918

Heterogeneous Iron catalysts

L2SiO2

CF3F3C

NO

F3C CF3

O N

N

OHO

OO

OH

0 20 40 60 80 1000

40

80

120

160

200

To

tal y

ield

(%

)

H2O2 μmol

FeL2Cl2

FeL2-( SiO3/2)n.zSiO2

0

10

20

30

40

50

60

70

80

90

100

To

tal y

ield

%

1st-use 2nd-use 3rd-use 4th-use

κυκλοεξενόνηκυκλοεξενόλη Εποξείδιο

G.Bilis, M.Louloudi et al. 2009, unpublished results


L1SiO2

N O

ON

NSi

HOO

OO

HO

0 20 40 60 80 100 1200

40

80

120

160

200

240

To

tal yie

ld (

%)

H2O2 (μmol)

FeL1Cl2

[FeL1-SiΟ3/2]m.zSiΟ2

0

10

20

30

40

50

60

70

80

90

tota

l yi

eld

(%

) %

1st-use 2nd-use 3rd-use 4th-use 5th-use

cyclohexenone

cyclohexenol

epoxide

G.Bilis, M.Louloudi et al. 2009, unpublished results


OxidationCatalysis

HeterogeneousCatalysts

Biomimetics

‘Green Chemistry’

CATALYSIS

HETEROGENEOUS CATALYSTS

Ο2 AND Η2Ο2 AS OXIDANTS

Advanced Catalysis: Biomimetic Oxidation Catalysis

Current Processes New Processes

stoichiometric catalytichigh temperature low temperature

homogeneous catalysts supported catalysts

energy saving

pollutant oxidants(Cr, Mn, Co salts, ClO-, peracids)

clean oxidants(O2, H2O2)

environmental friendly oxidants

Remove pollutants

Remove pollutants

phenols

New oxidations to be found

New oxidations to be found

for selective oxidation of hydrocarbons

fine chemical applications

University of Ioannina, GREECE

Thank you for your attention

Lab of Inorganic Chemistry Department of Chemistry, University of Ioannina, 45110 Ioannina, GREECE...

Documents

Transcript of Lab of Inorganic Chemistry Department of Chemistry, University of Ioannina, 45110 Ioannina, GREECE...