Departament de Química Física i Inorgànica

Grup de Catálisi Homogènia i Síntesi Orgánica Estereoselectiva

2001 SGR 00316

Prof. Carmen ClaverOrganometál.lics i Catàlisi HomogéniaOMICH

Prof. Sergio CastillónSíntesis Orgánica

Departament de Química Análitica I Química Orgánica

Metallic nanoparticles as catalyst

Hydrogenation Hydrosilylation

Oxidation C-C coupling reactions

N

HO N Chem. Eur. J., 1997, 3, 1200Tetrahedron Lett. 1998, 39, 1941

“Probing Catalysis on the Nanoscale” Science & Technology, C&EN,September 27,2004

-Only one example in enantioselective catalyst

-High activity and selectivity (large specific surface)

-Activity in reactions where other catalysts are not active

-Efficient catalysts for several proceses

Metallic nanoparticles stabilized by organic ligands

Stabilisation and reproducibility.

Control of nanoparticles.

Uniformity in particle size, composition and morphology.

Systematic modification of the ligands: Effect on the properties of the nanoparticles.

Organometallic complexes as starting materials.

NANOCATALYST

Metal Nanoparticles Stabilized by Organic Ligands. Applications in Catalysis

Synthesis of nanoparticles of transition metals stabilized by organic ligands:

-Perfluorinated ligands.

Application in hydrogenation reaction.

-Chiral ligands with carbohydrate backbone.

Application C-C coupling reactions

-Synthesis of pyridine derivative perfluorinated ligands

-Metal nanoparticles stabilization of different transition metals

-Application as catalyst for arene hydrogenation in supercritic CO2

1. Synthesis of nanoparticles of transition metals stabilized by organic ligands.

Application in hydrogenation reaction

N

C8F17(CH2)4

N

C8F17(CH2)4

N

C8F17(CH2)4

N

C8F17(CH2)4

CH3-(CH2)15-NH2

Ph2P-(CH2)10-PPh2

PhP(-(CH2)2-PPh2)2

(a)

(b)

(HDA)

[Pd(C3H5)Cl]2

Ligand

3 bar H2; r.t.; 20h

THF or Toluene

[Pd/Ligand]0or

Ligands: CH3-(CH2)15-NH2

Ph2P-(CH2)10-PPh2

PhP(-(CH2)2-PPh2)2

Pd nanoparticles

Pd2(dba)3

Influence of Organic Ligands on the Stabilization Organometallic Palladium Nanoparticles. E. Ramirez, S. Jansat, K. Philippot, P. Lecante, M. Gomez, A.Masdeu, B. ChaudretJ. Organomet. Chem. 2004, (submitted)

-Design and synthesis of new carbohydrate ligands

-Synthesis and characterization of metal nanoparticles(Rh,Pd, Ru) with new chiral ligands

-Application in palladium catalyzed C-C bond reactions and other catalytic processes.

2. Metal nanoparticles stabilized by organic chiral ligands with carbohydrate

backbone.

OO

OOO

PO

O

P

O

O

OPh2P

OOPh2P

Ph2P

OOO

P

O

O

O

[Pd2(dba)3] [Pdx(dba)y(THF)zLw] dba-H2

3 bar H2

L, THF+

OO

OO

OPP

O

OO

O

tBu

But

But tBuBut

tBu

tBu

tBu

A case for Enantioselective Allylic Alkylation Catalyzed by Palladium NanoparticlesS.Jansat,M. Gomez, K. Philippot, G.Muller, E. Guiu, C. Claver, S. Castillón, B. ChaudretJ. Am. Chem. Soc., 2004, 126, 1593

Synthesis of palladium nanoparticles

L=

Ph Ph

OAcH2C(COOMe)2

Ph Ph

CH(COOMe)2

BSA, KOAcCH2Cl2, rt

[Pd/L*]

+

IIrac-I

Catalyst I / Pd/ L* Time (h)

Conv. (% )

ee I I (% )

ee I (% )

Coll.1 100/1/0.2 24 56 94 (S) 92 (S)

Coll.1 100/1/0.2 168 59 94 (S) 98 (S)

Mol.1 100/1/1.25 1.5 83 90 (S) 0

Catalysis. Reaction of allylic alkylation

-Homogeneous catalyst and nanocatalyst behave differently-First example of kinetic resolution with nanocatalyst

J. Am. Chem. Soc., 2004, 126, 1593

[Pd2(dba)3] [Pdx(dba)y(THF)zLw] dba-H2

3 bar H2

L, THF+

OO

OOO

P

P

O

O

O

O

tBuBut

But

tBuBut

But

But

tBu

X 100000

X 150000

Pd/L 1/0.1 R: 43 %

L=

Aurora RuizElena FernándezMontse DiéguezOscar PàmiesYolanda Díaz

Montse Gómez UBGuillermo Muller UBIsabelle Favier UB

Asymmetric CatalysisDr. Carmen ClaverDr. Sergio CastillónRosa AxetEster Guiu

Supercritic CO2

Dr. Anna M. Masdeu-Bultó Dr. Nuria Ruiz Marta Giménez Clara Tortosa

Dr. Bruno Chaudret LCCDr. Karine Philippot LCCDr. Susanna Jansat LCC

Financial SupportI+D- MCyT - Spain

DGR- Generalitat Catalunya

Acción Integrada-Picasso HF 2003

PICS Project- NANOMETCAT 2003

Collaborations

PICS Project- NANOMETCAT 2003

Universitat de Barcelona (Prof.G. Muller, Dra. M. Gómez)

Universitat Autónoma de Barcelona (Prof. M. Moreno)

ICIQ (Prof. M. Pericás)

Université de Montpellier (Prof. M.Corriu)

Université de Rennes ( Prof. A. Roucoux)

Université de Strasbourg (Prof. M. Pfeiffer)