Professional Documents
Culture Documents
University of Amsterdam
Definition of Catalysis and Catalyst
A B
CAT
Importance of Catalysis
• increasingly important in synthesis
• selectivity in production of fine chemicals
• clean processes, high atom economy (bulk processes)
• production of high-tech products / materials
• mild conditions (low energy consumption)
• environmentally friendly
O HO CN 1. H2SO4
+ HCN + NH4SO4
2. CH3OH COOCH3
active
By-product D Substrate A
catalyst
inactive
Reagent C Product B
catalyst
catalyst precursor
−
δ
AlCl3 AlCl3
O O
+
δ
−
δ
Frontier orbitals overlap
O
fast O
O
O O
O HOMO
O
O O LUMO
O
slow O
O
O O
O
Frontier orbital interactions for DA reactions
energy
LUMO
LUMO
LUMO LUMO LUMO
LUMO
HOMO
HOMO HOMO HOMO
HOMO
HOMO
Z X
+ H + CO2Me
CO2Me
CO2Me H
O AlCl3 H
O O
+ AlCl3
H H H
Frontier orbital energies and coefficients acrolein
O .51
LUMO 2.5
-.48
-.39 H H
.59 O .37
-.70
-.09
H -7
LUMO
.60
-.58
O
-.30
HOMO -14.5 .48 H
H
.58 O -.54
-.10
acrolein .65 H
-23.5 HOMO
.53
protonated
acrolein
Increased regioselectivity acid catalyzed DA
X H
O X O
-.39 H -.09 H
.59 .60
-.48
-.7
O
HO
without catalysis with catalysis
Catalysts
Diels Alder +
H2
100%
R R
R R
"Ru" 100%
+
"Pd"
26/28
br
-HBR (69 mass percent)
E factor
Advantages:
- understandable kinetics
- reproducibility
- relatively mild reaction conditions
- high selectivity
- easy modification of catalyst properties
- efficiency; all molecules are accessible
- mechanistic studies are relatively easy to perform (complex
identification by IR, NMR, UV etc.)
Disadvantages:
- water and oxygen sensitivity
- separation of catalyst and products often difficult
Development of Transition Metal Catalysts
Choice of metal
Steric effects
Electronic effects
Bite Angle
Secondary interactions
Substrate-metal
Substrate-ligand
Medium effects
level of sophistication
Rational catalyst design
alkene metathesis
R1 R2 R1 R2
R
+ + catalyst: LnM
4 3 R'
R R 4 3
R R
alkyne metathesis
R1 R2
R1 R2 catalyst: Mo(CO)6 + HO
+ + rate: 2 mol / mol / h
R4 R3 Mortreux (1974) Cl
4 3
R R
O t-Bu
rate: 300,000 mol / mol / h
"designed catalyst": t-Bu W O t-Bu
Schrock (1984)
O t-Bu
Selectivity in nickel catalyzed butadiene reactions
n
n n
''Ni''
OH
H2, kat
O O
OH
H2
Regioselectivity
CHO
CO / H2
CHO
Enantioselectivity
COOR' H2 COOR'
+ * + *
R NHCOR" [HRh L 2] R NHCOR"
99 % ee
Diastereoselectivity
R OH
*
R OH
* H2
R OH
*
Heterogeneous catalysis
Advantages:
- easy separation of catalyst and products
- low sensitivity to water and oxygen
- high temperature stability
- shape selectivity (zeolites)
Disadvantages:
- kinetics can be complex
- often high pressures and temperatures required
- catalyst poisoning by sulfur compounds
- sintering
- heat transfer
- surface chemistry; using a few atoms only
Immobilization of transition metal complexes
Supported Homogeneous Catalysts - Organic Polymers
- Dendrimers
- Inorganic Metal Oxides
Si
Si Ph2P Ph2P
Si Ph2P Ph2P
Si Me Si PPh2
Ph2P 2 Me2Si
SiMe2 Me2Si SiMe PPh2
Si Si Si Ph2P SiMe2 2PPh PPh2
Si Si Si 2
Si SiMe2 Me Si
Si Ph2P Si Si Si 2
SiMe2 PPh2
Si Me2
Si Si Si
Si Ph2P Me2 SiMe2 PPh2
Si Si
Si Si Si Ph2P Si Si Me 2SiMe
SiMe2 2 PPh
Si 2
SiMe2 Si
Si Si Ph2P Si
Si Me2Si SiMe2
Ph2P Si Si Si PPh
Si P Me2Si Si SiMe2 2
Si Fe Si Si PPh2
Si Me2Si
Si P Ph2P Me2 Me 2 Si
Si Si SiMe2 Si Si PPh2
Si Ph2P Me2Si Me2PPh2
Me2 Si Si
Si Si Si
Si Si Ph2P Me2Si Si Si
Si SiMe2 Si PPh2
Ph2P Ph2PMe2Si Me 2Si Me2 PPh2
Si Si Si PPh2 SiMe
Si SiMe2SiMeSiMe 2 PPh2
Si Si Ph2P 2 2
Si Si PPh2
Si PPh2 PPh2
Si PPh2
Si Si Si Si Si Si
Si
G.E. Oosterom et al. Chem. Commun.1999, 1119 D. de Groot et al. Chem. Commun.2000, 711
Dendritic transition metal catalysts: covalent approach
Core functionalization Periphery functionalization
CAT CAT CAT CAT
CAT CAT
CAT CAT
CAT CAT
CAT CAT
CAT
CAT
CAT
CAT
CAT CAT
CAT CAT
CAT CAT
Ph2P Me2N
OAc [Pd] Fe PPh2
Ph2P Me2N
Fe PPh2
N N N N Me2N SiMe2
Fe
SiMe2 SiMe2
Ph2P NMe2 PPh2
Fe
Ph2P Si Fe PPh2
SiMe2 SiMe2
Me2N
Ph2P NMe2
90 linear, trans linear, cis branched Fe
Me2
Si Si Si Si
PPh2
Si
Me2 Fe
80
Ph2P
Me2N PPh2
Me2Si NMe2
70
Ph2P Me2Si
Fe Si PPh2
Fe
60 Ph2P Me N
conversion / %
2
PPh2
Me2Si Me2Si
50 Fe
Me2Si
Fe
NMe2
Ph2P PPh2
40 Ph2P
NMe2 Fe
NMe2 PPh2
Ph2P PPh2
30 Me3Si
SiMe3 SiMe3
SiMe3
20 Me3Si
Me3Si
Me3Si SiMe3
Si Si
SiMe3
SiMe3 SiMe3
Me3Si
10 Me3Si
Si
Si
Si
Si
SiMe3
0
SiMe3
Me3Si
Si
Si P
0 2 4 6 8 10 Me3Si
Me3Si P
Fe SiMe3
Si SiMe3
Me3Si Si SiMe3
Si
Enzyme optimization:
• protein “engineering”
• molecular evolution
• enzyme “engineering”
Enzymes can be applied in:
• Water
• Organic solvents
• Supercritical CO2
• Ionic liquids
Energy profile of an enzyme catalyzed reaction
Enzymes give great rate enhancements
• Atom economic
• No or as little as possible waste
• decrease in solvent use
• Mild reaction conditions
• Catalytic use of reagents instead of stochiometrisch
• Non-toxic reagents,
• New sustainable starting materials