2012 Katalisis Oganologam
2012 Katalisis Oganologam
2012 Katalisis Oganologam
KATALIS HOMOGEN
Catalytic Deuteration
Hydroformylation
Monsanto Acetic Acid Process
Wacker (SMIDT) Process
Hydrogenation by Wilkinsons Catalyst
Olefin Metathesis
KATALIS HETEROGEN
Ziegler-Natta Polymerization
Catalyzed rxn
proceeding through
an intermediate
Ea
Ea
catalyzed
G
Reactants
G
Products
Reaction Coordinate
the catalyst and substrates for the reaction are in the same phase in the
homogeneous, but not in the heterogeneous type, where catalysis takes
place at the surface of a solid catalyst.
Advantages/Disadvantages of Homogeneous Catalysts Relative to
Heterogeneous Catalysts
Good homogeneous catalysts are:
Good
Green Chemistry!!!
Bad
+ H2
Polymer
Polymer
Catalyst
Homo/Hetero
% Yield
RhCl(PPh3)3
homo
100
Ni(OAc)2 + NaBH4
hetero
--
[Rh(nbd)(PR3)2]+
homo
90
Pd/C
hetero
--
[Ir(cod){P(i-pr)3}(py)]+
homo
100
sampling from
autoclave causes
pressure glitches
2,000
1,800
4.5
Uptake curve
1,600
4
1,400
Equiv
Aldehyde
Prod
3.5
-1
1,200
1,000
Ln plot
800
2.5
600
Initial TOF
8 TO/min
476 TO/hr
400
2
1.5
200
0
0
10
Time (hours)
15
20
Ln P)
Turnover Number (TON) -- the absolute number of passes through the catalytic
cycle before the catalyst becomes deactivated.
Academic chemists sometimes report only the turnover number when the catalyst is
very slow (they dont want to be embarassed by reporting a very low TOF), or
decomposes quite rapidly.
Industrial chemists are interested in both TON and TOF. A large TON (e.g., 106 1010) indicates a stable, very long-lived catalyst. TON is defined as the amount of
reactant (moles) divided by the amount of catalyst (moles) times the % yield of
product.
Authors often report mole % of catalyst used. This refers to the fraction of catalyst
used relative to the amount of limiting reactant present.
10 mole % catalyst
5 mole % catalyst
1 mole % catalyst
0.1 mole % catalyst
0.01 mole % catalyst
=
10 turnovers
=
20 turnovers
=
100 turnovers
= 1000 turnovers
= 10,000 turnovers
Process
Petroleum Refining
Cracking
Reforming
Hydrocracking
Hydrodesulfurization
Hydrodenitrogenation
Chemical Manufacturing
Natural Gas desulfurization
Hydrogenations
Methanol synthesis
Dehydrogenation
Oxidations
Polymerizations
Hydroformylation
Typical Catalysts
Rank
#4
Chemical
Ethylene
33 billion lbs
#10
Propylene
18 billion lbs
#12
#16
Production
Steam Cracking of Hydrocarbons:
larger hydrocarbon smaller hydrocarbon + H2
C2H6(g) C2H4(g) + H2(g)
Catalyst: Zeolites, Pt/Re on Al2O3 support
Conditions: 850C, 20-50 atm
Steam Cracking of Hydrocarbons:
C3H8(g) C3H6(g) + C2H4(g) + CH4(g) H2(g)
Benzene
10 billion lbs
Oxychlorination:
2C2H4(g) + 4HCl(g) + O2 2ClCH2CH2Cl(g) + 2H2O
Catalyst: Cu salts on SiO2 or Al2O3 supports
Hydrocarbon Reforming (dehydrogenation)
C6H14(g) C6H12(g) + H2(g)
C6H12(g) C6H6(g) + 3H2(g)
toluene benzene + methane
Endothermic!
Endothermic!
#19
#20
Styrene
8 billion lbs
#21
Conditions: 550-600C
Terephthalic Amoco Process:
Acid
p-CH3-C6H4-CH3 + 3O2 p-HOOC-C6H4-COOH + H2O
8 billion lbs
#22
Methanol
7 billion lbs
CO + H2 CH3OH
Catalyst: ZnO/Cu salt
Conditions: > 100 atm, 200-300C
Toluene
6 billion lbs
#27
Xylenes
5.5 billion lbs
#28
Ethylene
Glycol
5 billion lbs
#31
Cummene
3.7 billion lbs
#32
Acetic Acid
3.5 billion lbs
CH3OH + CO CH3COOH
Catalyst: homogeneous RhI2(CO)2(Monsanto Acetic Acid process)
Conditions: 150C, 35 atm
CATALYTIC DEUTERATION
Hydroformylation
Rh or Co
+ CO + H2
linear (normal)
side reactions
R
alkene isomerization
Aldehydes
+
branched (iso)
R
alkene hydrogenation
HYDROFORMYLATION
H
O C
Co
C O
C
O
18e
- CO
(disosiasi ligan)
+ alkena
(cordination
of olefin)
Co
C O
C
O
Reductive
elimination
R
O
16e
H
C O
Co
H
Co
CO
CO
C
18e
C
O
C
O
+ H2
(Oxidative
addition)
18e
R
Co
C
Co
16e
16e
R
O C
alkyl migration
Co
C
O
18e
+ CO
addition of CO)
19
Industrial proses:
CH3OH + CO CH3COOH, 2 juta ton per tahun
Katalisis menggunakan kompleks rhodium.
O
H 3C
+ HI
CH3OH
OH
OC
+ H2O
(hydrolisis)
Rh
HI
(+ H2O)
CH3I
CO
oxidative
addition
Rh(I) 16e
O
H 3C
CH3
OC
Rh
I
OC
Rh
+ CO
CH3
I
Rh(III) 18e
I
Rh(III) 18e
alkyl
migration
reductive
elimination
CO O
CO
ligand coordinaton
O
OC
Rh
CH3
I
Rh(III) 16e
23
Pd
Cl
+ OH
Cl
H2O
Pd
Cl
OH
6/6/2012
available.
H
H
enantioselectivity mechanism
27
coord
red elim
H
H
M
H
M
ins
ox add
H2
M
Alternative mechanism
M
H
H
mechanisms using
29
H2/D2 mixtures or PHIP.
ox add
coord
Distinguish between
H2
ins
red elim
H
M
H
Wilkinsons Catalyst
Ph3P
Rh
Ph3P
PPh3
+ H2
Cl
Ph3P
Rh
PPh3
- PPh3
Rh
Ph3P
PPh3
- PPh3
Cl
+ H2
R
H
H
Rh
Ph3P
PPh3
Cl
Rh
Cl
Ph3P
H
H
Rh
Ph3P
R
PPh3
Cl
PPh3
PPh3
Cl
OLEFIN METATHESIS
M C
+
C C
.
M C
C C
ALKYNE METATHESIS
C
C
Metathesis
Reaksi antara dua substrat tidak jenuh (biasanya
C8
+
C14
C2
migratory
insertion
elimination
ethylene
dissociation
diene
addition
elimination
migratory
insertion
N/A
N/A
N/A
Polymerization Catalysis
Polymerization is the reaction of an unsaturated organic reactant, typically a C=C,
with itself over and over again to produce a polymer chain:
*
n
When only a few alkenes couple together to make a short chain, we refer to that
as oligomerization (oligomers are very short polymers).
Initiation: generating the active catalyst from a less active catalyst
precursor:
LnM-Cl + AlR3
LnM-R
+ AlR2Cl
+ MAO (methylalumoxane)
+ ZnR2
LnM-Cl + H-
LnM-H
+ Cl-
45
Propagation: the polymer chain growth portion of the reaction that occurs
H3C
-
CH3
CH3
CH3
CH3
H2
CH3
CH3
H3C
-
CH3
CH3
CH3
However in 1978 Malcolm Green and John Rooney proposed a rather different
mechanism based on the recently reported Schrock alkylidenes:
ZIEGLER-NATTA POLIMERIZATION
H2O + C H2 + CO
T & P tinggi
Fischer-Tropsch process
H2 + CO alkana
;
3H2 + CO CH4 + H2O ;
2H2 + CO CH3OH
;
Steam reforming, pada P & T tinggi
CH4 + H2O CO + 3H2
Water gas shift reaction
CO + H2O CO2 + H2
Co catalyst
Ni catalyst
Co or Zn/Cu catalyst
;
Ni catalyst, 700-10000C
Fe/Cr or Zn/Cu catalyst, 4000C
Rasio CO:H2 syn gas dapat diubah melalui watergas shif treaction,
maka reaksi dapat berjalan kedua arah sehingga dapat dianggap sebagai
aktivasi CO maupun CO2.
Heck reaction:
R-X
organotin
R-X
+ HX
R'
aryl or
vinyl halide
Stille coupling:
Pd(0)
R'-SnR3
R'
Pd(0)
R-R' + XSnR3
aryl or
vinyl halide
organozinc
Negishi coupling:
R-X
R'-ZnR
Pd(0)
R-R' + XZnR
aryl or
vinyl halide
organoboron
Suzuki coupling:
R-X
R'-B(OH)2
Pd(0)
R-R' + XB(OH)2
aryl or
vinyl halide
alkyne
Sonogashira coupling:
R-X
aryl or
vinyl halide
R'
Pd(0)
R' + HX
COOH
O
O
MeO
Taxol
CH3
MeO
Skeleton
(s)-Naproxen
2-Ethylhexyl
trans-4-methoxycinnamate
MeO
Heck reaction
Br
Isoamyl
trans-4-methoxycinnamate
O
O
J.J. Masters, D.K. Jung,
W.G. Bornmann and
S.J. Danishefsky,
Tetrahedron Lett., 1993, 34, 7253
MeO
SO2Ph
CC-1065
N
H
Skeleton
O
MeO
Ar
alkene
R-X
aryl or
vinyl halide
+ HX
R'
R'
H+
Pd(0)
ArX
Pd
ox add
Ar
Pd
X
subst
+
Ar
ins
Ar
Pd
R
X-
60
RX
Pd
ox add
red elim
the mechanism of
the substitution step.
The literature mentions
Pd
Pd
Ar
subst
EX
ArE
R-X
R'-M
Pd(0)
R-R' + MX
The mechanism involves oxidative addition of the halide or triflate to the initial Pd(0) phosphine
complex to form a Pd(II) species. The key slow step is a transmetallation, so called because
the nucleophile (R') is transferred from the metal in the organometallic reagent to the palladium
and the counterion (X = halide or triflate) moves in the opposite direction. The new Pd(II)
complex with two organic ligands undergoes reductive elimination to give the coupled product
and the Pd(0) catalyst ready for another cycle.
The halide partner (RX)
L
Pd L
must be chosen with care,
as -hydride elimination
R'-R
would decompose the first
+ R-X
intermediate during the
slow transmetallation step.
The choice for R is
L
L
restricted to substituents
R
R
Pd
Pd
without -hydrogen atoms:
vinyl, allyl, benzyl, and
L
R'
L
X
polyfluoroalkyl halides,
triflates, and phosphates
R'-M
M-X
have all been coupled
successfully.
transmetallation
alkene
Heck reaction:
R-X
R'
aryl or
vinyl halide
+ [HBase]X
R'
R 3P
Pd
+X+ Base
+ R-X
H
R3P
oxidative
addition
R 3P
Pd
X
R 3P
R'
PR3
R'
H
R'
R'
H
R3P
R
R 3P
-hydride
elimination
migratory
insertion
migratory
insertion
R 3P
Pd
PR3
R'
Pd
R'
H
R
+ Base
Pd
X
elimination
PR3
- PR3 +
R3P
-X- +
Pd
R'
PR3
Pd
-hydride
R3P
+ PR3
Pd
R'
+ [HBase]X
PR3
+ Base-HX
Base
PR3
Pd(0)
Pd
X
H
R
H
R'
R'
Big Summary
Dari keseluruhan kuliah MRA anda telah mendapatkan (setidaknya
salah satunya):
+/- 3 bab dari buku teks kimia anorganik
Pengetahuan tentang berbagai mekanisme reaksi baik stoikiometrik
BIOKIMIA