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KATALIS ORGANOLOGAM

KATALIS HOMOGEN • Catalytic Deuteration • Hydroformylation • Monsanto Acetic Acid Process • Wacker (SMIDT)
KATALIS HOMOGEN • Catalytic Deuteration • Hydroformylation • Monsanto Acetic Acid Process • Wacker (SMIDT)

KATALIS HOMOGEN Catalytic Deuteration Hydroformylation Monsanto Acetic Acid Process Wacker (SMIDT) Process

HOMOGEN • Catalytic Deuteration • Hydroformylation • Monsanto Acetic Acid Process • Wacker (SMIDT) Process

Hydrogenation by Wilkinson’s Catalyst Olefin Metathesis

KATALIS HETEROGEN Ziegler-Natta Polymerization

Water Gas Reaction

Why should you care ?

Kimia Organologam: basis dari homogeneous catalysis, katalis homogen, alternatif metode sintesis yang bersih dan

efisien untuk pembuatan farmasetika dan berbagai

kemikalia skala besar plastics (polythene, polypropene, butadiene rubber, dan deterjen dibuat via katalisis organologam. Kimia Organologam: juga basis pemahaman tahapan reaksi heterogeneous catalysis misalnya hidrogenasi olefin dan oksidasi CO.

)

Senyawa organologam digunakan dalam skala besar sebagai

prekursor semikonduktor (AlN, GaAs, etc). Silicone rubbers are one of the few classes of organometallic compounds used as "final products".

2

Homogeneous Catalysis - Introduction

Homogeneous Catalysis - Introduction  G Catalyzed rxn proceeding through an intermediate E a E a

G

Catalyzed rxn

proceeding through an intermediate E a E a catalyzed Reactants G
proceeding through
an intermediate
E
a
E a
catalyzed
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

generally far more selective for a single product

far more active

far more easily studied from chemical & mechanistic aspects (NMR)

far more easily modified for optimizing selectivity

Green Chemistry!!!

Bad

far more sensitive to permanent deactivation

far more difficult for achieving product/catalyst separations

Heterogeneous catalysts dominate chemical and petro-chemical industry: ~ 95% of all chemical processes use heterogenous catalysts. Homogenous catalysts are used when selectivity is critical and product- catalyst separation problems can be solved.

Homogeneous or Heterogeneous? (N/A)

There are several general ways to test whether a catalyst is homogeneous or heterogeneous.

Exposure to elemental Hg will generally poison a heterogeneous catalyst

Exposure to polythiols will poison most homogeneous catalysts

Light scattering studies to identify the presence of colloids (heterogeneous)

Product selectivity studies:

e.g., polymer bound alkenes:

Polymer

selectivity studies: e.g., polymer bound alkenes: Polymer + H 2 Catalyst Polymer Catalyst Homo / Hetero

+

H 2

Catalyst

e.g., polymer bound alkenes: Polymer + H 2 Catalyst Polymer Catalyst Homo / Hetero % Yield

Polymer

e.g., polymer bound alkenes: Polymer + H 2 Catalyst Polymer Catalyst Homo / Hetero % Yield

Catalyst

Homo/Hetero

% Yield

RhCl(PPh 3 ) 3

homo

100

Ni(OAc) 2 + NaBH 4

hetero

--

[Rh(nbd)(PR 3 ) 2 ] +

homo

90

Pd/C

hetero

--

[Ir(cod){P(i-pr) 3 }(py)] +

homo

100

Some Catalysis Terminology (N/A)

Turnover (TO) -- one loop through the catalyst cycle. Typically one equivalent of reactant is converted to one equivalent of product (per equivalent of catalyst).

Turnover Frequency (TOF) or Turnover Rate -- the number of passes through

the catalytic cycle per unit time (typically sec, min or hrs). This number is usually

determined by taking the # of moles of product produced, dividing that by the # of moles of catalyst used in the reaction, then dividing that by the time to produce the given amount of product.

Equiv

Aldehyde

Prod

2,000

1,800

1,600

1,400

1,200

1,000

800

600

400

200

0

Vinyl Acetate Hydroformylation

0.3mM catalyst -- 85°C/90 psi H /CO

2

Hydroformylation 0.3mM catalyst -- 85°C/90 psi H /CO 2 sampling from autoclave causes pressure glitches Uptake

sampling from

autoclave causes

pressure glitches

Uptake curve kobs = 0.0076 min -1 Ln plot Initial TOF 8 TO/min 476 TO/hr
Uptake curve
kobs = 0.0076 min -1
Ln plot
Initial TOF
8 TO/min
476 TO/hr

4.5

4

3.5

3

2.5

2

1.5

1

Ln   P)

0

5

10

15

20

Time (hours)

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 don’t 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., 10 6 - 10 10 ) 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

=

10 turnovers

5 mole % catalyst

=

20 turnovers

1 mole % catalyst

=

100 turnovers

0.1 mole % catalyst

=

1000 turnovers

0.01 mole % catalyst

= 10,000 turnovers

These represent the theoretical maximum # of turnovers. One also has to note the % yield or the % conversion of

substrate into product to

figure out the actual # of turnovers!!

Process

Petroleum Refining

Cracking

Reforming

Hydrocracking

Hydrodesulfurization

Hydrodenitrogenation

Chemical Manufacturing

Natural Gas desulfurization Hydrogenations Methanol synthesis Dehydrogenation

Oxidations

Polymerizations

Hydroformylation

Typical Catalysts

Pt/Re on alumina, Zeolites

Pt/Re/Ge/Sn on alumina (dehydrogenation)

alumina, zeolites, Pt (Mo-Co) oxides, (Mo-Ni) oxides (W-Ni) oxides

ZnO, Cu, Fe on activated C Raney Ni, Raney Co, Pt, Rh Cu-ZnO Butadiene: Fe2O3, Pt/Re on alumina; styrene: Zn, Cr, Fe

or Mn oxides

ethylene oxide: Ag, nitric acid: Pt/Rh mesh/gauze sulfuric acid: V2O5, maleic, phthalic anhydrides: V2O5, formaldehyde: Ag or Cu; Mo, Fe, V oxides Ziegler-Natta polypropylene: Al alkyls + TiCl3 Dow single site polypropylene: Ti metallocene Phillips -- Cr oxide on silica, Polyethylene (low density):

peroxides, peresters; Polystyrene: benzoyl peroxide; Urethanes: amines, organo-tin, phosphine oxides Union Carbide/Hoechst/BASF: Rh/PPh3

Exxon/BASF: HCo(CO)4 , Shell: HCo(CO)4(PR3) (R =

bulky alkyl)

Rank

Chemical

 

Production

#4

Ethylene

Steam Cracking of Hydrocarbons:

33

billion lbs

larger hydrocarbon

smaller hydrocarbon + H2

 

C2H6(g)

C2H4(g) + H2(g)

 

Catalyst: Zeolites, Pt/Re on Al2O3 support Conditions: 850°C, 20-50 atm

#10

Propylene

Steam Cracking of Hydrocarbons:

18

billion lbs

C3H8(g)

C3H6(g) + C2H4(g) + CH4(g) H2(g)

 

Catalyst: Zeolites, Pt/Re on Al2O3 support Conditions: 850°C, 20-50 atm

#12

Dichloroethane

Direct Chlorination:

15 billion lbs

C2H4(g) + Cl2(g)

ClCH2CH2Cl(g)

 

Catalyst: FeCl3 or AlCl3

Oxychlorination:

 
 

2C2H4(g) + 4HCl(g) + O2

2ClCH2CH2Cl(g) + 2H2O

 

Catalyst: Cu salts on SiO2 or Al2O3 supports

#16

Benzene

Hydrocarbon Reforming (dehydrogenation)

10

billion lbs

C6H14(g)

C6H12(g) + H2(g)

Endothermic!

 

C6H12(g)

C6H6(g) + 3H2(g)

Endothermic!

toluene

benzene + methane

Catalyst: Pt/Re/Ge/Sn on Al2O3 support

#17

Ethyl Benzene

9 billion lbs

C6H6(g) + C2H4(g)

C6H5C2H5

1. Catalyst: Liquid phase system with AlCl3

2. Catalyst: Zelolite Lewis Acid based gas phase process

Classic Friedel-Crafts rxn.

#19

Vinyl Chloride

ClCH2CH2Cl(g)

H2C=CHCl(g) + HCl(g)

 

8

billion lbs

This reaction is often coupled with the oxychlorination reaction to produce dichloroethane, this allows recycling of the HCl.

#20

Styrene

Dehydrogenation of ethyl benzene

 

8

billion lbs

Catalyst: Fe oxides on Al2O3 support

Conditions: 550-600°C

#21

Terephthalic

Acid

8 billion lbs

Amoco Process:

p-CH3-C6H4-CH3 + 3O2

Catalyst: Co/Mn salts (with some heavy metal bromides)

Conditions: liquid acetic acid solution, 200°C, 20 atm Ti or Hastelloy C lined reactor (very corrosive)

p-HOOC-C6H4-COOH + H2O

#22

Methanol

CO + H2

CH3OH

 

7

billion lbs

Catalyst: ZnO/Cu salt Conditions: > 100 atm, 200-300°C

#24

Ethylene Oxide C2H4(g) + ½O2

ethylene oxide

 

6

billion lbs

Catalyst: Ag Conditions: 300°C

#26

Toluene

Catalytic Reforming of methyl cyclohexane and derivatives

 

6

billion lbs

Catalyst: Pt/Re on Al2O3 support

 

Conditions: 500°C and 25 atm

#27

Xylenes

Catalytic Reforming of 1,4-dimethylcyclohexane

 

5.5 billion lbs

Catalyst: Pt/Re on Al2O3 support Conditions: 500°C and 25 atm

#28

Ethylene Glycol 5 billion lbs

ethylene oxide + H2O

HOCH2CH2OH

Catalyst: H2SO4 (0.5 - 1%), 50°-70°C Conditions: Thermal @ 195°C and 15 atm.

#29

Butylaldehyde

Hydroformylation -- Union Carbide/Celanese/BASF

5 billion lbs

propylene + H2 + CO

CH3CH2CH2CHO

Catalyst: homogeneous Rh/PPh3 catalyst Conditions: 100-125°C, 8-25 atm

#31

Cummene 3.7 billion lbs

 

benzene + propene

C6H5CH(CH3)2

1.

Liquid phase catalysts: H2SO4, AlCl3, HF

 

2.

Gas phase catalyst: H3PO4 on SiO2

Friedel Crafts reaction Conditions: 35-40ºC, 7 bar (liquid); 200-300ºC, 20-40 bar (gas) Cumene is mainly used to produce phenol and acetone.

#32

Acetic Acid 3.5 billion lbs

 

CH3OH + CO

CH3COOH

Catalyst: homogeneous RhI2(CO)2- (Monsanto Acetic Acid process) Conditions: 150°C, 35 atm

CATALYTIC DEUTERATION

.

CATALYTIC DEUTERATION .

Hydroformylation

Aldehydes

O Rh or Co R R + CO + H 2 H linear (normal) side
O
Rh or Co
R
R
+
CO
+
H 2
H
linear (normal)
side reactions
R
R

alkene isomerization

alkene hydrogenation

* Proses katalisis homogen terbesar

* > 15 billion pounds of aldehydes (alcohols) per year

Katalis komersial menggunakan kompleks Co atau Rh

Selektivitas menghasilkan aldehid linear (normal) merupakan hal yang penting

+

H O *
H
O
*

R

branched (iso)

Otto Roelen (1897-1993)

Otto Roelen (1897-1993)

.

HYDROFORMYLATION

O

O

H O C C Co 18e C O - CO C (disosiasi ligan) O H
H
O
C
C
Co
18e
C
O
- CO
C
(disosiasi ligan)
O
H
O
C
Co
C
O
C

O

16e

H R Reductive elimination O R H CO Co 18e CO H
H
R
Reductive
elimination
O
R
H
CO
Co
18e
CO
H

C

+ alkena

(cordination of olefin) R R H O C Co 18e C O C
(cordination
of olefin)
R
R
H
O
C
Co
18e
C
O
C

O

O + H 2 (Oxidative addition) O R O C Co 16e C O C
O
+ H 2
(Oxidative
addition)
O
R
O
C
Co
16e
C
O
C
O

alkyl migration

O

1,2 migratory insertionaddition) O R O C Co 16e C O C O alkyl migration O R O

R O C Co C 16e O C
R
O
C
Co
C
16e
O
C
O R O C C Co + CO C addition of CO) O C
O
R
O
C
C
Co
+ CO
C
addition of CO)
O
C

O

18e

Mekanisme lain tersedia : HYDROFORMYLATION USING HRh(CO) 2 (PPh 3 ) 2

Mekanisme lain tersedia : HYDROFORMYLATION USING HRh(CO) 2 (PPh 3 ) 2

Sintesis asam asetat

Asam asetat berperan penting dalam industri kimia.

Proses tradisional menggunakan fermentasi : bio-oksidasi alkohol C 6 H 12 O 6 2 C 2 H 5 OH + 2 CO 2 C 2 H 5 OH + O 2 CH 3 COOH + H 2 O Bukan proses yang bersih dan efisien

Industrial proses:

CH 3 OH + CO CH 3 COOH, 2 juta ton per tahun

19 Katalisis menggunakan kompleks rhodium.

MONSANTO ACETIC ACID PROCESS

MONSANTO ACETIC ACID PROCESS .

.

HI sebagai side product

dipakai lagi berikatan dengan methanol

HI

(+ H 2 O)

CH 3 I

lagi berikatan dengan methanol H I (+ H 2 O) CH 3 I CH 3 CO
CH 3 CO Rh I
CH 3
CO
Rh
I

OC

dengan methanol H I (+ H 2 O) CH 3 I CH 3 CO Rh I

I Rh(III) 18e

O + HI H 3 C OH
O
+ HI
H
3 C
OH

Rh3 I CH 3 CO Rh I OC I Rh(III) 18e O + HI H 3

I CH 3 CO Rh I OC I Rh(III) 18e O + HI H 3 C

CH 3 OH

CO
CO

I

I OC I Rh(III) 18e O + HI H 3 C OH Rh CH 3 OH
I OC I Rh(III) 18e O + HI H 3 C OH Rh CH 3 OH

oxidative

I

addition

Rh(I) 16e
O

H

Rh CH 3 OH CO I oxidative I addition Rh(I) 16e O H 3 C I

3 C

I

3 OH CO I oxidative I addition Rh(I) 16e O H 3 C I reductive elimination

reductive

elimination

alkyl

migration

CO O OC CH 3 Rh I I I
CO
O
OC
CH 3
Rh
I
I
I

Rh(III) 18e

alkyl migration CO O OC CH 3 Rh I I I Rh(III) 18e + CO ligand

+ CO

migration CO O OC CH 3 Rh I I I Rh(III) 18e + CO ligand coordinaton

ligand coordinaton

O OC CH 3 Rh I I I
O
OC
CH 3
Rh
I
I
I

Rh(III) 16e

The reaction is independent of CO pressure

First order in both rhodium and MeI.

Rate determining step is the oxidative addition of MeI to the [Rh(CO) 2 I 2 ] - catalyst.

WACKER (SMIDT) PROCESS (Nucleophilic addition of H2O at ethylene)

untuk sintesis asetaldehida dari etilena, dimana melibatkan siklus katalitik menggunakan

PdCl 4 2-

reaksi kimia pada saat terikat pada Pd

dimana Pd mampu mengubah sifat kimia alkena sehingga mampu mengadakan

.

4 2 - reaksi kimia pada saat terikat pada Pd dimana Pd mampu mengubah sifat kimia

Nucleophilic attack at ligand

Nucleophilic:

requires an electron-poor ligand atom (acidic proton, coordinated C=X bond)

H

Cl 2 O
Cl
2 O
Cl Pd
Cl
Pd

+ OH -

ligand atom (acidic proton, coordinated C=X bond) H Cl 2 O Cl Pd + OH -

H

Cl 2 O
Cl
2 O

Pd

Cl OH
Cl
OH

-

The Wacker process (N/A)

karakteristik Wacker process:

Oksigen pada produk berasal dari air bukan dari oksigen langung sebagai oksidan

4 juta ton aldehid per tahun

Olefin rantai lebih panjang menghasilkan keton, bukan

aldehid

Korosif karena perlu banyak halida

Produk sampingan dihasilkan dari proses serangan nukleofilik halida pada olefin

No longer important for acetic acid synthesis Several variations (with more complicated nucleophiles) used in organic synthesis

The Wacker process (N/A)

Characteristics of the Wacker process:

Alkena dapat menyerang nukleus membentuk kompleks logam

alkil, lalu menata ulang membentuk produk lainnya. Hal ini

adalah dasar pengetahuan penting bagi proses industri

Fakta bahwa PdCl 2 (aq) dapat mengoksidasi etilen menjadi

asetaldehid telah diketahui sejak abad 19 meski mekanismenya

belum dimengerti saat itu

Reaksinya mengkonsumsi PdCl 2 menghasilkan Pd(0), Pd Cl 2 cukup mahal jika hanya digunakan sebagai reagen stoikiometri

J.Smidt pada Wacker Chemie (1950’) menyadari bahwa Pd(0) dapat dihalangi pengendapannya menggunakan CuCl 2 yang mengoksidasi Pd sementara tereduksi menjadi CuCl.

Catalytic olefin hydrogenation (N/A)

Many chiral variations available.

enantioselectivity mechanism can be very subtle

For achiral hydrogenation, heterogeneous catalysts ("Pd

black") are often a good

alternative.

Extremely high turnovers

possible.

H M
H
M
H H red elim
H
H
red elim

H

H H M ox add H 2
H
H
M
ox add
H
2
coord H M
coord
H
M
ins
ins
H M
H
M
. KatalisWilkinson, RhCl(PPh 3 ) 3 Ligan phosphine mempunyai peranan penting yang membuat kompleks ini

. KatalisWilkinson, RhCl(PPh 3 ) 3 Ligan phosphine mempunyai peranan penting yang membuat kompleks ini selektif Rh hanya akan bereaksi dengan senyawaan olefin yang tidak mempunyai hambatan sterik. Sehingga katalis wilkinson digunakan

untuk hidrogenasi selektif dari ikatan

C=C dengan tidak ada hambatan sterik.

Catalytic olefin hydrogenation (N/A)

Alternative mechanism for metals not forming a "stable" hydride.

Requires oxidative addition, not observed for early transition metals.

Distinguish between mechanisms using H 2 /D 2 mixtures or PHIP.

29

M
M
coord M
coord
M
H 2 ox add
H 2
ox add
M H
M
H

H

red elim H H
red elim
H
H
ins
ins
M H H
M
H
H

Wilkinson’s Catalyst

Ph

Ph 3

3 P Rh P
3 P
Rh
P

PPh 3

+ H 2

Cl

H

Ph 3 P

H PPh 3 Rh Cl
H
PPh 3
Rh
Cl
R R Ph 3 P H H PPh 3 Rh Cl Ph 3 P
R
R
Ph 3 P
H
H
PPh 3
Rh
Cl
Ph 3 P
P H PPh 3 Rh Cl R R Ph 3 P H H PPh 3 Rh
- PPh 3 PPh 3 Rh Cl + H 2
- PPh 3
PPh 3
Rh
Cl
+
H 2

PPh 3

PPh 3 Rh Cl Ph 3 P - PPh 3 PPh 3 Rh Cl + H

- PPh 3

H

H

H PPh 3 Rh Cl Ph 3 P R
H
PPh 3
Rh
Cl
Ph 3 P
R
H PPh 3 Rh Cl Ph 3 P R
H
PPh 3
Rh
Cl
Ph 3 P
R

OLEFIN METATHESIS

M

C

COLEFIN METATHESIS M C + . C M C C C M C + C C OLEFIN METATHESIS M C + . C M C C C M C + C C

+

.

COLEFIN METATHESIS M C C + . M C C C M C + C C OLEFIN METATHESIS M C C + . M C C C M C + C C

M C
M
C
OLEFIN METATHESIS M C C + . C M C C C M C + C

C

C
C
M C +
M
C
+

C C

ALKYNE METATHESIS

OLEFIN METATHESIS M C C + . C M C C C M C + C

Metathesis

Reaksi antara dua substrat tidak jenuh (biasanya alkena atau alkuna) yang menggabungkan kedua

gugus pada kedua ujungnya yang mempunyai ikatan rangkap

alkuna) yang menggabungkan kedua gugus pada kedua ujungnya yang mempunyai ikatan rangkap C 8 + C
alkuna) yang menggabungkan kedua gugus pada kedua ujungnya yang mempunyai ikatan rangkap C 8 + C

C 8

+

alkuna) yang menggabungkan kedua gugus pada kedua ujungnya yang mempunyai ikatan rangkap C 8 + C
C 8 +
C
8
+
alkuna) yang menggabungkan kedua gugus pada kedua ujungnya yang mempunyai ikatan rangkap C 8 + C

The proposed mechanism for this involves metal-alkylidenes and is shown below:

migratory

insertion M
insertion
M
elimination M
elimination
M
ethylene dissociation M
ethylene
dissociation
M

M

migratory insertion M elimination M ethylene dissociation M M diene addition migratory elimination M insertion M
migratory insertion M elimination M ethylene dissociation M M diene addition migratory elimination M insertion M

diene

addition

migratory

elimination

migratory insertion M elimination M ethylene dissociation M M diene addition migratory elimination M insertion M
M
M
insertion M
insertion
M
migratory insertion M elimination M ethylene dissociation M M diene addition migratory elimination M insertion M
M
M
N/A

N/A

N/A

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

itself over and over again to produce a polymer chain: n * * n When only

*

* n
*
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:

L

n M-Cl

+

AlR 3

a less active catalyst precursor: L n M - Cl + AlR 3 L n M-R
L n M-R
L n M-R

+ AlR 2 Cl

+ MAO (methylalumoxane)

L

n M-Cl

+ ZnR 2

+

H

-

L n M - Cl + AlR 3 L n M-R + AlR 2 Cl +
M-H L n
M-H
L n

+

Cl -

Applications of oligomers and polymers

Ethene and propene come directly from crude oil "crackers"

Primary petrochemical products, basic chemical feedstocks

Dimerization rarely desired

Making butene costs $$$ !

Oligomers: surfactants, comonomers

High added value, but limited market

Polymers: plastics, construction materials, foils and films

Very large market, bulk products

45
45

Propagation: the polymer chain growth portion of the reaction that occurs over and over again:

M

CH 3

of the reaction that occurs over and over again: M CH 3 H 3 C -
of the reaction that occurs over and over again: M CH 3 H 3 C -
H 3 C -  M CH 3 M
H
3 C
-
M
CH 3
M

M

over and over again: M CH 3 H 3 C -  M CH 3 M
H 3 C M
H
3 C
M

CH 3

again: M CH 3 H 3 C -  M CH 3 M M H 3

Termination: a reaction step that stops the polymer chain growth:

M

M H 3 C M CH 3 Termination: a reaction step that stops the polymer chain

CH 3

MM M H 3 C M CH 3 Termination: a reaction step that stops the polymer

H 2

MM M H 3 C M CH 3 Termination: a reaction step that stops the polymer

H

H

+

+

CH 3 CH 3
CH 3
CH 3

Cossee (migatory insertion) Propagation Mechanism

The commonly accepted mechanism for polymer chain growth on a transition metal catalyst is the very simple migratory insertion mechanism initially proposed by Piet Cossee (Royal Shell labs) in 1964.

M

CH 3

initially proposed by Piet Cossee (Royal Shell labs) in 1964. M CH 3 H 3 C
initially proposed by Piet Cossee (Royal Shell labs) in 1964. M CH 3 H 3 C
H 3 C -  M CH 3 M
H
3 C
-
M
CH 3
M

M

initially proposed by Piet Cossee (Royal Shell labs) in 1964. M CH 3 H 3 C
H 3 C M
H
3 C
M

CH 3

initially proposed by Piet Cossee (Royal Shell labs) in 1964. M CH 3 H 3 C

Green-Rooney (alkyidene metallacycle) Propagation Mechanism

However in 1978 Malcolm Green and John Rooney proposed a rather different

mechanism based on the recently reported Schrock alkylidenes:

Malcolm Green and John Rooney proposed a rather different mechanism based on the recently reported Schrock
Malcolm Green and John Rooney proposed a rather different mechanism based on the recently reported Schrock
Malcolm Green and John Rooney proposed a rather different mechanism based on the recently reported Schrock
Malcolm Green and John Rooney proposed a rather different mechanism based on the recently reported Schrock
Malcolm Green and John Rooney proposed a rather different mechanism based on the recently reported Schrock
Malcolm Green and John Rooney proposed a rather different mechanism based on the recently reported Schrock

ZIEGLER-NATTA POLIMERIZATION

.
.

CO 2 and CO activation

Berbagai reagen organik saat ini dibuat secara komersial dari

etilena, turunan proses pemurnian minyak bumi

Di masa depan perlu mencari sumber karbon lain

Batu bara atau natural gas (metana) dapat diubah menjadi campuran CO/H 2 (water gas/synthesis gas/syn gas) dengan udara dan uap yang nantinya dapat diubah menjadi metanol dan bahan bakar alkana melalui berbagai katalis heterogen.

dengan udara dan uap yang nantinya dapat diubah menjadi metanol dan bahan bakar alkana melalui berbagai

WATER GAS REACTION

H 2 O

+

C

H 2

+

CO

Fischer-Tropsch process

H 2

3H 2

2H 2

+

CO alkana CO CH 4

+

+ CO CH 3 OH

+

H 2 O

;

;

;

Steam reforming, pada P & T tinggi

CH 4 +

H 2 O CO

+

3H 2

;

T & P tinggi

Co catalyst

Ni catalyst Co or Zn/Cu catalyst

Ni catalyst, 700-1000 0 C

Water gas shift reaction CO + H 2 O CO 2 + H 2 ; Fe/Cr or Zn/Cu catalyst, 400 0 C

Solusi Green Chemistry : Chem.Rev. 2007, 107, 4022−4047 Hydrogen Production by Molecular Photocatalysis

Arthur J. Esswein and Daniel G. Nocera fotokatalisis dengan bantuan katalis organologam dll. untuk mengubah berbagai substrat kimia menjadi sumber

hidrogen

Misal reaksi FischerTropsch mengubah syn gas menjadi campuran

alkana rantai panjang dan alkohol dengan katalis heterogen( biasanya Co, Fe atau Ru)

alkohol dengan katalis heterogen( biasanya Co, Fe atau Ru)  Rasio CO:H 2 syn gas dapat

Rasio CO:H 2 syn gas dapat diubah melalui watergas shif treaction, yang terkatalis heterogen (Fe 3 O 4 or Cu/ZnO) atau berbagai katalis homogen Fe(CO) 5 atau Pt(i-Pr 3 P) 3 .

katalis homogen Fe(CO) 5 atau Pt(i-Pr 3 P) 3 .  Baik reagen maupun produk mempunyai

Baik reagen maupun produk mempunyai energi bebas yang serupa maka reaksi dapat berjalan kedua arah sehingga dapat dianggap sebagai aktivasi CO maupun CO2.

Homogeneous Catalysis of Water Gas shift reaction

.
.

Pd-Catalyzed C-C Coupling Rxns

Heck reaction:

alkene

Pd(0)

R

 
R-X + R' aryl or vinyl halide organotin R-X + R'-SnR 3
R-X
+
R'
aryl or
vinyl halide
organotin
R-X
+
R'-SnR 3
R-X + R' aryl or vinyl halide organotin R-X + R'-SnR 3 + H X

+

HX

   
R'

R'

 

Pd(0)

Stille coupling:

Stille coupling: R- R' + X SnR 3

R-R'

+

XSnR 3

aryl or

vinyl halide

 
 

organozinc

Pd(0)

Negishi coupling:

R-X

+

R'-ZnR

Negishi coupling: R- X + R' -ZnR R- R' + X ZnR

R-R'

+

XZnR

aryl or

vinyl halide

 
 

organoboron

Pd(0)

Suzuki coupling:

R-X

+

R'-B(OH) 2

Suzuki coupling: R- X + R' -B(OH) 2 R- R' + X B(OH) 2  

R-R'

+

XB(OH) 2

 

aryl or

vinyl halide

 
 

alkyne

Pd(0)

Sonogashira coupling:

R-X

+

Sonogashira coupling: R- X + R' R R' + H X

R'

RR'

R R'

R'

+

HX

aryl or

vinyl halide

Why the “Heck” Bother with the Heck Reaction:

Applications in Industry and Total Synthesis

Sunscreen Agents Flavourings Cosmetic Additives O O MeO 2-Ethylhexyl trans-4-methoxycinnamate O O MeO Isoamyl
Sunscreen Agents
Flavourings
Cosmetic Additives
O
O
MeO
2-Ethylhexyl
trans-4-methoxycinnamate
O
O
MeO
Isoamyl
trans-4-methoxycinnamate
Non-Steroidal Anti-inflammatory drugs CH 3 COOH MeO (s)-Naproxen MeO Heck reaction Br MeO
Non-Steroidal
Anti-inflammatory drugs
CH 3
COOH
MeO
(s)-Naproxen
MeO
Heck reaction
Br
MeO

Anorg. Chem. Inst. der Technischen Universität München

Key Steps in Total Synthesis O Taxol B C Skeleton A J.J. Masters, D.K. Jung,
Key Steps in Total Synthesis
O
Taxol
B
C
Skeleton
A
J.J. Masters, D.K. Jung,
W.G. Bornmann and
S.J. Danishefsky,
Tetrahedron Lett., 1993, 34, 7253
O
O
N
SO 2 Ph
CC-1065
N
Skeleton
H
O
L.F. Tietze and T. Grote,
J. Org. Chem., 1994, 59, 192

The Heck reaction

R-X

+

aryl or

vinyl halide

alkene

The Heck reaction R- X + aryl or vinyl halide alkene R ' Pd(0) R R'

R'

Pd(0) R
Pd(0)
R
R- X + aryl or vinyl halide alkene R ' Pd(0) R R' + H X

R'

+

HX

For most systems,

we don't know the

coordination environment of Pd during catalysis.

At best, we can detect one or more resting states.

The dramatic effects of ligand variation show

that at least one ligand

is bound to Pd for at least part of the cycle.

59

+
H

Ar

is bound to Pd for at least part of the cycle. 59 + H Ar R

R

ArX ox add Ar Pd X
ArX
ox add
Ar
Pd
X
part of the cycle. 59 + H Ar R ArX ox add Ar Pd X Pd

Pd

+ H Ar Pd
+
H
Ar
Pd

R

-
-

subst

+

X

R

-elim -elim

part of the cycle. 59 + H Ar R ArX ox add Ar Pd X Pd

Pd

+

part of the cycle. 59 + H Ar R ArX ox add Ar Pd X Pd
Ar
Ar

Pd

part of the cycle. 59 + H Ar R ArX ox add Ar Pd X Pd

R

ins

part of the cycle. 59 + H Ar R ArX ox add Ar Pd X Pd

Ar

part of the cycle. 59 + H Ar R ArX ox add Ar Pd X Pd

R

The Heck reaction

Works well with aryl iodides, bromides Slow with chlorides

Hardly any activity with acetates etc

Challenges for "green chemistry"

Pt is ineffective

Probably gets "stuck" somewhere in the cycle

60 Oxidative addition, reductive elimination

Suzuki and Stille coupling

The oxidative addition and

Pd

RX ox add
RX
ox add

R

coupling  The oxidative addition and Pd RX ox add R Pd X red elim R

Pd

X
X

 The oxidative addition and Pd RX ox add R Pd X red elim R Pd
red elim
red elim

R

The oxidative addition and Pd RX ox add R Pd X red elim R Pd Ar

Pd

Ar

reductive elimination steps

have been studied extensively.

RAr

Much less is known about the mechanism of the substitution step.

The literature mentions "open" (3-center) and

subst ArE EX
subst
ArE
EX

"closed" (4-center) mechanisms

This may well be different

for different electrophiles.
61

Cross-Coupling of Organometallics and Halides

R-X

+

R'-M

Pd(0)

Organometallics and Halides R- X + R' -M P d ( 0 ) R- R' +

R-R'

+

MX

M = MgX, ZrCp 2 Cl, ZnX, SnR 3 , B(OR) 2 , AlMe 2 , SiR 3 , Cu,…

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.

R'-R -R

L Pd
L
Pd
L + R-X
L
+ R-X
L L
L
L

Pd

ready for another cycle. R' -R L Pd L + R-X L L Pd R R'

R

R'ready for another cycle. R' -R L Pd L + R-X L L Pd R M-X

M-X R'-M
M-X
R'-M
L Pd L
L
Pd
L

transmetallation

The halide partner (RX) must be chosen with care, as -hydride elimination would decompose the first intermediate during the

slow transmetallation step.

The choice for R is restricted to substituents without The choice for R  -hydrogen atoms: -hydrogen atoms: The choice for R is restricted to substituents without 

R

X

vinyl, allyl, benzyl, and polyfluoroalkyl halides, triflates, and phosphates have all been coupled successfully.

Heck reaction:

R-X

+

aryl or

vinyl halide

alkene R'
alkene
R'
Pd(0) R
Pd(0)
R

Base

+ R'
+
R'

Base-HX

+ [HBase]X R' R
+ [HBase]X
R'
R

R 3 P

R Base + R' Base -H X + [HBase]X R' R R 3 P + X

+X -

+ Base

R

3

P

H R Pd R' PR 3
H
R
Pd
R'
PR 3

Pd

+ [HBase]X PR 3 + PR 3 R R' R oxidative R Pd PR 3
+ [HBase]X
PR 3
+ PR 3
R
R'
R
oxidative
R
Pd
PR 3
3 P
addition
+ R-X
X
- PR 3
+
+ Base
R'
H
R
R
R
R
3
R
Pd
P
Pd
X
R
P
3
Pd
P
3
R'
R'
X
PR 3
X
-X - + -hydride elimination H H R R R P Pd R P Pd
-X -
+
-hydride
elimination
H
H
R
R
R
P
Pd
R
P
Pd
3
H
3
migratory
R'
R'
PR 3
PR 3
insertion

R'

migratory

insertion

R P 3
R
P
3
-hydride elimination H H R Pd H R' X
-hydride
elimination
H
H
R
Pd
H
R'
X

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 maupun katalisis kimia koordinasi dan khususnya kimia organologam

Bekal tambahan ketika anda menghadapi kuliah kimia tingkat

advance: kimia bioanorganik, sintesis kimia organik,+ anorganik

(organologam)! (sintesis kimia merupakan kajian terpenting ilmu kimia !)

gambaran bagaimana sebagian besar reagen kimia yang anda kenal

dihasilkan melalui proses katalisis dari source minyak bumi (syn-gas)

oleh perusahaan terkemuka dunia

Gambaran bagaimana mempelajarinya dalam skala laboratorium

Mengetahui perkembangan terakhir katalisis dan sintesis kimia (eq. nobel: ziegler-natta 1963, ferrocene1973, sintesis L-DOPA 2001)

Aplikasi kimia dalam industri

Aplikasi kimia dalam industri

Sintesis kimia organik!

Sintesis kimia organik!

Sintesis kimia organik!

KIMIA BIOANORGANIK, MEDISINAL

KIMIA BIOANORGANIK, MEDISINAL
BIOKIMIA

BIOKIMIA

BIOKIMIA

KIMIA LINGKUNGAN GREEN CHEMISTRY

KIMIA LINGKUNGAN – GREEN CHEMISTRY