32
KATALYSE – EINE „NATÜRLICHE“
CHEMISCHE SCHLÜSSELTECHNOLOGIE
Antrittsvorlesung Univ.-Prof. Dr. Marko Hapke, Institut für Katalyse
27. März 2017
„Natürlich versus chemisch“?!?
K. Roth, Chem. Unserer Zeit 2016, 50, 226-232
Catalysts: A plethora of uses and possibilities
By Emw - Own work, CC BY-SA 3.0, https://commons.wikimedia.org/w/index.php?curid=8761857
The task of a catalyst: lowering the energy barrier!
A B
C
Highlights from the early history of catalysis…
6000 BC Yeast fermentation for the production of wine, acetic acid, beer and bread
1783 J. Priestley: Dehydratisation of alcohol to ethylene using heated clay
1818 L. J. Thénard: Decomposition of H2O2 by metals, oxides, organic compounds
1820 E. Davy: Oxidation of whiskey to acetic acid using platinum powder (at rt)
1823 J. W. Döbereiner: Ignition of hydrogen in the presence of platinum sponge at room temperature(„Döbereiner‘s Feuerzeug“)
1894 W. Ostwald: Classical definition of catalysis
The origin of catalysis…
Definition of the term „catalysis“:
J. J. Berzelius:
Sinngemäßes Zitat aus einem Brief an Justus von Liebig (1835):„Es kommt hier in unseren Untersuchungen eine neue Kraft hinein, auf die wir aufmerksam sein müssen. […] Ich nenne die Kraft (mag sie sein, was sie will) katalytische Kraft der Körper und das Zerlegen durch katalytische Kraft […] Katalyse.“
F. W. Ostwald (NP 1909, kinetic definition of catalysis):
„Katalyse ist die Beschleunigung eines langsam verlaufenden chemischen Vorganges durch die Gegenwart eines fremden Stoffes.“
Ein Katalysator ist jeder Stoff, der die Geschwindigkeit einer chemischen Reaktion erhöht, ohne dabei selbst verbraucht zu werden oder im Endprodukt der chemischen Reaktion zu erscheinen, und ohne die Lage des thermodynamischen Gleichgewichts zu verändern.
Greek: κατάλυση = Auflösung,Zersetzung Chinese: meaning: „Katalyse“ and
„Heiratsvermittler“(!)
…to eminently important processes for our daily lives
1908 F. Haber, A. Mittasch: Synthesis of ammonia from atmospheric nitrogen based on an iron catalyst(NP 1918 for Haber)
1913 Introduction of the Haber-Bosch industrial process for the production of ammonia andfollow-up products
Overall equation:
The Haber-Bosch process
Source: GFDL, https://commons.wikimedia.org/w/index.php?curid=3167578
Some key facts:
– Extreme energy intense process (up to 2% of annual world energy consumption)
– Annual production of ca. 120 million tons ammonia (increasing)
The Haber-Bosch process
Some key facts:
– Extreme energy intense process (up to 2% of annual world energy consumption)
– Annual production of ca. 120 m tons ammonia (increasing)
The Haber-Bosch process – mechanistic details
Chemical Kinetics Chapter 14 Copyright © The McGraw-Hill Companies, Inc.
General mechanism:
…to eminently important processes for our world
1913 Introduction of the Haber-Bosch industrial process for the production of ammonia and follow-upproducts
1925 Fischer-Tropsch process; alkanes and other compounds from H2 and CO
1937-… Catalytic cracking of crude oil, production of gasoline, alkenes, aromatics; basic chemicals forbasically EVERYTHING
1953-55 K. Ziegler/G. Natta: Low pressure polymerisation of ethylene using organometalliccatalysts/stereoselectivity of the polymerisation (NP 1963)
1981 J. J. Mooney, C. D. Keith: Three-way catalytic converter in automobiles
TiCl4AlEt3 n
Cleaning the traffic: Three-Way Catalyst (TWC)
catalytic converter
ceramicmonolith
1 mm 1 m
-aluminawashcoat Pt/Pd/Rh
catalyst
CO + 1/2O2 CO2Pt, Pd
HC's + O2 CO2 + H2OPt, Pd
CO + NO CO2 + 1/2N2
H2 + NO H2O + 1/2N2
Rh
Rh
Modes of catalysis
Catalysis
Homogeneouscatalysis Biocatalysis Special
variations
Catalyst(s) andreactandsare in the same phase
Classical:Liquid phasereactions
Catalyst(s)and reactandsare in differentphases
Classical:Solid-gas reactions
High molecularweight peptides = enzymes
Highly specificcatalysts
Featuringproperties ofhomogeneous/heterogeneouscatalysis
► Photocatalysis► Organocatalysis► Asymmetric
catalysis
Heterogeneouscatalysis
Green Chemistry: more than just a buzz word
Green chemistry
Lesshazardous materials
High fines for waste
Producerresponsibility
Government legislation
Lowercapital investment
Loweroperating costs
Economic benefit
Pollution control
Saferand smaller plants
Improvedpublic image
Societal pressure
Source: G. Rothenberg, Catalysis – Concepts and Green Applications, Wiley-VCH
Homogeneous catalysis: empowering synthesis!
R. Willstätter, E. Waser, Ber. Dtsch. Chem. Ges. 1911, 44, 3423R. Willstätter, M. Heidelberger, Ber. Dtsch. Chem. Ges. 1913, 46, 517
W. Reppe, O. Schlichting, K. Klager, T. Toepel, Liebigs Ann. Chem. 1948, 560, 1HC CH
Ni catalyst:Ni(acac)2 or
Ni(CN)24
N OMe
Pseudopelletierine
O
NMe
1. Na, C2H5OH2. H2SO4 N
Me
1. CH3I2. Ag2O N
Me Me
OH-
Me2N
1. CH3I2. Ag2O,
NMe2Me2N
1. Br22. HN(CH3)2
1. CH3I2. Ag2O,
10 steps
A little bit of aromatic history
2015: 150th Anniversary of the Kekulé benzene structure:
Ber. Dtsch. Chem. Ges. 1890, 23, 1305
August Kekulé (1829-1896)
A. J. Rocke, Angew. Chem. Int. Ed.2015, 54, 46
No history – Use of benzene derivatives today
Steamcrackingor reforming of
naphtha
Pt/Al2O3/SiO2- H2
-3 H2
Production Basis of materials, compounds, polymers of daily life
Styrene Polystyrene
Nitrobenzene Aniline
Polyurethanes,plasticiser,
dyes, pigments,drugs
Cumene
Acetone
Phenol
Plexiglass
Solvents
Epoxy resin
Cyclohexane CaprolactamAdipic acid Polyamides
“From dusk till dawn“ of cyclotrimerisationFirst observation from Berthelot in 1866:
In 1876 Sir William Ramsey noted the formation of pyridines:
The first cyclotrimerisation of acetylene with defined transition metal complexeswas reported by Reppe (BASF) in 1949:
Ni catalyst:
T
H
H H
H
HH H H
H
HH
H
red-glowingiron tube
N
H
H H
HH
N
H H
H
H
H
L2Ni(CO)2
L = PPh3
Hetero(arenes) in more complex structures
OHO
HO
H
H
Me
H
O
Estrone
N
N
HNNH
Me
Me
Complanadine A
Sporolide B
N
COOH
OMe
Me
Me
Illudinine(R)-Alcyopterosine E
Me
OO
H
ONO2
Me
Me
NH
HO
Me
OHHO
Cl
Vitamine B6
Cl
OH
OH
O
OHO
OMe
O
O
MeO
HO
N
NO
O
OHO
Me
Camptothecin
N
N
O
OH
HH
H
Strychnine
Molecular defined vs. in situ prepared catalysts
Active Catalyst
- Synthetic effort- Modification can be labour-intensive+ Defined systems, potentiallyeasier to investigate+ Systematic change of structure
+ High variability in ligands andmetal sources- Derivation from several components cancomplicate investigation of catalytic system- Side reactions
Molecular defined In situ generationSteering Ligand
"Dummy" ligands
Cyclisation catalysts from group 9 metals
Metal source: CoX2 (X = halides)Ligands: bisphosphines, pyridylimines, N,N' donor ligandsReductants + additives: Zn, Mn, ZnI2
Molecularly defined pre-catalysts:
In situ generation of catalysts:
CoCOOC
Co Co CoOC
CO2Me
MeO2CJonasVollhardt Gandon
Development of novel cobalt precatalysts
with N. Weding, A. Spannenberg: Organometallics 2010, 29, 4298Organometallics 2012, 31, 5660
Most reactive CpCo(I)-precatalyst:
with I. Thiel, H. Jiao, A. Spannenberg:Chem. Eur. J. 2013, 19, 2548
J. Organomet. Chem. 2014, 763-764, 60Thin Solid Films 2015, 578, 180
Access to novel classes of reactive precatalysts:
Airstable & recyclable precatalyst:
with I. Thiel, A. Spannenberg: ChemCatChem 2013, 5, 2865 (commercialisation with TCI)
Air-stable precatalyst for solid phase application:
with I. Thiel: J. Mol. Catal. A: Chem. 2014, 383-384, 153
Co(EtO)3P
COOMe
MeOOC
SiO2 SiO
OO
Influence of the involved metal on the reactivity
[cat] T [º C] t Yield [%]
Co 0 ~1 min >99
Rh 100 19 h 7
Ir 100 19 h traces
Cocyclisation for the formation of pyridines:
N. Weding, R. Jackstell, H. Jiao, A. Spannenberg, M. Hapke, Adv. Synth. Catal. 2011, 353, 3423
M
SiMe3
Me3Si
M = Co
M = Rh
M = Ir
[cat] T [º C] t Yield [%]
Co 0 10 min 82
Rh 100 19 h 32
Ir 100 19 h traces
The “dummy” ligand as moderator of reactivity
I. Thiel, H. Jiao, A. Spannenberg, M. Hapke, Chem. Eur. J. 2013, 19, 2548
[Catalyst]:
Testing of catalyst reactivity:
0
25
5075
100 0
20
40
60
80
100
[CpCo(H2C=CHSiMe3)2] (1) [CpCo(H2C=CHSiMe3){P(OPh)3}] (7a) [CpCo{P(OPh)3}2] (6a)
yiel
d of
pyr
idin
e [%
]
temperature [°C]
after 1min
after 1 h
after 24 h
(2)(3)
Test reaction:
A strategy to raise molecular complexity…
Beside the catalyst systems the selection of reaction substrates is profund for the reaction outcome:
Completelyintermolecular:
Partiallyintramolecular:
Completelyintramolecular: H/R
H/RCatalyst
H/R
R/H
… and asymmetric catalysis with cobalt complexes
M. Hapke, C. Fischer, K. Kral, A. Spannenberg, B. Heller et al., J. Org. Chem. 2010, 75, 3993
N
OMe
t-Bu
N
OMe
NMe2
44%; 94% ee64%; 91% ee
97%; 81% ee 59%; 86% ee 66%; 90% ee 79%; 91% ee
81%; 91% ee 45%; 75% ee 89%; 87% ee
h
Probing of the biaryl axes‘ configurational stability
F. Fischer, A. F. Siegle, M. Checinski, C. Fischer, K. Kral, R. Thede, O. Trapp, M. Hapke, J. Org. Chem. 2016, 81, 3087
Determination of activation barriers: proper substitution energetically adjusts five- and six-membered rings!
N
OMe
R
Co catalystR N
OMe
Future challenges for catalysis?
Quite a few!!!
Novel and atom efficient transformations; complex molecules from simple building blocks
Substitute rare metals in catalysts by earth-abundant metals Sustainable energy
production and storage
Transformation of „waste“ into new resources
Realisation of dreamreactions:
e. g. CH4 CH3OH
Acknowledgement… warm bodies
Dr. Nico Weding Dr. Karolin Kral Dr. Indre Thiel Dr. Phillip Jungk M.Sc. Helge Lange M.Sc. Tim Gläsel M.Sc. Tobias Pientka M.Sc. Tobias Täufer
Fabian Fischer
Dr. Barbara Heller
Prof. Dr. Uwe Rosenthal
Acknowledgement… warm bodies
Institute for Catalysis: 3rd floor TNF tower andKopfgebäude
Team at JKU:
DI Dr. Christoph Topf M.Sc. Tim Gläsel DI Stefan Humer M.Sc. Kirill Faust Regina Mayrhofer Romana Kolovski
Thank you for yourkind attention!
