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Catalysis
SARI EDI C
Nucleophlic Displacement
(attack by a Lewis base)
A strong nucleophile would be a ligand with strong
electron-donating character.
Organometallic complexes can behave as nucleophiles
in displacement reactions (especially negativelycharged complexes).
[Co(CO)4]- + RX RCo(CO)4 + XRCo(CO)4 + CO R(C=O)Co(CO)4 (acyl complex)
R(C=O)Co(CO)4 +ROH R(C=O)OR + HCo(CO)4
(generates the ester from an alcohol).
Modification of Ligands
Insertion a molecular fragment appears to
insert itself into a metal-ligand bond.
Many reaction mechanism can be complicated.
1,1-insertion (both bonds are made to the same
atom).
illustrate
Insertion of Ligands
How is CO inserted in the complex shown
previously (1,1-insertion)?
Work through this and understand.
1,2-insertions
Hydride Elimination
Transfer of a hydrogen atom from a ligand
to a metal.
elimination is the most common type.
position on the alkyl ligand.
Stability
Alkyl complexes that lack hydrogens are more
stable.
Coordinatively saturated complexes containing
alkyl ligands are also more stable.
Abstraction
Removal of a substituent from a ligand in
which the coordination number of the metal
does not change (can be removed by an
acid).
Organometallic Catalysts
(hydroformylation)
Converting terminal alkenes into other organic products.
(oxo process) H and HCO are formally added across a double
bond.
Show reaction
Largest-scale industrial process that is homogeneous
Comments on the
Hydroformylation Mechanism
CO pressure has to be controlled carefully.
Why?
Rate-determining step is the insertion of the
olefin (alkene).
Main purpose of the reaction is to produce
butanal from propene.
CH3CH=CH2CH3CH2CH2CHO
Hydrogenation of Alkenes
Wilkinsons catalyst
Show reaction (alkenes and alkynes)
Hydrogenation Catalyst
Selective hydrogenation can be observed if the
ligand contains multiple double bonds.
Another hydrogenation catalyst, (PPh3)2Rh(CO)H, is
very selective toward hydrogenation of only terminal
olefins.
Asymmetric hydrogenation
If the catalyst, [L2RHS2]+, bears an optically active
diphosphane, prochiral unsaturated molecules can be
hydrogenated to chiral products (enantiomeric selectivity).
L-Dopa (treatment of Parkinsons disease).
Alkene Metathesis
Demonstrate
Propene and 1-butene (what are the 4 new products that may form
from methathesis?)
Heterogeneous Catalysis
Used much more
extensively in industry
than homogeneous
catalysts.
Robust at high
temperatures.
Easy to separate out the
catalyst.
Composition of Heterogeneous
Catalysts
Uniform bulk of the
high-surface area serves
as the catalyst.
ZSM-5 (zeolite)
Surface Ligands
In many cases, the nature of the surface ligand is
inferred by comparison of IR spectra with those of
organometallic or inorganic complex.
Terminal and bridging CO.
Surface-Sensitive Techniqus
Temperature-programmed desorption (mass
spectroscopy).
Photoelectron spectroscopy (XPS and Auger)
Low-Energy Electron Diffraction (LEED)
Scanning Tunneling and Atomic Force
Microscopies.
Vibrational Techniques (RAIRS and HREELS).
Many othes.
Catalytic Steps
Many parallels can be drawn in comparison
to organometallic mechanisms studied
previously.
Chemisorption and physisorption
Similar to interactions present in complexes
with low oxidation states.
Physisorption and chemisorption.
Catalytic Steps
Similar to homogeneous
catalysis, there is also a
balance between strong
enough adsorption for the
reaction to occur and weak
enough desorption that the
species can be removed
for further reactions.
HCOOH CO + H2O
(on a metal surface)
Diversity of Sites
Real surfaces possess a
large diversity of surface
types. Each surface type
may have a different
reactivity and/or produce
different products.
Lower selectivity.
Most reactive sites.
Examples of Heterogeneous
Catalysts
Hydrogenation of alkenes on
metal surfaces.
H2 is dissociatively
chemisorbed
Ethylene is associated
Hydrogen adds to produce an
alkyl species
Another hydrogen atom
coordinates and ethane leaves.
Actual species produced
Ziegler-Natta Polymerization
TiCl4 + Al(C2H5)3
A titanium alkyl complex is produce.
Ethylene or propylene associates and inserts
into the titanium-carbon bond.
The 1,2-insertion continues.
Mechanism has proved difficult to understand.
In Miessler and Tarr
Fundamental Studies of
Hydrocarbons on Platinum Surfaces
The techniques used.
Reflection-absorption infrared spectroscopy.
Auger electron spectroscopy
Temperature-programmed desorption/reaction
spectroscopy.
Others as needed.
Reflection-Absorption Infrared
Spectroscopy (RAIRS)
The dynamic dipole moment must have a component normal to the
surface to be visible.
The intensity of the vibration signature reveals orientation
information.
Position of the signature indicates identity of species on the surface.
_
q(t)
+
qcos
+
_
+
_
+
_
qsin
250-325 K
cyclooctene
cyclooctenediyl
C8H12
C8H14
1,3-cyclooctadiene
C8H12
.
250-300 K
1,5-cyclooctadiene
C8H12
. or
cyclooctadienediyl
C8H10
cyclooctatetraene
1,5-dihydropentalene
Stable to ~500 K,
decomposes to yield
predominantly surfacebound carbon,
hydrogen desorbs.
cyclooctatetraene
C8H8
bicyclo[3.3.0]2-octene
C8H12
Pentalene
C8H6
1,5-dihydropentalene
C8H8
1,4-Cyclohexadiene on Pt(111)
Hdistal
Hproximal
Hdistal
Hproximal