Lecture 10 INTRO TO CATALYSIS

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A catalyst
◦ speeds up a reaction
◦ enables a reaction to proceed that otherwise does not without
it
◦ added in non-stoichiometric amounts ( ~ 10-6 to 10-1X)
◦ unchanged at the end of the reaction

INTRODUCTION TO CATALYSIS
Catalysis is a kinetic phenomenon:
C atalyzed rxn
pro ceeding thro ug h
an interm ed iate

Ea
k1
A + B + [CAT] C
Ea k-1
G catalyzed
k1
K=
Reactants k-1
G

Products

Reaction Coordinate

INTRODUCTION TO 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

IMPORTANCE OF CATALYSIS
IMPORTANCE OF CATALYSIS
Catalyst turnover frequencies, rates and numbers:

Turnover Frequency, TOF = number of turnovers per mol catalyst

per unit time. For most relevant industrial applications TOF is in
the range of 10-1 to 102 s-1
(= TON/time)

Turnover Number, TON = number of moles of substrate that a

mole of catalyst can convert before becoming inactivated.

The lifetime of the catalyst before deactivation is measured in

terms of total turnovers.

INTRODUCTION TO CATALYSIS
There are different types of catalysis:
Acid-base catalysis
Electrocatalysis
Photocatalysis
Redox Catalysis
Homogeneous Catalysis
Enzymatic Catalysis
Heterogeneous catalysis
Supported Catalysis
Metallodendritic Catalysis
Biphasic Catalysis

INTRODUCTION TO CATALYSIS
 The catalysts we look at are soluble complexes, or
homogeneous catalysts, as opposed to catalysts such as
palladium on carbon, or heterogeneous catalysts.

 These terms are used because 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.

 Catalyticmechanisms are considerably easier to study in

homogeneous systems, where such powerful methods as NMR
can be used to both assign structures and follow reaction
kinetics.

HOMOGENEOUS CATALYSIS
 Homogeneous catalysts have the disadvantage that they can be
difficult to separate from the product.

 Homogeneous catalysts can also be chemically grafted on to

solid supports for greater ease of separation of the catalyst from
the reaction products.

 Although the catalyst is now technically heterogeneous, it often

retains the characteristic reactivity pattern that it showed as a
homogeneous catalyst, and its properties are usually distinct
from those of any of the classical heterogeneous catalysts—
these are sometimes called “heterogenized” homogeneous
catalysts.

HOMOGENEOUS CATALYSIS
HOMOGENEOUS CATALYSIS
 The mechanistic ideas developed in homogeneous catalysis
are also becoming more influential in the field of classical
heterogeneous catalysis by suggesting structures for
intermediates and mechanisms for reaction steps.

 Bybringing about a reaction at lower temperature, a catalyst

can save energy in commercial applications. It often gives
higher selectivity for the desired product, minimizing product
separation problems and avoiding the need to discard the
undesired product as waste.

HOMOGENEOUS CATALYSIS
Environmental concerns have promoted the idea of
atom economy, which values a process most highly
when all the atoms in the reagents are used to form
the product, minimizing waste.

Catalysis is Green Chemistry !!!!

HOMOGENEOUS CATALYSIS
 OH O
 The selectivity O O
can be changed
by altering the OH

ligands, allowing Hydrogenation Hydrofomylation

O
synthesis of Chemoselectivity Regioselectivity

products not R OH COOR'

formed in the
un‐catalyzed R OH COOR' R NHCOR"

process.
R OH R NHCOR" COOR'

Hydrogenation Hydrogenation R NHCOR"

Diastereoselectivity Enantioselectivity

HOMOGENEOUS CATALYSIS
With growing regulatory pressure to synthesize drugs
in enantiopure form, asymmetric catalysis has come to
the fore, along with enzyme catalysis, as the only
practical way to make such products on a large scale.

HOMOGENEOUS CATALYSIS
 For most transition metal catalysts, the catalyzed pathway is
completely changed from the pathway of the uncatalyzed
reaction. Instead of passing by way of the high‐energy
uncatalyzed transition state TS, the catalyzed reaction normally
goes by a multistep mechanism in which the metal stabilizes
intermediates that are stable only when bound to the metal.
 Normally, the catalyst only increases the rate of a process but
does not alter its position of equilibrium, which is decided
by the relative thermodynamic stabilities of substrate and
products.
 For example, if the substrate S is slightly less stable than the
product P, so the reaction will eventually reach an equilibrium
favoring P.
 TheTS structure in the absence of the metal would be
extremely unstable, but the energy of binding is so high that
M.TS is now much more favorable than TS and the reaction all
passes through the catalyzed route.

 Differentmetal species may be able to stabilize other transition

states TS—which may lead to entirely different products—hence
different catalysts products can give different products from the
same starting materials.

 Theslow step in a catalytic process is called the turnover

limiting step. Any change that lowers the barrier for this
step will increase the turnover frequency (TOF).
 Changes in other barriers will not affect the TOF. For a high TOF,
we require that none of the intermediates be bound too strongly
(otherwise they may be too stable and not react further) and
that none of the transition states be prohibitively high in energy

 Indeed,the whole reaction profile must not stray from a rather

narrow range of free energies, accessible at the reaction
temperature. Even if all this is arranged, a catalyst may
undergo a catalytic cycle only a few times and then “die.”

 Thishappens if undesired deactivation reactions are faster than

the productive reactions of the catalytic cycle itself.
 start here
The catalytically active species must
have a vacant coordination site (total precatalyst
valence electrons = 16 or 14) to
allow the substrate to coordinate.
catalyst
products
A substrate
Noble metals (2 and 3 period of
nd rd

groups 8-10) are privileged catalysts

(form 16 e species easily).
D B

substrate
C
HOMOGENEOUS CATALYSIS – GUIDING PRINCIPLES
 start here
 In general, the total electron count
alternates between 16 and 18.
precatalyst

catalyst • Ancillary ligands insure stability

products
and a good stereoelectronic
A substrate balance.

• One of the catalytic steps in the

D B catalytic cycle is rate-determining.

substrate
C
HOMOGENEOUS CATALYSIS – GUIDING PRINCIPLES
 Cl PAr3 H2 adds to the catalyst before the
Rh
Ar3P PAr3 olefin.
S ligand dissociation The last step of the catalytic cycle is
PAr3 irreversible. This is very useful
CH3CH3
Ar3P S H-H because a kinetic product ratio can
reductive Rh
elimination Cl PAr3 oxidative be obtained
addition
irreversible Relative rates
for hydrogenation
H H Ligand: of cyclohexene:
Ar3P CH2CH2H Ar3P H
Rh Rh (4-ClC6H4)3P 1.7
Cl PAr3 Cl PAr3 PPh3 41
S S (4-CH3C6H4)3P 86
(4-CH3OC6H4)3P 100
insertion/
migration H
rearrangement Ar3P
Rh
H substrate Simplistically, the relative rates
coordination
Cl PAr3 suggest that the rate-
S S
determining step is OA of H2.

OXIDATIVE ADDITION OF H2 TO AN ALKENE