Lecture 1:

General principles of catalysis

• Revision, definitions (interactive content)

• Reaction profiles
• Catalytic mechanisms
• Catalyst resting state and the rate
determining step (RDS)
• The identity of the catalyst
• Homogeneous vs heterogeneous catalysis

1
 Reaction profiles: conversion over time

• Catalysts 1 and 2 are of similar initial • Sampled at t1, catalysts 2, 3 and 4' would
________ but of very different ________ give ~ the same yield. Many researchers
try to use productivity at a single time point
to assess activity.
• The order of initial activity is
(highest)______________(lowest) • Catalyst 4' has a similar activity to 4 but
features an ________________________
• What can we say about the comparative
productivity of 3 and 4? ______________ • Note that such complicating factors
(catalyst degradation, catalyst activation)
because __________________________ may not respond in the same way to
• The productivity of 4 is higher than 1 and 2. conditions (temp, solvent, concentration) as
does the catalytic reaction. 2
 Lowering RDS or changing mechanism?

ΔG
(all reaction
components)

reaction
coordinate

3
 Lowering RDS or changing mechanism?

ΔG
(all reaction
components)

reaction
coordinate

3
 Lowering RDS or changing mechanism?

ΔG
(all reaction
components)

reaction
coordinate

3
Catalytic mechanism
This is a description of the elementary steps in a
catalytic cycle
• Individual reactions may obey a simple rate
equation but the overall rate equation can be
very complicated.
• The observed rate constant kobs usually hides
real constants and assumptions.
• The events between the resting state up to
and including the TS of the RDS determine the
rate law. In other words: the concentration
factors in the rate law indicate the composition
of the transition state
• They will be raised to some +ve or –ve order
depending on e.g. how many are involved and
whether they are leaving or adding to the
reaction centre.
• Rate law here?

4
DG‡cycle determines the TOF
The rate of formation of product is
determined by the activation free energy
of the cycle, ∆G‡cycle
• In a reaction coordinate diagram the
resting state is the lowest energy
combination of the catalyst and
reaction components, but note the
cyclic nature of the reaction.
• ∆G‡cycle is the energy difference
between the resting state and the TS
of the RDS: the highest energy
combination of the catalyst and
reaction components.
• The resting state does not have to be
at the start of the catalytic cycle as
drawn….this leads to the question:
what is the catalyst exactly?

5
Worked exercise: which new mechanism is catalytic?

ΔG ΔG

ΔG ΔG

6
Which is the catalyst?

• Any intermediate within the cycle

can be considered a viable catalyst.
• The precatalyst? – a stable
compound from which a
“catalytically active” species is
generated, perhaps:
– using an activator
– by reaction with a substrate

• A species obtained when the

reaction product is released i.e.
after the cycle has completed
once?
• An off-cycle species formed
reversibly?

7
 Off-cycle species

These are compounds generated from

catalytic intermediates and not directly
implicated in the productive cycle.
• Commonly, precatalyst à Cat is
irreversible
• If an off-cycle reaction like A is…

…irreversible, this corresponds to ….reversible, then this may be the

catalyst deactivation over time catalyst resting state, which affects rate

8
 Selectivity
In this example, the selectivity-
determining step happens after the RDS
• Ratio of products depends on…
ΔG
S + Cat
P2 + Cat
• What are the prospects for selective
S-Cat P1 + Cat catalysis here?

ΔG
The major product does not have to
come from the major species.
• A is predominant adduct at eqm, but
conversion of B is faster

• What kind of selectivity is this?

9
A B
 Homogeneous vs heterogeneous catalysis
Homogeneous catalysts Heterogeneous catalysts

• The catalyst and substrate are in the • The “catalytic site" is located at a phase
same fluid phase boundary. Only some of the surface atoms
• Advantages are active catalysts.
– High selectivity (tailoring of catalyst) • Advantages
– Low reaction temp/high activity – The product is in a different phase to
– Mechanisms studied more easily catalyst e.g. gas phase

• Disadvantages – Reagents continuously flow over

catalyst.
– Separation of catalyst from the
– Catalysts can be recycled by
reaction mixture often problematic.
“activation” e.g. washing, baking,
– More sensitive to permanent
deactivation • Disadvantages
– Many catalyst sites, so many products
– Less amenable to continuous
processes. – Phase change requires high temp
– Large plants required – Kinetics and spectroscopy not simple

Heterogenised homogeneous catalysts

Attempts to marry the advantages of both homo- and heterogeneous processes,
e.g. by attaching a homogeneous catalyst on a polymer support or by performing
10
the reaction in a two-phase liquid/liquid system using a water soluble catalyst.
 Lectures 2 – 5:
Metal-centred reactions
• Covalent bond classification (CBC) and electron
accountancy
• Oxidative addition (three-centre, nucleophilic, radical)
and reductive elimination reactions
• Insertion and elimination reactions

11
 Covalent bond classification
and electron accountancy

• MOELDs and the 18 VE “rule”

• Revision of electron counting methods
• Simple classes of ligand (L and X)
• Composite ligands
• Formal oxidation state and valence number
• Coordination number and ambiguities

12
 Octahedral complexes

M [ML6] 6L
Filling up the t2g (i.e. d6) gives 18 VE and is the
t1u* origin of the 18 VE “rule”, but…

a1g* The t2g orbitals are non-bonding, so < 18 VE

systems are perfectly viable.
p
If ligands are weak or M is first row, the eg*
orbital is only weakly antibonding so up to 22
s
VE complexes are possible, e.g. [Zn(en)3]2+
e g*
Complexes with large Δoct more likely to be 18
VE, e.g. 2nd/3rd row TM, strong σ-donors, π-
t2g
d
accepting ligands such as CO.
Steric effects and coordination number are
eg very important

t1u
A minimum of 12 VE is required to fill the M-L
a1g
s-bonding orbitals, e.g. [TiF6]2-, [WMe6]

13
 Square planar complexes

M [ML4] 4L
This is often the preferred metal coordination
e u* geometry for the late 2nd/3rd row TM that are
formally d8 ions, i.e. Rh(I), Ir(I), Pd(II), Pt(II).
a1g*
You do not have to remember this MOELD, but
a2u
p its important to note that the HOMO is largely
b1g* non-bonding with dz2 character and the LUMO is
s strongly anti-bonding (e.g. [Pd(NH3)4]2+ below)

a1g′

eg + b2g
d

b1g
HOMO (a1g′) LUMO (b1g*)
eu

Typical stable configuration is now

a1g 16 VE (d8) and not 18 VE
14
 Simple classes of ligand
There are two different ways of counting electrons: the “ionic method” and “neutral
method”. Both give the same count, but organometallic chemists tend to use the
neutral method = Covalent Bond Classification (CBC) method, which involves
treating ALL ligands as neutral species:

L ligands (2 VE donors) X ligands (1 VE donors)

usually observed as neutral species usually observed as anions, as this is
often a closed shell configuration

M L d M X d
s s
M L M X

M complex L M complex X

• and arguably • •
• • • •

• • • •

•
cf. Ionic method: M X
15
 Electron counting examples
• We will use the “neutral” method for electron counting
VE donated by metal = group number
e.g. Nb donates 5 electrons, Ni donates 10
• VE = number of valence electrons in ligand sphere

[Mo(CO)6]

[Pt(C2H4)3]

[W(PiPr3)2(CO)3(H2)]

[Pt(CO)2Cl2]

[Mn(CO)5Me]

[(OC)5Mn–Mn(CO)5]
16
 Composite ligands

Many common organometallic ligands can be described as composites of L and X

Ligand structure class VE-count

h1-allyl X 1

h3-allyl

h4-butadiene

h5-pentadienyl

17
 Formal Oxidation State (OS) and valency
OS is defined as…
“The charge left on the metal when all the ligands in their normal,
closed-shell, configurations are removed”
e.g. Cp2ZrCl2 à Cp- Cp- Cl- Cl- Zr4+ i.e. OS = Zr(IV)
This so-called ionic approach to working out the formal oxidation
state of the metal in a complex is the one favoured generally by
coordination chemists.
Organometallic chemists tend to think about their compounds as
being more covalent in nature often prefer the neutral method and
may refer to Valency (or Valence Number VN).
Cp2ZrCl2 VN = 4
We will always use the neutral method, but you should feel free to
use another method if you prefer that. Most of the time OS = VN so
feel free to continue to use OS, but there are some differences.
18
 Valence Number (VN)

VN = number of X type ligands + charge on complex

[Mo(CO)6] ≡ MoL6 OS = VN =

[Mn(CO)5Me] ≡ MnL5X OS = VN =

[Os(PR3)H8] ≡ OsLX8 OS = VN =

[Pt(CO)2Cl2] ≡ PtL2X2 OS = VN =

[W(PiPr3)2(CO)3(h2-H2)] ≡ WL6 OS = VN =

19
 Composite ligands, sandwich compounds

VN = number of X type ligands + charge on complex

[ML5X]+ [ML5X2]+ [ML4X]- [ML4X4] (17 VE)

VN (= OS) = VN (= OS) = VN (= OS) = OS =

VN =

Note that the charge is often drawn “on the metal”, while in fact it is
best described as the charge on the complex. In the first two
examples there would be a counter-ion such as Cl- or PF6-
20
 Coordination Number (CN) and
Ligand Bond Number (LBN)
CN = number of atoms bonded to the metal, or
CN = number of ligands bonded to the metal
LBN = Sum of L and X ligands, i.e. for MLlXx, LBN = l +x

[ML5X]+ [ML5X2]+ [ML5X]-

CN = CN = CN =
LBN = LBN = LBN =
21
 Summary
• Why count VE in complexes?
– Gives us some idea about stability if we understand the trends
– Can allow us to predict some aspects of reactivity
– You don’t have to use the CBC method. The ”ionic” method will give the same
count, but never mix the two approaches!

• The concept of formal metal oxidation state also gives us information

on stability and reactivity, but
– There are some ambiguities
– The related concept, Valence Number (VN) is mostly the same but unambiguous

• Coordination number can also be ambiguous

– The Ligand Bond Number (LBN) is very well defined

• More information on the CBC method

– Established by Malcolm Green FRS (cf. 4th floor teaching labs)
– Read: J. Chem. Educ. 2014, 91, 807−816 (DOI: 10.1021/ed400504f)
– Used by a few textbooks like Crabtree, Spessard & Miessler
22
 Oxidative Addition (OA) &
Reductive Elimination (RE)

• Definitions and requirements

• Types of OA (three-centre, nucleophilic, radical)
• Reductive elimination from octahedral d6 centres
• Reductive elimination from square planar d8 centres
• Stereochemistry at metal and carbon

23
 Definitions and requirements

In MOST oxidative additions Reductive elimination

• One 2e A-B bond is broken ...formed
• Two 2e “M-X” bonds formed ...broken
• Two vacant coordination sites required …produced
• Metal needs stable OS two units higher ...lower

More generally, if OS and CN go up during a reaction, then it is an oxidative

addition; we will see examples where DOS = +1 and DCN = +1
The forward and back mechanisms follow the same pathway.
24
 Three-centre (concerted) OA

H
L H2 L
Cl Ir CO H Ir CO
L L
Cl

• Square planar d8 • octahedral d6

• ≡M • ≡M
• OS = • OS =
• CN = • CN =
• VE = • VE =

Oxidative addition occurs at many other sorts of metal centre,

so long as the requirements (previous slide) are satisfied.
25
 Reaction coordinate diagram
• Ebde of H2 = 436 kJmol-1
• Ebde of Ir-H ~ 251 kJmol-1

Exothermic by ~ 66 kJmol-1
(expt = 63 kJmol-1 for Vaska’s compound)

Reactions have DS < 0, so DG

closer to zero
(expt = -25 kJmol-1 for
Vaska’s compound at 298 K)

Note: difference with the

Wilkinson’s catalyst
([Rh(PPh3)3Cl], see later) where
dissociation of L is preferred. Ir
being a 3rd row metal forms
Vaska’s compound stronger bonds than Rh
(L = PPh3) 26
Characteristics of three-centre (concerted) OA
• Low polarity X-Y bonds e.g. H-H, Si-H, B-H or
unsaturated organic electrophiles (see below)
• _______ order kinetics
• ____ kinetic product expected, although it may rearrange
to other thermodynamic product
• ________ DS‡ (ordered transition state)
• No effect/weak affect of solvent polarity on rate (why?)
• Where appropriate, reaction leads to retention of
stereochemistry at carbon centres
• Ar-X rates, X = Cl < Br < I (opposite order to SNAr, follows
order of reduction in bond strength)

If a reaction has these characteristics, it’s a 3-centre OA

27
 Nucleophilic OA

• Square planar d8 • Sq. pyr or TBP d6 • octahedral d6

• ML3X • [ML3X2]+ • ML3X3
• OS = 1 • OS = 3 • OS = 3
• CN = 4 • CN = 5 • CN = 6
• VE = 16 • VE = 16 • VE = 18

• The metal complex acts as a nucleophile (hence low OS, low CN)
• Overall, DOS = 2 and DCN = 2 but RDS has DCN = 1 only. Still an OA however!
28
 Characteristics of nucleophilic OA
• Polar A-B bonds
• Benzyl, acyl, allyl, methyl are the best electrophiles, just as
for “organic” SN2
• Second order kinetics
• Rate increases with leaving group stability
R-X: X = OTs > I > Br > Cl >> F
• Rate increases with use of electron donating ligands (such
as phosphines PR3).
• Negative DS‡ (ordered transition state)
• Reaction leads to inversion of stereochemistry at the
electrophile carbon centre
• Promoted by polar solvents (polar transition state)
If a reaction has these characteristics, it’s a nucleophilic OA
29
 Stereochemistry of OA and RE

• Nucleophilic OA occurs with inversion of configuration at the

electrophile carbon, like SN2
• 3-centre OA and more importantly cis-RE occur with retention of
configuration
• Note that R and S labels do not actually describe shape or any other
physical property. They are dependent on the priority of the groups
attached to the metal, so you need to look at the actual shape of the
molecule and not rely on whether R changes to S or not.

RE

OA – [Pt]

30
 Radical OA
• Some reactions (e.g. right) occur via
radical propagation mechanism (see
problems)
– Rate increases in presence of light
– Radical propagation kinetics e.g.
Rice-Herzfeld
– ~ Unaffected by solvent type
– Sometimes several products formed
– Often DOS = +1 and DCN = +1

• With many zerovalent group 10 metals,

Single Electron Transfer (SET) is a
common mechanism.
– The SET is rate-determining and the
kinetics relatively simple
– If the radical ion pair is not strongly
associated, the radical can escape to
produce a radical chain process as
above 31
 Reductive Elimination (RE) at octahedral centres

1. I expect this reaction to be

A. Reversible because the product is coordinatively unsaturated
B. Irreversible because oxidative addition of C-H bonds is difficult

2. If the phosphine is changed to PMe3, I expect that this reaction will be:
A. Slower because the starting material is less sterically crowded
B. Slower because the more electron-donating PMe3 stabilises the Rh(III)
starting material

32
 RE at octahedral centres
Larger ligands commonly promote RE reactions but this not usually because steric
crowding promotes the actual elimination step.
• For (d6) octahedral complexes, RE is commonly preceded by dissociation

• 18 VE A is stereochemically quite rigid, and although the two X ligands are cis
they cannot readily move together.
• A loses PPh3 at equilibrium at r.t.; the analogous Ir complex cannot readily do this.
• The five-coordinate system B is stereochemically labile; with (as usual) several
isomeric structures of similar energy. One of these is the Y-shaped distorted TBP
shown in which the Me and H ligands are quite close together.
• Loss of methane (via a s-complex? See later) gives the three-coordinate C which
rapidly adds PPh3 to give the stable 16 VE square planar D (Wilkinson’s Catalyst)
33
 Nature of the eliminating species
• Many species X-Y are eliminated but those involving hydrides are usually the
faster.

– H carries no electrons other than bonding electrons, and these are in a

spherically symmetrical 1s orbital, making/breaking bonds in any
direction in the transition state below.
– An intermediate σ-bond complex is probably formed, and indeed C-H
activation reactions are thought to occur via formation of such a complex
(microscopic reversibility).

34
RE from d8 complexes (e.g. Pd, Pt)
The eliminating ligands need to be cis:
• The cis complex here gives exclusively
butane on thermolysis.
• The trans isomer cannot eliminate
directly so is more stable….

35
 Three RE pathways for cis d8 complexes

Starting from the 16 VE system:

A. Rate-determining
dissociation, promoted by big
ligands L, precedes
elimination.
B. Relatively rare path, but
important for chelating L-L
e.g. diphosphines.
C. Induced by addition of e.g.
additional phosphine – a
more common pathway for Ni
(because 18e complexes of
that metal are more readily
formed).

EA A<B<C
Metal product viability > > 36
 Insertion and a/b-Elimination
• Definitions and key points
• Mechanistic studies on 1,1-insertion and stereochemistry
• Preventing b-elimination
• Frontier orbital picture for 1,2-insertion
• Reaction energetics and the agostic interaction
• Competition between alkyl migration and b-elimination

37
 Definitions: Migratory Insertion (MI)

Numbering describes which atoms of the inserted ligand are

bonded to M and X after the insertion
38
 Definitions: Elimination (E)

The opposite to MI is elimination (not the same as reductive elimination)

39
 1,1-Migratory Insertion and a-Elimination:
Mechanistic questions

The above reaction has been studied in detail, and much is known
about the mechanism

40
 Where does the CO come from?

• When 13CO is added to this compound, it appears cis to the acyl and
the acyl itself (arising from CO insertion into Mn-Me bond) is
“unlabelled”.
• Hence the mechanism is intramolecular
• The 13CO in the product has remained cis to acyl and has not moved
at all to the trans site. In other words, the reaction is under kinetic
control (i.e. we are observing the first-formed product). Convenient!
41
 Is 1,1-MI a cis process?

• The 13C labelled acyl product was synthesised by the route shown above
(mechanism = ), and was then heated to
promote elimination
• Only the cis isomer was observed, so the a-elimination is a cis process
• Since…. (the Principle of Microscopic Reversibility)
In a single step reversible reaction, the mechanism of the forward reaction
is the same as that of the reverse reaction
• …then the reverse reaction (the 1,1-MI) must be a cis process.
42
 Which Moves? The CO or the Me?
Consider the two possibilities…

CO insertion
or
“CO moves”

Me migration
or
“Me moves”

The two products are the same, so how do we tell which

mechanism is happening?
43
 Which Moves? The CO or the Me?
Study reverse reaction, then apply Principle of Microscopic Reversibility

Expected product if
“CO moves”
CO moves (a non-13C
product is also formed)

“Me moves”

Experiment shows mixture Expected products if

of cis and trans in ratio 2:1 methyl moves (a non-13C
so ALKYL MIGRATION is product is also formed)
the mechanism
44
 Stereochemistry at carbon

Ph
Me
CO O
Ph H
CO
Pt Cl
Me Pt Cl
retention OC
H
CO
CO

• Configuration at a stereogenic carbon is retained

• Same applies to the reverse, i.e. a-elimination
• Alkyl group moves

45
 1,2-Migratory Insertion and b-Elimination:
Definitions and conditions
1,2-migratory insertion

a
b
LnM LnM LnM
H H H

CN = n+2 coplanar CN = n+1

b-elimination

• Change in CN = -1 for 1,2-MI, but no change in OS

• Free coordination site needed for b-elimination
• Both forward and reverse reactions go through a planar transition state

46
 Preventing b-elimination
• Although b-elimination is slightly endothermic, it is a
common decomposition pathway for alkyls
• Can be prevented by
– not having any b-hydrogens (a very effective strategy!)
– saturating the coordination sphere (i.e. no free
coordination site available)
– preventing planarization (metallacycle, or unstable
alkene product)
• Sometimes, the coordinated C-H is an intermediate or
even a ground state rather than a TS: the agostic
interaction (see later)

47
 Agostic CH∙∙∙M Interaction
• This is an intramolecular interaction
B
between a C-H bond and metal: a 3-centre,
2-electron bond.
• From the Greek "to hold close to oneself”
like a shield (MLH Green)
• In 1,2-MI, conversion AàE normally goes
C
via (undetectable) TS B but sometimes
there is an agostic pathway via an
intermediate C. There is also the possibility
that the agostic is the ground state i.e. D.
A D
• Strength 40–65 kJmol-1
(more than
hydrogen bonds such as OH∙∙∙N) E

• X-ray crystallography & neutron diffraction:

C-H elongated by 5-20%, M---H 1.8 - 2.3 Å,
M-H-C 90 - 140°
• Convention for agostic bond is
• 1HNMR of C-H often in hydride region (0 the straight half-arrow
ppm or higher field) and 1JCH 70-100 Hz c.f.
125 Hz for regular C(sp3) • Commonly a or b C-H (shown)
for alkyls, but sometimes g etc.
• IR n(C-H) ~2500 cm-1 from 2950 cm-1 48
 Frontier orbital picture for 1,2-MI

• Left: the Dewar-Chatt-Duncanson bonding model where filled alkene

p-orbital is a s-donor towards the metal and the empty alkene p* is
an acceptor.
• As the alkene moves toward the 4-centre TS it is polarised so that
the donor orbital has more density on the atom nearest M and the
acceptor orbital is more concentrated on the orbital nearest CH3.
• This shows how the new M-C and C-C bonds might be formed and
how the C=C and M-C bonds are weakened
• The process is most efficient for d0 metals as there is no competition
from M-alkene back-bonding 49
 1,2-Migratory Insertion of alkyl v b-Elimination

• Methyl 1,2-MI AàC via TS B is a common and important reaction (e.g. in

coordination polymerisation such as Ziegler-Natta)
• The reverse b-Me elimination CàA is much more rare (slow)
– The newly-formed C-C bond in C is not an effective ligand to the free
coordination site: in fact g-agostic interactions are more realistic
– The methyl group can rotate out of the way to allow a b-agostic such
as D if this is favourable in the given system (see previous slide) or
indeed allow b-elimination to give E.
• In Ziegler-Natta catalysis the balance between 1,2-alkyl insertion
(propagation) and b-elimination (termination) may determine polymer Mw
50
 Lectures 6 – 8:
Homogenous hydrogenation
• Activation of dihydrogen by transition
metals
• Mechanisms (inner and outer sphere)
• Chemoselective reactions
• Stereoselective reactions

51
 The hydrogenation reaction
H O O H
H2 H2
H R'
R R R R' R
H

• Very important reaction with favorable thermodynamics.

• Direct addition of H2 is symmetry forbidden
HOMO (H2) LUMO (H2)

H H
H2 + H2C CH2 H3C CH3
H2C CH2
ΔG298K = -100 kJ mol-1
Concerted reaction?
LUMO (C2H4) HOMO (C2H4)
• Stoichiometric addition of hydride and proton
e.g. LiAlH4 or NaBH4 reduction of ketones and aldehydes (H–, then H+)
• Catalytic activation of hydrogen using transition metals
– Metal nanoparticles / metal surfaces = Heterogeneous catalysis
– Single transition metal center = Homogeneous catalysis
• Transfer hydrogenation; extraction of hydrogen from sacrificial organic
molecules. 52
 Activation of dihydrogen

• Very stable molecule:

• Strong and completely non-polar H-H bond

Bond dissociation Deprotonation

Homolytic cleavage Heterolytic cleavage
H2 2H H2 H + H
ΔH = 436 kJ mol-1 pKa (aq) = 36

• Typically require activation with a (reactive) transition metal. Possible outcomes?

H H H
H
[M] + [M] [M] cis [M]n&1 + H+
H H H
No reaction Stable η2-H2 bis-hydride complex mono hydride complex
complex (oxidative addition = (deprotonation =
(σ-complex) homolytic cleavage) heterolytic cleavage)

53
 Dihydrogen complexes
PiPr3 PiPr3
OC CO H2 OC CO
W W H
OC – H2 OC
vacuum H
PiPr3 PiPr3
16 VE 18 VE
Kubas, 1984

H H
[W]
D D
1J 1J
HD$=$34$Hz HD$=$43$Hz

Neutron diffraction 1
H NMR spectroscopy (ID = 1)
H–H = 0.82(1) Å (cf. H2 = 0.74 Å) 54
 Bonding in dihydrogen complexes (overview)
• Formed by interaction of both HOMO and LUMO of H2 with frontier MOs
of transition metal. In CBC method = L donor.
• Results in “population” of σ*HH orbital and H–H bond elongation

σ-donation σ-donation
C O

spndm hybrid HOMO (H2) spndm hybrid lp (:C O)

π-back bonding π-back bonding

dπ orbital LUMO (H2) dπ orbital π*(CO)

Similar bonding interactions to those in metal

carbonyl compounds

55
 Bonding in dihydrogen complexes (MO diagram)
[M] H2
H H (generic)
[M]

σ*HH

Side on approach
maximises orbital
overlap spndm hybrid

σHH
dπ

Both σ donation and π back bonding are important

• No known early transition metal complexes (d0).
BH3$(pz) σHH
• Stable dihydrogen complexes often have low
Very weak interaction
oxidation states (unstable compounds)
56
 H–H bond length elongation (activation)
• π-Back donation leads to reduction of H2 bond order.
• Complete donation results in oxidative addition of H2

H H H Dihydride
Free H2 H [M] H
[M] [M] [M] [M] (OA)
(BO = 1) H H H H H (BO = 0)
0.74)A+ 0.8)–)1.0)A+ 1.0)–)1.3)A+ 1.3)–)1.6)A+ >)1.6)A+

• Metal-ligand composition:
σ*HH

Increased π-
back donation
Orbital overlap:
1st vs. 2nd vs. 3rd row TM
• Oxidation state
• Overall charge dπ
• Ligand donation
• Trans-influence

Decreased π-
back donation 57
 Examples
• Using your knowledge of their electronic structure, order the following
complexes in increasing H–H bond length:

Ph2 H2 + + Ph2 H2 + Ph2 H2 2+

Ph2 Ph2 H2 Ph2 Ph2 Ph2 Ph2 H2 Ph2 +
P P P P P P P P P P
Ru Os Os Ru Ru
P P P P P P P P P P
Ph2 Cl Ph2 Ph2 H Ph2 Ph2 Cl Ph2 Ph2 CO Ph2 Ph2 H Ph2
1 2 3 4 5
0.987-A/ 0.994-A/ 1.19-A/ 0.85-A/ 0.89-A/

r(H–H)-&=&4-<-5-<-1-≤-2-<-3

58
 Reactivity of dihydrogen complexes
Low-coordinate
metal centre with [M] X-type ligand [M]
d(π) electrons (i.e. hydride, alkyl, aryl)
X

Stable (equilibrium?), H compare H

intermediate or [M] [M]
transition state H H [M] H
X
Base (σ-CAM) X H

H Concerted
[M]
transition state
H H
X H
[M] cis [M]n&1 + HBase+
H
homolytic cleavage heterolytic cleavage [M] H + X H
(oxidative addition) (deprotonation)
Electron rich Metal centre Electron deficient

Accessible Higher OS Not accessible “Sigma-bond metathesis”

heterolytic cleavage
2 Free Coord. sites 1 Free
(deprotonation)
Non-bulky Ancillary ligands Bulky 59
 Wilkinson’s (pre-)catalyst
• Mechanism (“hydride”) is well understood and involves OA
of H2 – common for group 9 metals – before coordination of
the olefin.
• Primary kinetic pathway:
Cl PPh3 Geoffrey Wilkinson
Rh The Nobel Prize 1973
Ph3P PPh3
(Ferrocene)
–(PPh3

H Cl PPh3
Rh H2
H
R Ph3P

H R H
Ph2P Ph2P H
Rh H Rh
Cl PPh3 Cl PPh3

H
RDS Ph2P H
Rh R
Cl PPh3
60
R RS
 Wilkinson’s (pre-)catalyst
• Alterative H2 activation pathways and catalyst deactivation:

H
Ph3P Cl PPh3 Cl PPh3 H2 Ph3P H
Rh Rh Rh Rh
Ph3P Cl PPh3 Ph3P PPh3 Cl PPh3
PPh3
K = 10-5 –(PPh3
Inactive dimeric 14 VE complex reacts
species formed Cl PPh3 104 times faster
H
(K = 106) Rh H2 than 16 VE
H –(PPh3
R Ph3P complex
SIGNIFICANT
DEACTIVATION NOT UNCOMMON
PATHWAY H R H
Ph2P Ph2P H FOR TEXTBOOKS
Rh H Rh TO USE SLOWER
Cl PPh3 Cl PPh3 PATHWAY

H
Ph2P H
Rh R
Cl PPh3

R
61
 “Mono-hydride” mechanism
• Another common hydrogenation mechanism, where a single hydride ligand is
present prior to coordination of the alkene cf. Wilkinson's catalyst.

Ph2 PPh3
P H
Ru
Cl
H PPh3

–+PPh3
H
(PPh3)2ClRu H
H
R R

H
H
H
(PPh3)2ClRu (PPh3)2ClRu
R

H R

(PPh3)2ClRu
H2 R
H
62
 “Olefin” hydrogenation mechanism
• Common for pre-catalysts with bidentate ligands, e.g. diphosphine ligands (P–P).
• Generally used for alkenes containing an additional donor group
• Example: [Rh(diphosphine)(diene)]+ (best with weakly donating solvent)

H2 P + 2 H2 R
Rh
P D R
– Rate
P H2 determining
Rh step
P D
P – H
Rh P P H
P H H
P Rh Rh R
H P P
Rh
P R D
H
P
H Rh
P P R P D
Rh Rh
P H P H
D
P
Rh H2
P

Irreversible formation of active catalyst Catalytic cycle 63

 Asymmetric hydrogenation catalysis
• Ability to control stereochemistry has very important applications.
• Selectivity reported as enantiomeric excess ee(%) = %major - %minor

[cat], H 2
COOH COOH + COOH

MeO MeO MeO

(S)-enantiomer (R)-enantiomer
Pro-chiral carbon
Important anti-inflammatory Harmful to the liver!
(naproxen)

"H2"
(Re face)
1 1
COOH
3 2 2 3
MeO
(Re face) (Si face)
(Si face) Priority by Chan-Ingold-Prelong (CIP) rules
"H2"
64
 Examples

AcHN COOMe (Re-face H 2 addition to alkene)

?
Ph H

O
N (Si-face H 2 addition to imine)
?

* P P *
* *

What stereochemistry is present at * ?

65
 Control of enantioselectivity
Use chiral, enantiopure metal catalyst [M]
H2
[M]-substrate (A) Product (PA)
– [M]
+ [M]
Pro-chiral substrate
H2
[M]-substrate (B) Product (PB)
– [M]
ΔG
ΔGA‡ ΔΔGA‡/B‡
ΔGB‡

B
A
ΔΔGA/B
PA PB
+ [M] + [M]

Curtin-Hammett Principle
If A and B are in fast equilibrium (relative to product formation) then the product
composition is determined by ΔΔGA‡/B‡ and not ΔΔGA/B or ΔGA‡ - ΔGB‡ 66
 Reaction profiles
ΔG ΔG

B B
A
A

PA PB PA PB
+ [M] + [M] + [M] + [M]

Not selective, PA/PB = 1 A is major diastereomer observed

during reaction and PA/PB > 1
ΔG ΔG

B
A B A

PA PB PA PB
+ [M] + [M] + [M] + [M]

Achiral metal catalyst A = B during reaction and 67

PA/PB temp dependant
 Chiral chelating ligands

P
P* * Rh View
*P * P
P P *
MeO OMe
* *

(R,R)-DIPAMP (R,R)-Me-DuPHOS
Me Me

O
PPh 2 P Rh P
* PPh 2 Ph 2P N
*

Me Me
(S)-BINAP (S)-iPr-PHOX

Steric bulk around coordination pocket

(quadrant diagram)
68
 Case study: Enamide hydrogenation
H
N CN H
[Rh{(R,R)-Me-DuPHOS}]+ N CN
Donating (R)-product
O H
group H H O Me
Alkene
Substrate binding?
Steric clash

Coord. Re-face Coord. Si-face

(major) (minor)

69
ΔG298K = 15 kJmol-1 (500 : 1)
 Case study: Enamide hydrogenation
Calculated energy profile:

ΔG ΔΔGRe‡/Si‡ = 18
ΔGRe = 85
kJmol-1
ΔGSi = 52

Low
Si
H
Re N CN
ΔΔGRe/Si = 15 O Me H

(S)-prod (R)-prod
+ [Rh] + [Rh]

Recall the rate determining step = activation of dihydrogen

Resulting calculated ee?
99.9%
70
 Case study: Enamide hydrogenation
Why such different barriers?

Coord. Re-face Coord. Si-face

Approach of dihydrogen from above H H H H

Is lowest energy pathway for both

Forced into Minor changes in

steric clash conformation

Major diasteromer Minor diasteromer

Minor product (S) Major product (R) 71

 Hydrogenation of carbonyl compounds
(we will focus on ketones)
H2

R' R'
[M] O [M] O H [M]+ [M] H δ– " H+ "
R R
H
R
R' δ+ O δ–
R' O
H2 + HO R'
HO H
H R R' R
R

“Inner sphere” “Outer sphere”

Coordination of the unsaturated substrate No direct coordination of the
(e.g. “mono-hydride” mechanism) unsaturated substrate

Alkenes > Ketones Ketones > Alkenes

Strongly coordinating double bond Polar double bond

(see exercise) 72
 Outer sphere hydrogenation – “ionic” mechanism
+

W Et
OC O
Ph 3P CO Et

– O=CEt 2
Turn over limiting

OH +
[Cp(CO) 2(PPh 3)W]
H2
Et
Et
H

Oxidative addition of
+ H dihydrogen. Cationic
[Cp(CO) 2(PPh 3)W] H [Cp(CO) 2(PPh 3)W] dihydride is acidic.
H Conjugate base is a
OH + OH relatively weak base.

Et + Et Et Et
O
Ketone is basic enough to
Ketone becomes significantly more deprotonate the dihydride.
Et Et
electrophilic and activated to hydride
transfer from the metal. 73
Outer sphere hydrogenation – “bifunctional” mechanism
H
Cl
P P NH
= diphosphine or amino
Ru Deprotonation
P bis-phosphine 2.176(1) Å
P N yields amido
NH2 H H2 group; remains
= diamine Ru(II)
NH2 + Base
– Base.HCl

OH
P NH
R R' Ru H2
H N
P amido
H H2
1.967(1) Å

O ‡
R H H
R'H P NH Amino ligand
Ru
H P N M NH 2R L type ligand
P NH H H2
Ru
P N Amido ligand
H H2
H Heterolytic M NHR LX type ligand
O H cleavage of
Concerted P NH
outer sphere Ru dihydrogen is
R R P N the RDS M NHR X type ligand
hydride and
H H2
proton
transfer 74
 Transfer hydrogenation of ketones
O H H Catalyst OH
+ X Y R' + X Y
R R' R
H

Mechanism (Outer sphere) Thermodynamics

O OH ΔGrxn = ΔG (desired hyd.) + ΔG (sacrificial dehyd.)

for ΔGrxn < 0: ΔG (desired hyd.) < ΔG (sacrificial hyd.)
Desired R'
R R' R Assuming ΔSrxn ~ 0, for ΔGrxn < 0:
H
ΔH (desired hyd.) < ΔH (sacrificial hyd.)

H H ΔH298K,g = +15 kJmol -1 H

CO 2+ H 2 OH
[M] L [M] L O

ΔH298K,g = -55 kJmol -1 H

O + H2 OH
H H
Sacrificial
X Y X Y
ΔH298K,g = -63 kJmol -1 H
O + H2 OH
Commonly carried out using 2-propanol
Ph Ph
or formic acid. Why?
(see exercise)
75
 Worked exercise
Pre-catalyst 1 effects the transfer hydrogenation of acetophenone in
2-propanol (in the presence of KOH).
(a) Draw the mechanism for this reaction.
(b) Predict the stereochemistry of the product
(c) Draw a free energy profile for the selectivity determining step

Ru 1, KOH H
NTs O OH
Cl Ph 2-propanol
H 2N Ph Ph
Ph
1

76
(a) Mechanism

77
Ru-NH2 = 2.117(9) Å Ru-NH = 1.897(6) Å Ru-NH2 = 2.110(1) Å

X-Ray structure of every species:

Angew. Chem. Int. Ed. EngI. 1997, 36, 285
78
(b) Product stereochemistry

Ru NTs
H H
H N Ph
O

Ph

Ru NTs
H H
H N Ph
O

Ph

79
(c) Free energy diagram

ΔG

Ph Me

OH OH

Ph Me Ph Me
(R)-alcohol (S)-alcohol

80
 Homogenous hydrogenation: Summary
• Activation of H2 generally requires a transition metal
– Extent depends on the metal-ligand composition
– Homolytic vs. heterolytic cleavage

• Alkene hydrogenation
– Typically inner sphere: hydride, mono-hydride, and olefin mechanisms that exploit strong
alkene coordination and MI reactions of hydride ligands.
– Importance of pre-catalyst activation by ligand dissociation

• Carbonyl hydrogenation
– Most effective process mediated in the outer sphere sphere: exploit polarity of the C=O bond
and concerted hydride and proton transfer reactions, following heterolytic H2 activation.
– Bifunctional ligands
– Transfer hydrogenation reactions possible (reversible reactions under thermodynamic control)

• Inner sphere vs. outer sphere and chemoselectivity

• Stereoselectivity possible using enantiopure catalysts
– Case study: use of chiral diphosphine ligands that lead to diastereomeric M-alkene
intermediates (can invoke Curtin-Hammett principle)
– Case study: use of chiral diamine ligands that lead to diastereomeric transition states

81
 Lectures 9 – 11:
Carbonyl containing products
• Hydroformylation of alkenes
• Methanol carbonylation: The Monsanto
and Cativa processes
• The Wacker process

82
 Hydroformylation of alkenes: Key issues

Linear (normal) Branched (iso)

• Elements of formaldehyde H2CO added to an alkene

• Co catalysed process developed in 1930s. Rh developed in 1970s
• Key issue – linear:branched (normal:iso) selectivity
– Linear most valuable
– When internal alkene feedstocks are used (e.g. 2-hexene), linear
aldehydes can still be produced via alkene isomerisation catalysis.
– Bulky ligands promote the formation of a linear metal alkyl intermediate
• Key issue – selectivity for hydroformylation over hydrogenation
– Rh process has similar catalyst to Wilkinson’s catalyst

83
Co catalysed hydroformylation

• The precatalyst is 1 but species 2 is the

resting state (from IR).

• Rate equation (note that this varies with

experimental conditions)

d[aldehyde] alkene Co [H3 ]

≈ 𝑘obs
d𝑡 [CO]

• On the basis of the above information,

suggest which is the RDS

84
Co catalysed hydroformylation
• Species 2 is only 5-coordinate, but we
expect 2à3 to be dissociative. Why?

• i-4 goes on to produce the branched

aldehyde via i-5 (not shown).Selectivity
is ~3:1 normal:iso. Why?
1. Sterics

2. Electronics

• Higher CO pressure improves

selectivity, but its not clear why (see
problem). Why not simply increase
[CO] to improve selectivity?

• How can we otherwise modify the

catalyst to improve n:i ratio?
85
Co catalysed hydroformylation

• Off-cycle reactions of 4?

• Note the proposed dissociation step

6à7 prior to the irreversible RE – this
may be the source of the -1 order in
[CO]
• What about direct reductive elimination
6à [CoH(CO)3]?

• This aspect of the mechanism differs

from shown in any source I have found,
but it does seem to be consistent with
the rate law and also with what we know
about cis-elimination.

86
 Alkene isomerisation

• Alkene feedstocks are commonly mixtures of isomers, predominantly…

• Alkene isomerisation, or “chain walking” is very common.
• Many processes that involve alkene hydrides like 3 are subject to isomerisation.
• _______________ alkenes are the more stable but ________________ alkyls undergo
faster migratory insertion.
87
 Phosphine-modified Co hydroformylation
• The industrial phosphine-free conditions are governed
by catalyst decomposition kinetics; if T is increased (to
increase the overall rate) the CO pressure needed to
prevent catalyst death (dotted arrow) becomes high.
– This is because step 8à2 has to be fast
• Increased CO pressure reduces the rate since µ [CO]-1
• Shell workers showed that addition of phosphines gave
much higher catalyst stability, but lower activity.
– Higher stability comes from P s-donation leading to
_______ MàCO back-bonding, so ____________
M-CO bonds. 8' will be more stable than 8 on
previous slides.
– Lower activity probably arises because CO loss is a
key step! (e.g. 7' is formed by loss of CO).
– Reductive elimination is not helped by presence of
phosphine, which stabilises higher OS (although
maybe the RDS has changed).
– Phosphines cause hydrogenation to become an
important side-reaction.
– Linear selectivity is enhanced (bulkier system
Compare with 7 & 8 on previous slides promotes linear product in 1,2-insertion step.) 88
Rh catalysed hydroformylation
The Rh catalysts system:
• posses higher catalytic activity; ≈ 1000 × Co
• much more stable than Co (longer cat lifetime)
• gives much higher, tuneable regioselectivity
• less hydrogenation

At low [H2] the formation of dimers like 1 becomes

important.
Rate equation under low [PPh3] and high [H2]
industrial conditions (orders are approximate):

d[aldehyde] Rh alkene
≈ 𝑘obs
d𝑡 [CO]

• 2 is observed by IR/NMR as resting state

• RDS…

89
Methanol carbonylation: Important feedstocks

Syngas

“Fischer-Tropsch” type

Monsanto

• Acetic acid and anhydride are needed on a large scale for

polymers, fibres, paints, dyes and pharmaceuticals.
• Previously synthesised via acetaldehyde oxidation
• 75% made by methanol carbonylation using the products of
Syngas and Fischer-Tropsch technologies (i.e. from
coal/methane)
• Fermentation is still used for foodstuffs
90
Monsanto Process: kinetics
• Resting state is 1 (IR), and:

d[CH3COI]
≈ 𝑘obs[Rh][MeI]
d𝑡

• What might the rate determining step be?

• Migratory insertion step is known to be

____ so…

• Anionic catalyst promotes OA. Why?

• Why use MeI rather than say MeBr?

91
Monsanto Process: MI and RE mechanisms
• The structure of 3 is expected on the basis of
the _________________ mechanism

• 3 is five-coordinate Rh(III), but does not

readily undergo RE because:

• The CO adduct 4 undergoes reductive

elimination to 1. Mechanism?

• Why do you think that a high pressure of CO

(30-40 atm.) is used if [CO] is not in the rate
equation?

92
Monsanto Process: co-catalysis & deactivation

• The feedstock is MeOH which is converted

by the co-catalyst HI to MeI.
• This is required because MeOH cannot
undergo OA (breaking C-O bond)
• Classic example of a co-catalyst cycle

• The HI causes corrosion – need to use

expensive alloy or glass-lined reactors

• Also, HI is probably responsible for the co-

production of acetaldehyde, and the
catalytically inactive 6.
• A we will see, the regeneration of catalyst
from 6 is one of the reasons that high
concentrations of water is used…

93
Monsanto Process: WGSR
• 6 eventually decomposing to
insoluble sludge of RhI3, but the
water gas shift reaction keeps the
catalyst alive. This is why high
[H2O] is used.

• Attack at CO by water only occurs

at 7 rather than 6. Why?

• 8 is reduced to 1 (curly arrows!)

• 1 undergoes OA with HI, as before

with MeI, to afford 9.

• Of course, WGSR happens

anyway, so long as there is water,
so low-water processes have been
developed to save on CO…

94
Cativa Process (BP, 1996)
• Uses Ir and is similar in mechanism to
Monsanto (and HI as co-catalyst, not shown)
• Resting state for this productive cycle is now
the OA product 2′ (from IR).
• The OA step is ~150 x faster than for Rh
– Stability of higher oxidation states for 3rd
row metal, lower electronegativity of Ir
• Rate equation is complex, but it is now
independent of [MeI].

d[CH3COI] Ir [CO]
≈ 𝑘obs −
d𝑡 [I ]

• Rate-limiting step is…

• There is an accompanying WGSR, not

shown here!
95
Cativa Process: Iodide is promoter and poison

• Problem – iodide is essential for catalyst

stability and forming the anionic nucleophile
1, but it slows the RDS.
• Need a species that will scavenge free iodide
but will not compete with the active species

96
The Wacker Process
• In the 19th century it was known that PdCl2
in water oxidises ethylene to acetaldehyde
(red bit) giving a Pd(0) metal precipitate.
• The key discovery (by Wacker Chemie
scientists) that made this catalytically
feasible is that acidified Cu(II) will oxidise
the Pd to Pd(II) again (blue bit)
• After the Pd(II) is reduced by the ethylene
it is quickly re-oxidised by two moles of
Cu(II). The Cu(I) product is air-sensitive
and is reoxidised itself to Cu(II) (black bit).
Pd(0) is not oxidised by air at a significant
rate under these conditions.
• Overall C2H4 + ½ O2 à CH3CHO $$$

97
 Nucleophilic addition

• Complexes of alkenes often undergo attack by external nucleophiles to

give metal alkyls
• This is used as the basis for production of millions of tons of aldehydes
p.a. in the Wacker Process.
• A range of other very important commodities are also produced in
similar processes, e.g. vinyl acetate.
• Compare the reaction of A with that between ethene and Br2.
• When the metal has a low electron count and free site, the mechanism
may be attack at the metal (see B) followed by the familiar 1,2-MI
98
Wacker (Schmidt) cycle: Outline
• This is a complex process and many
kinetic, synthetic and computational
studies have been performed. The
scheme here is now thought to be the
most important pathway at low [Cl-].
• The step 2 à 3 is an example of

• Now the complex is no longer negatively

charged so the alkene is more
electrophilic and undergoes
hydroxypalladation (3 à 4).
• For b-elimination (à6) a cis coordination
site is needed. The RDS is somewhere
between 4 and 6.

• Step 6à7 is an example of

• You will see a step like 7à8 in the

problems.

99
 Rate expressions and hydroxypalladation

The key controversy is over the

process of hydroxypalladation

• Both the outer-sphere anti

mechanism and inner-sphere syn
Outer sphere Inner sphere
mechanism are consistent with the
low [Cl-] rate law:

−d[C3 H; ] PdCl3>
; [C3 H; ]
=𝑘
d𝑡 H3O? [Cl> ]3

• Recent computational results

favour the outer-sphere anti
mechanism, but we will examine
both mechanisms.
• Another rate law operates at high
[Cl-] but we will not consider it.

100
 Wacker case study
With the Wacker catalyst at very high concentrations of chloride ions, 2-chloro-
ethanol or ethylene oxide is formed as a reaction product:

Consider the labelled substrate:

What product stereochemistry do you expect with the outer-sphere anti mechanism?

What product stereochemistry do you expect with the inner-sphere syn mechanism?

3′

101
 Early steps: trans effect
• We know 1 to be the resting state and it
reacts quickly with ethylene
• The step 2 à 3/3′ is governed by the
trans effect. The ligands in this system
are in the trans effect order:

Outer sphere Inner sphere and so _____ is preferred kinetically.

• ______ is more stable than ______ by

~60 kJ/mol so is favoured
thermodynamically (computational).

• This all means that the inner-sphere

mechanism can only be important
kinetically (it can only lead to a
reasonable amount of product) if the
subsequent hydroxypalladation is of
very low DG‡.

102
Outer/inner-sphere hydroxypalladation
Outer sphere
• The coordinated ethylene in 3 slips
towards h1 before attack of water.
• 3 is neutral, so there is less
_______________ than there is in
anionic 2.
• This, and the slip to h1 makes one
carbon atom more electrophilic.
• See video on Moodle

Inner sphere

• The addition and the deprotonation

take place simultaneously
• This inner sphere process has a
barrier 125 kJ/mol higher than the
outer sphere (computational).
103
 b-elimination

Video of b-elimination
available on Moodle

• The b-elimination step requires a cis coordination site, but the labile site is trans to the alkyl
(trans effect).
• T-shaped 5′ is more stable with trans Cl ligands than with cis 5 (trans influence!)
• The RDS for the catalytic reaction is probably the distortion of this structure to Y shape,
accompanied by coordination of the C-H bond in the planar transition state we need for b-
elimination. 104
 Releasing aldehyde
• The C-O bond has been formed with no change in Pd OS/VN
and 6 contains a tautomer of acetaldehyde.
• Why does it not simply get substituted by e.g. H2O to give the
product?

• The 1,2-MI step puts the Pd atom at the more substituted

carbon (4 à 6 à 7 is like the isomerisation mechanism we
looked at in hydroformylation).
• There are a few options for 7:
- b-elimination from the O atom, but this needs a free
coord site
- E2 type elimination with Cl- or solvent as base.

• Note the OS/VN of 8

• The aldehyde in 8 is a poor ligand, and is readily substituted to
give 9. This would decompose rapidly to “palladium black”
without….
105
 Carbonyl containing products: Summary

• Hydroformylation of alkenes
– Prototypical Co and Rh mechanisms involve 1,1-MI reactions of alkyl carbonyl intermediates.
– Rh more active and stable than Co catalysts, but use of bulky phosphine ligands leads to
enhanced production of linear products in both cases (cf. demands of 1° vs 2° alkyl ligands).

• Methanol carbonylation
– Monsanto (Rh) and Cativa (Ir) process: similar mechanisms, which both involve HI as a co-
catalyst and formation of organometallic intermediates by OA of MeI.
– Nucleophilic OA of MeI to Rh is the RDS in the former: in the latter this step is ~150x faster
and 1,1-MI of an alkyl carbonyl intermediate becomes the RDS

• The Wacker process

– Oxo functionality is introduced in an alternative manner to the above: via an initial
nucleophilic addition of water to a coordinated alkene ligand (outer-sphere
hydroxypalladation)

• Identification of resting state + kinetics

– Provides valuable mechanistic insights
– Not always the answer: often further insight can be gained by computational analysis

106
 Lectures 12 – 13:
Metathesis and polymerisation
• Alkene metathesis
• Alkyne metathesis
• Ziegler-Natta polymerisation

107
 Alkene metathesis
R1 R1
R2 [catalyst] R3

R3 R2
R4 R4
HOMO
• Used extensively in modern synthetic chemistry.
H 2C CH 2
• Equilibrium reaction, involving redistribution of alkene
substituents. H 2C CH 2

Concerted
• Requires metal catalyst.
reaction is
symmetry
• Reaction manifolds: forbidden
LUMO
Cross metathesis R2
R1 + R2 R1 +
R1
Ring closing metathesis R1
+
Ring opening metathesis R2
R2
Polymerisation
–
n

• How can these reactions be promoted? Ethylene loss, Relief of ring strain…. 108
 Alkene metathesis catalysts: A brief history
Schrock Mo Ru(NHC)
catalyst catalysts
Evidence for Chauvin
mechanism

1950 1960 1970 1980 1990 2000

Single component
Discovery catalysts developed
Chauvin Grubbs’s Ru
• Poorly defined multi- mechansim catalyst (1st gen)
component systems. e.g.
WCl6/Bu4Sn, 2005 Nobel Prize
WOCl4/EtAlCl2,
MoO3/SiO2, Re2O7/Al2O3
• Harsh reaction conditions,
difficult to initiate and
control reactions.
• Industrial applications:
Shell higher olefin process
(SHOP). 109
 Mechanism of olefin metathesis
• Which bonds are broken? Consider the “crossover” experiment:

D H H
[catalyst]
D 3C H C
CD3 + 3 CH3 2 D 3C CH3
D H D

The double bonds (the strongest bonds) are broken exclusively.

• How are the bonds broken? Chauvin’s mechanism:

H
[M] R' R'
R' [M] [M]
+ +
R R R R H R
R

• [2 + 2] cycloaddition reaction and cycloreversion reactions

• Carbene and metallacyclobutane intermediates

110
 Homogeneous alkene metathesis catalysts
H • Well defined single component catalysts
[M]
R • Based on metal carbene complexes

iPr

N N
PCy 3
F 3C N Cl
O iPr Cl
F 3C Mo Ru Ru
O Cl Ph Cl Ph
F 3C PCy 3 PCy 3
CF3
Ph

Schrock Catalyst Grubbs’ catalysts (1st and 2nd generation)

• Commercial ca £550/mmol • Commercial (I ca £60/mmol; II ca £280/mmol)

• High activity • Grubbs II significantly more active than Grubbs I

• Modest tolerance of functional • Good tolerance of functional groups

groups (Mo = oxophilic metal)
• Air (relatively) and moisture stable – variants
• Very air and moisture can by used in water
sensitive
111
 Carbene ligands

Triplet carbene = R R Singlet carbene =

Schrock carbene C C Fisher carbene
(when complexed) R R (when complexed)

sp2 hybridised carbon

N N N N
Cl
Ru
Cl Ph N-heterocyclic carbene (NHC)
PCy 3
– Persistent (can be isolated)
Why drawn different? – Strong σ-donors, poor π-acceptors

H N N
C M C C M
Ph N N

Double metal carbon bond (CBC ⇒ X2) Mesomeric Dative bond (CBC ⇒ L)
(FYI: Organometallics, 2011, 30, 3522) π-stabilisation 112
 Grubbs-type catalysts: A closer look

L L L
Cl Cl Cl
Ru Ru H2C Ru
Cl
Cl R Cl
R R
R
R
R R
Initiation R R

L L L
Cl – L' + R Cl Cl
Ru Ru Propagation H2C Ru
Cl Ph – Cl R Cl
Ph
L'

R
L L L
Cl Cl Cl
Ru Ru H2C Ru
Cl
Cl R Cl
H 2C R
All steps are reversible! R

Reversible coordination of R
2 R R +
L’ slows down catalytic
turnover! Net transformation

113
 Grubbs-type catalysts: A closer look
L L L L
Cl Cl Cl Cl
Ru Ru Ru Ru
R
vs Cl R
Cl
R Cl
Cl
R R
R R R

Degenerate [2 + 2]
Equivalent
cycloadditions

L L L L
Cl Cl Cl Cl
Ru CH2
Cl
Ru H2C Ru vs H2C Ru
Cl Cl Cl

R R R
R

114
 Grubbs-type catalysts: Initiation
• Probed using the following kinetic scheme. Why is the ethoxy-carbene more stable?

L k1 L L L
Cl – L' Cl k2 Cl fast Cl
Ru Ru Ru Ru + Ph
Cl Ph k-1 Cl Ph OEt Cl Ph Cl OEt
L' L'
EtO

• Data obtained:

N N
PCy3
Cl Cl
Grubbs I Ru Ru Grubbs II
Cl Ph Cl Ph
PCy3 PCy3

k1 0.3 s-1 0.003 s-1

@ 50oC
k-1/k2 13,000 1.25

• PCy3 promotes fast dissociation

• NHC ligand promotes cycloaddition 115

 Grubbs-type catalysts: Improvement
• Piers’ 14 VE catalyst

N N N N
Cl Cl
H+
Ru C Ru
Cl Cl PCy 3+
PCy 3

– No initiation required
– No ligands present during reaction
– Very reactive (difficult to handle)

• Grubbs-Hoveyda

N N N N
Cl R Cl
Ru Ru + O
Cl R
Cl
O

– Essentially irreversible dissociation of

co-ligand (weakly coordinating)

116
 Grubbs-type catalysts: Improvement
EtO 2C CO 2Et [catalyst] EtO 2C CO 2Et
• Comparison of catalytic activity in ring 1 mol%
closing metathesis (low temperature!) 0oC, CH 2Cl 2
+

N N
iPr
Cl
Ru
Cl PCy 3+ F 3C N iPr
F 3C O
Mo
Piers' 14VE catalyst O
F 3C
CF3
Ph
Schrock

N N
Cl
Ru
Cl
O
N N
Cl
Grubbs-Hoveyda
Ru
Cl Ph
PCy 3
Grubbs II

117
 Alkene metathesis applications

Grubbs-Hoveyda
J. Am. Chem. Soc. 2010, 132, 16805

Grubbs I
n

(Review, Angew. Chem. Int. Ed. 2010, 49, 34)

n
118
(Nature 2001, 409, 794)
 Alkyne metathesis
R1 R2 [catalyst] R1 R3

R3 R4 R2 R4

• Catalysts are less well developed compared to alkene metathesis

• Based on group 6 carbyne complexes (Mo, W)

• Similar mechanism: [2 + 2] cycloaddition reaction and cycloreversion

R' R' [M] R'

[M] R'
[M] [M]
+ +
R R R R R R R
R

• Example:

(CH 2) 4
(CH 2) 6 [(tBuO) 3W CMe]
O O
- MeCCMe
(CH 2) 6
(CH 2) 4

119
 Polyolefins from coordination polymerisation
• This accounts for the of the majority global thermoplastics & elastomer market of ~200 Mt.
• Polyethylene (PE) and polypropylene (PP) dwarf all other polymers in volume and total
value, although value/t and margins are low.
• They are simple, low energy polymers manufactured very efficiently with high atom
economy.
• We will be dependent on PE and PP for the foreseeable future.
• Most will be produced by heterogeneous Ziegler-Natta processes.

120
 Heterogeneous Ziegler-Natta

• Ziegler showed that a combination of Ti or Zr halides with Al alkyls give

heterogeneous catalysts for polymerisation of ethylene. Shared 1963 Nobel
Prize in Chemistry with Natta (tacticity control in PP).
• Several generations of catalyst, enabling productivity up to 104 gPE gcat-1
and stereoselectivity for iPP.

121
Cossee-Arlman mechanism
(enantiomorphic site control)

122
Chain termination mechanisms #1

123
Chain termination mechanisms #2

124
 Metallocenes: Commercial Relevance

• Metallocene based catalyst technology has revolutionized the very large polyolefin
industry, and also the organometallic chemistry of the early TMs
• Metallocene-derived polyolefins are penetrating a broad array of polymer markets.
– First in the higher priced specialty markets
– Next the high volume and commodity markets.
– New markets from new classes of polymer not available with conventional Ziegler-
Natta technologies.
• 20 million tons p.a. of metallocene based polymer is produced or >10% of the global
thermoplastics and elastomer market. Advantages over conventional Z-N include:
– Many catalysts are available that operate under similar conditions.
– The polymer properties can be changed rationally by changing the catalyst and
feedstock.
– One plant can produce many different products 125
 General polymerisation cycle
(Modified Green-Rooney mechanism)
H H
P
[M]

H ‡
H H H
CH2P P
–X P
[M] [M] [M]
X

H
H P

[M]

• The most active polymerisation catalysts typically have an “extra” empty

coordination site after alkene coordination
• The mechanism above adds to the Cossee-Arlman mechanism an a-agostic
interaction with that “extra” site. This is thought to tilt the sp3 alkyl towards the
alkene ligand and open up access to the alkene, thus promoting the 1,2-MI.
• Note the g-agostic interaction in the product which may have a role in slowing b-
elimination (terminating the chain). 126
 Metallocene activators: MAO

• Kaminsky (1976) discovered that partial hydrolysis of the AlMe3 produces a far
superior co-catalyst, now known as MAO (methylaluminoxane).
• Contains aluminoxane polymers, rings, clusters and some free AlMe3. Exact
composition and structure of MAO are still not entirely clear or well understood.

Chem. Rev. 2000, 100, 13391

127
 MAO and the alkyl cation

The functions of the MAO activator/co-catalyst appear to be to

1. alkylate the metal chloride precatalyst
2. Abstract “methide” Me-, leaving a highly electrophilic cation (the “alkyl cation”)
3. Provide a counter-anion that does not interfere with this electrophile
4. Scavenge the system for protic impurities

• Pyrophoric
• Expensive and wasteful (200-1000 equivalents are needed!)
• Leaves Al residues in polymer unless expensive work-up used

128
Stoichiometric activators

129
Chain-end versus enantiomorphic site control
Stereoerror

• The consequences of whether polymer stereochemistry results from site

control or chain-end control are significant.
• When the relative configuration is controlled by the last monomer
inserted, a “stereoerror” inverts the relative configuration of the
subsequent enchained monomers until another stereoerror is made.
• Enantiomorphic site control therefore is preferable and is the domain of
homogeneous catalysts.

130
 Ansa-Metallocene catalysts

Cl Me
X Zr X X Zr X X Zr X Si Ti
Zr Me
Cl N

t
Bu

Brintzinger Ewen CGC-Ti

• A wide range of metallocenes have been developed in which the Cp rings have been
connected together; the so-called ansa-metallocenes
• The purpose behind this is two-fold
– Since the rings are no longer free to rotate, chiral C2-symmetric metallocenes such as
the Brintzinger compounds can be made by placing substituents in appropriate
positions on the rings. Key early compounds contained tetrahydroindenyl ligands. This
leads to tacticity control in e.g. PP
– The bridge pulls the Cp rings back, opening the wedge a little and increasing
reactivity.
• The effects of the symmetry are very important; the growing polymer chain will orient itself
to avoid steric clashes, and the alkene (propylene) will orient itself so as avoid steric
clashes with the polymer and the ligands.
– The so-called Constrained Geometry Catalysts are fast but give poor tacticity control. 131
Iso- and syndio- specific PP mechanisms

132
 Metathesis and polymerisation: Summary

• Alkene metathesis
– Equilibrium reactions
– Chauvin’s mechanism: cycloaddition and cycloreversion steps; carbene and
metallacyclobutane intermediates
– Importance of pre-catalyst activation by (reversible) ligand dissociation
– Productive and degenerate cycloaddition

• Alkyne metathesis
– Catalysed by carbyne complexes via a similar mechanism to alkene metathesis.

• Ziegler-Natta Catalysis
– Heterogeneous and homogenous mechanisms: both involving 1,2-MI reactions of
metal alkyls and alkene coordination.
– Metallocene alkyl cations: catalysts generated by alkylation and methide abstraction
– Important role of agostic interactions in these processes
– Stereoregular polymerization engineered by design of ancillary ligands

133
 CH3F0: Advanced Inorganic Chemistry

Fundamentals of catalysis and metal-centred reactions

Professor Richard Walton

Segment 1: Concepts and Definitions

 Heterogeneous Catalysis
Homogeneous Heterogeneous

Single Phase Multi-Phase

substrate(s) + catalyst solid catalyst + liquid/solution substrate(s)

dissolved in solvent OR solid catalyst + gaseous substrate(s)
 Importance of Heterogeneous Catalysis
Chemical Industry
>90% of global chemical output relies on heterogeneous catalysts
(refining petroleum and gas; production of ammonia; SO2 oxidation, etc.)

Economics
~ 20% of world GNP is dependent on these process and their products
>$10,000 billion per annum
global catalyst market size was valued at $33.9 billion in 2019

Environmental Aspects
• Ozone depletion catalysed over aerosol surfaces (particulate matter) in
stratospheric clouds
• Pollution control is now legislated (catalytic converters; destruction of organic
contaminants)
• Clean (‘green’) synthesis is required (benign solvents, low temperature) for large-
scale manufacture of chemicals
Most heterogeneous catalysts are metal containing, inorganic solids
 Nature of Heterogeneous Catalysts
Uniform Multi-Phase
Single Phase Active species + support
e.g. crystalline particle

surface of a
porous metal particle
aluminosilicate metal nanocrystals on
zeolite (see later) carbon support porous particles
in ceramic matrix

J.M. Thomas, Angewandte Chemie International Edition in English, 127 (1988)

1673-1691 https://onlinelibrary.wiley.com/doi/abs/10.1002/anie.198816731
 Example of Active Sites
IUPAC definition:
“sites for adsorption which are the effective sites for a particular heterogeneous catalytic reaction”

H H H
O O O Al Al Al
Al Al Al Al O O O O
Al2O3 Al2O3

Brønsted acid sites Lewis acid sites

Tethered
edge
corner organometallic

faces

Elemental metal crystal (e.g. Fe)

Silica surface
 CH3F0: Advanced Inorganic Chemistry

Fundamentals of catalysis and metal-centred reactions

Professor Richard Walton

Segment 2: Binding of molecules at surfaces

Heterogeneous Catalysis: Surface Chemistry
Heterogeneous Catalysis: Surface Interaction (Adsorption)

(1) Physisorption

(2) Chemisorption
 Examples of Surface Binding Modes

See Inorganic Chemistry, 7th Edition, Page 801

 Optimising Heterogeneous Catalysis

Sabatier principle:
Qualitative consideration of binding between
substrate and solid catalyst and the rate of reaction

Considers that an unstable intermediate is formed

between substrate and catalyst surface

Strong binding = favourable formation of surface complex, but product is not released

Weak binding = no interaction and no reaction

P. Sabatier, Ber. Deutch. Chem. Soc., 44, 2001 (1911)

 Example: Decomposition of Formic Acid
W. J. M. Rootsaert, W. M. H. Sachtler,
HCOOH CO + H2O Z. Phys. Chem. 26 (1960) 16.
Catalyst = M

350 Pt Ir

Pd
400 Ru
Rh
T/K Cu
450
Ni

Au Ag
500 Co
Fe
Au
W
550
240 280 320 360 400 440
-1
Hf / kJmol

‘Volcano plot’ (Baladin, Adv. Catal. Rel. Subj. 19 (1969) 1)

 CH3F0: Advanced Inorganic Chemistry

Fundamentals of catalysis and metal-centred reactions

Professor Richard Walton

Segment 3: Surface Reactivity

 Example: Hydrodesulfurization of Dibenzothiophene
H2
+ + + H 2S
Catalyst = MSx

H. Toulhoata, and Pascal Raybaud, Journal of Catalysis 216 (2003) 63–72

 Heterogeneous Catalysis: Bimolecular Reactions
Bimolecular Reaction A(gas) + B(gas) → C(gas)

Langmuir-Hinshelwood Eley-Rideal

bimolecular rate determining step: unimolecular rate determining step:

co-adsorption of both substrates adsorption of one substrate

A(gas) + B(gas) → A(ads) + B(ads) A(gas) → A(ads)

A(ads) + B(ads) → C(ads) A(ads) + B(gas) → C(ads)

C(ads) → C(gas) C(ads) → C(gas)

 Heterogeneous Catalysis: Bimolecular Reactions
Bimolecular Reaction A(gas) + B(gas) → C(gas)

Langmuir-Hinshelwood Eley-Rideal

A and B compete for binding sites Only A is adsorbed

Are All Crystal Surfaces the Same?
 Labelling of Crystal Surfaces
Miller indices: summary of CH272 (Solid-State Materials)

Miller plane (hkl) intersects a unit cell edge at a/h

b unit cell edge at b/k
c unit cell edge at c/l
where, h, k, l are integers

Intersects a at 1/2

Intersects b at 1/1

Intersects c at 1/2

(212) Miller plane

y
z

x
 Definition of Planes within a Unit Cell
Plane (hkl) is one of a set that run parallel including one that passes through the origin

y
z
x
{212} Set of Miller planes
 Definition of Planes within a Unit Cell
Plane (hkl) is one of a set that run parallel including one that passes through the origin

y
z
x
(212) Surface if crystal is terminated here
 Surface Reactivity Depends on Crystal Face

FCC
Surfaces
(Ni)

2.48 Å 3.51 Å 2.48 Å

2.48 Å 3.51 Å 2.48 Å

2.48 Å
 Surface Reactivity Depends on Crystal Face
Ethene adsorption on FCC Ni metal: dehydrogenation of ethene

Strain of ethene depends on Ni—Ni distance

 CH3F0: Advanced Inorganic Chemistry

Fundamentals of catalysis and metal-centred reactions

Professor Richard Walton

Segment 4: Surface Area

 How to Prepare High Surface Area Solid Catalysts?

(1) Ball milling

Mechanical grinding of large particles

(2) Solution growth of inorganic particles

Rapid precipitation

Hydrothermal

(3) Gas phase

Rapid combustion of volatile reagents - flame pyrolysis

(4) Porous materials (see later lectures)

 Surface Area Calculation 1
Consider a cube 10 × 10 × 10 nm3. Compare the surface area of this cube to
1 × 1 × 1 nm3 cubes that occupy the same volume.
 Surface Area Calculation 2
What is the specific surface area of Fe2O3 (r = 5.24 gcm-3) made up
of 1 nm3 cubes?
Advantages / Disadvantages of Heterogeneous Catalysts
(compared to homogeneous)
Advantage Disadvantage
 CH3F0: Advanced Inorganic Chemistry

Fundamentals of catalysis and metal-centred reactions

Professor Richard Walton

Segment 5: Example of industrial catalysts 1

Advantages / Disadvantages of Heterogeneous Catalysts
(compared to homogeneous)
Advantage Disadvantage
easy separation of catalyst from mechanism difficult to study:
products multiphase so various
techniques needed that are
surface sensitive
catalyst easily recycled deactivation by ‘clogging’ of
surface with products or
byproducts
can be used over wide only surface is active: inefficient
temperature and pressure use of materials
range
continuous process possible: if particles grow or change
fixed catalyst and flow of shape during use then activity
substrate lost
tunable properties from surface
area and particle shape
Examples of Industrial Heterogeneous Catalysis
1930 - 1970
Examples of Industrial Heterogeneous Catalysis
After 1970
 Ammonia Synthesis (1909)
N2 + 3H2 2NH3 DH(forward) = - 92 kJ mol-1

• production of artificial fertilizer.

Haber – Bosch process:
• also explosives, dyestuffs, plastics, and drugs
Fe catalyst
400 °C • in environmental catalysis as reducing agent
15 MPa
for nitrogen oxides emitted from power plants
and diesel vehicles

N2 has low sticking probability

H2 adsorbs and dissociated rapidly

Fritz Haber Carl Bosch

Nobel Prize 1918 Nobel Prize 1931
 Haber – Bosch: Mechanism
* = Surface site

NN bond strength 942 kJ mol-1

H-H bond strength 432 kJ mol-1

Ammonia Synthesis: Fe(111) most reactive
Fe(111) > Fe(100) > Fe(110) note: Fe is BCC
Three-Way Catalysis: Automotive Exhausts

precious metals Rh/Pt

ceria (CeO2)
γ-alumina (Al2O3)
cordierite monolith
 Three-Way Catalysis 1: Oxygen Concentration

Control of oxygen levels: CeO2

CeO2 CeO2-x + x/2 O2

 Three-Way Catalysis 2: Role of Precious Metal
(1)

(2)

(3)
Metal-Surface Catalysed Transformations

(1) Rh: CO oxidation

(2) Pt/Al2O3: hydrocarbon oxidation

(3) Pt: NO reduction to N2

 Three-Way Catalysis 3: Support

High Surface Area Support

High surface area: dispersion of catalyst

Flow of gases over catalyst optimised

High temperature operation (> 500 C)

cordierite (Mg,Fe)2Al3(Si5AlO18) monolith

 CH3F0: Advanced Inorganic Chemistry

Fundamentals of catalysis and metal-centred reactions

Professor Richard Walton

Segment 6: Example of industrial catalysts 2

 Hydrogen Production and Purification
Steam Reforming of Hydrocarbons:

CnHm + nH2O nCO + (n+m/2)H2 ‘Syn Gas’

Ni catalyst
supported on Al2O3
450 oC – 950 oC

Water
adsorption
enthalpy

HC adsorption energy
Jones et al. Journal of Catalysis 259 (2008) 147–160
 Hydrogen Purification: ‘Water Gas Shift’

CO + H2O CO2 + H2 DH(forward) = - 41 kJ mol-1

high temperature shift catalyst

oxides of iron and chromium
400–500 °C
CO reduced to < 2–5%.

low temperature shift catalyst

copper oxide, zinc oxide and alumina
200 and 400 °C
CO reduced to < 1%
 Hydrogen Purification: ‘Water Gas Shift’
An alternative low temperature catalyst: Au/CeO2

CO + H2O CO2 + H2

Chen et al. Faraday Discuss., 152 (2011) 121-133

 Hydrogen Purification: ‘Water Gas Shift’
An alternative low temperature catalyst: Au/CeO2

CO + H2O CO2 + H2

Redox chemistry of CeO2

 Oxidation Catalysis: Large-Scale Organic Chemistry

Catalyst = vanadium oxide

Temperature ~ 400 oC

Wachs, Dalton Trans., 42 (2013) 11762

 Vanadium Oxide Oxidation Catalysis

O OH HO OH
+ H+
V V
O O - H+ O O

+ H 2O - H2 O
+ ½ O2 - ½ O2

OH O
V V
O O - H+ O O

+ H+

Bond, Journal of Catalysis 116 (1989) 531

 Heterogeneous Catalysis: Key Points
 solid/liquid, solid/gas reactions used on large industrial scale

 uniform or multiphase catalysts are possible – each with specific active sites

 various active sites are possible: acid (Lewis and Brønsted), redox, metal surfaces…

 kinetic models / mechanism arise from consideration of adsorption of molecules at surfaces

 Sabatier principle/volcano plots relate catalysis to binding affinity of molecules

 equilibrium position can be shifted by temperature/pressure: an additional effect to catalysis

 surface binding sites on metals may depend on which crystal face is presented

LEARNING OUTCOME:

You should be able to interpret data/observations (unseen) on heterogeneous catalysis based

on the above considerations, in a qualitative way.
 CH3F0: Advanced Inorganic Chemistry

Fundamentals of catalysis and metal-centred reactions

Professor Richard Walton

Segment 7: Introduction to porous materials

 Porous Materials

1D pores: 2D pores: 3D pores:

parallel to one axis parallel to two axes parallel to three axes
non-intersecting intersecting intersecting

zig-zag
channels
 Classification of Porosity

IUPAC recommendations

Diameter (d) of pore defines scale of porosity

(1) Microporous d < 2 nm

(2) Mesoporous 2 < d < 50 nm

(3) Macroporous d > 50 nm

http://goldbook.iupac.org/P04762
ZEOLITES: Chemical Composition
MxDy[Al(x+2y)Si(n-(x+2y))O2n].mH2O

[Al(x+2y)Si(n-(x+2y))O2n](x+2y)-

aluminium silicate framework

M+ monovalent metal cation

D2+ divalent metal cation

exchangeable cations

Loosely bound H2O

Zeo-lite = ‘boiling stone’

 CH3F0: Advanced Inorganic Chemistry

Fundamentals of catalysis and metal-centred reactions

Professor Richard Walton

Segment 8: Zeolite examples

ZEOLITES: Chemical Composition
MxDy[Al(x+2y)Si(n-(x+2y))O2n].mH2O

[Al(x+2y)Si(n-(x+2y))O2n](x+2y)-

aluminium silicate framework

M+ monovalent metal cation

D2+ divalent metal cation

exchangeable cations

Loosely bound H2O

Zeo-lite = ‘boiling stone’

‘Zeolite A’: Structure

O
Si
Al
Na

View along [100]

 ‘Zeolite A’: Crystal Data
Fm-3c (226)
a = 24.5528(2) Å
Atom Multiplicity x y z Occupancy
Si 96 0 0.0931 0.1851 1
Al 96 0 0.1874 0.0903 1
O1 96 0 0.1122 0.2444 1
O2 96 0 0.1493 0.1419 1
O3 192 0.0511 0.0616 0.1711 1
Na1 64 0.1014 0.1014 0.1014 1
Na2 96 0 0.226 0.213 0.25
Na3 96 0.129 0.129 0.25 0.08
O4 48 0.154 1/4 1/4 0.20
O5 192 0.047 0.269(2) 0.287 0.15

“A synchrotron powder diffraction study of Na-LTA”

Hasegawa et al. Japanese Journal of Applied Physics (1999) 38 65-68
‘Zeolite A’: Composition
 ZEOLITES: Structures 1
Corner-sharing {AlO4} and {SiO4} tetrahedra

Al Si-O = 1.61 Å

Al-O = 1.75 Å

Si

primary building units

PBUs
 SiO2 Polymorphs

alpha-quartz (low) coesite

 ZEOLITES: Structures 2

4-ring

6 - ring

Double 4-ring

‘4-4’ or ‘D4R’

secondary building units Double 6-ring

SBUs ‘6-6’ or ‘D6R’

ZEOLITES: Secondary Building Units

23 unique SBUs
ZEOLITES: Structures 3
Larger structural units

The sodalite (b) cage

ZEOLITES: Structures 3
Larger structural units

The sodalite (b) cage

 Zeolite A: Simplified Structure

Sodalite cages linked by double-four-ring units  8-ring window

 Sodalite

Sodalite cages shared by 4-ring faces

 Zeolites X and Y ‘Faujasite’

Sodalite cages linked by double-six-ring units  12-ring window

 CH3F0: Advanced Inorganic Chemistry

Fundamentals of catalysis and metal-centred reactions

Professor Richard Walton

Segment 9: Classification of zeolite structures

 Zeolite A

Sodalite cages linked by double-four-ring units  8-ring window

Na96[Al96Si96O384].xH2O
 Classification of Zeolite Structures

241
Unique
Ordered
Frameworks

International Zeolite Association: http://www.iza-online.org/

 “Window-size” of zeolites

Si/Al ring size Maximum Aperture

4 2.6 Å
6 3.6 Å
8 6.3 Å
12 7.4 Å

Cage diameter of zeolites

Sodalite Cage: 6.6 Å

Zeolite A supercage: 11.4 Å

Faujasite supercage 11.8 Å

 Pore Structure of Zeolites
combination of window size and cage size
Zeolite A LTA
entrance to supercage through 8-ring windows

WINDOW

D4R

sodalite cage
supercage
 Surface Areas of Zeolites
Measured using gas adsorption

Zeolite External Surface Total Surface

Area / m2g-1 Area/ m2g-1
Ca-A 0.9 790
H-Mordenite 3.6 576
NaX 4.6 902
NaY 3.7 886

Suzuki et al. J. Catal. 100 (1986) 219

 Framework Densities
28

Framework density (T atoms per 1000 Å )

3
quartz
26

24
cristabolite
22
scapolite
20 BIK
JBW
18 ANA MFI
MOR
SOD STT MEL CAN
DON
16 MER BOG
GIS BEA
CHA MEI
14 RHO
EMT
LTA
12 TSC FAU

5 6 7 8 9 10 11 12 13 14 15
Largest Channel (number of T atoms)
 ZSM-5 / Silicalite (MFI)

5-1 SBU

Pentasil building block

 ZSM-5 / Silicalite (MFI)
Linked
Pentsil
Units

Three-dimensional Structure:
 ZSM-5 / Silicalite (MFI)

10-ring
window

Pore
system
 CH3F0: Advanced Inorganic Chemistry

Fundamentals of catalysis and metal-centred reactions

Professor Richard Walton

Segment 10: Zeolite synthesis

 Synthesis of Zeolites
Hydrothermal Synthesis
In Nature... In the laboratory ...

Teflon-lined steel autoclave

“heterogeneous reactions in aqueous media above 100 oC and 1 bar”[1]
non-aqueous solvents: solvothermal or solvatothermal

[1] A. Rabenau, Angew. Chem. Int. Ed. Engl. 24 (1981) 1026

 Synthesis of Zeolites: Reagents
5 components needed: one of each of the following

Al Source Si Source Solvent Counter-cation Mineraliser

Al2O3 SiO2 H2O Na+, K+, Rb+, Ca2+… OH-
Al(OiPr)3 Si(OEt)4 alcohol R4N+ (alkylammonium) F-
NaAlO2 Na2SiO3 amine

Reaction temperature: 100 – 200 oC

Reaction pressure: 1 – 20 bar (autogeneous)
Typical reaction times: hours – days

http://www.iza-online.org/synthesis/
 Organic Cations in Zeolite Synthesis

Cs+ Rb+ K+ Na+ Li+

1,3,4-trimethylimidazolium TPA+ TEA+ TMA+

Larger size, but same charge  fewer cations per cage

silicon rich (‘high silica’) zeolites
 Organic Cations in Zeolite Synthesis

Branched Molecules:
SDA = Structure Directing Agent intersecting channels
 Organic Cations in Zeolite Synthesis

Linear Molecules:
Linear channels

Spherical Molecules:
Large cages
SDA = Structure Directing Agent
 Tetrapropylammonium “template” in ZSM-5

SDA = Structure Directing Agent = “Template”

Mechanism for the Formation of High Silica Zeolites
Si clustering
+ O +
N
OH- N O
Si
F-
O O O O
Si Si +
N
O O
O O
nucleation
solution interactions condensation
(hydrophobic)

Burkett and Davis (1995) crystal growth

 Selectivity of template?

1 template = 3 different zeolites?

 Uniqueness of template?
ZSM-5 (MFI)
TPA
TEA
Tri-propylamine
EDA
Ethanolamine
Propanolamine
Methylquinuclidine
Alcohols 22 different
Glycerol
n-propylamine Templates
Di-n-butylamine
Di-n-propylamine possible!
1,5-diaminopentane
1,6-diaminohexane
Morpholine
Pentaerythritol
Dipropylenetriamine
Dihexarnethyle netriamine
Triethylenetet raamine
Diethylenetriamine
1-alkyl, 4-aza, 1 azoniabicyclo[2,2,2]octane, 4-oxide, halide
Hexanediol

Lok et al. Zeolites 3 (1983) 282

 Role of Fluoride in Zeolite Synthesis

five-coordinate
silicon

Zeolite STF
D4R zeolites made using fluoride Fyfe et al. J. Am. Chem. Soc., 2002, 124, 7770
 Calcination of As-Made Zeolite

F
F
T ~ 300 oC

F F
-NR4F
or NR4OH

[SinO2n] NR4+F- [SinO2n]

porous zeolite
 CH3F0: Advanced Inorganic Chemistry

Fundamentals of catalysis and metal-centred reactions

Professor Richard Walton

Segment 11: Applications of zeolites

 Applications of Zeolites

Ion-Exchange:

Separation of Ions

Molecular Sieving:

Separation and Storage of Molecules

Catalysis:

Selective Transformation of Organic Molecules

 Location of Cations in Zeolites
Na1 – O
3 x 2.3 Å
3 x 2.9 Å

Na2 – O
2 x 2.6 Å
sodium shows a 3.9 Å
range of oxygen distances:
2.9 Å
framework oxides +
water molecules

Various possible Na+ locations in zeolite structure  mobility?

 Ion-Exchange by Zeolites

MxDy[Al(x+2y)Si(n-(x+2y))O2n].mH2O
M+ D2+ : exchangeable cations

Ca2+(aq) Water softening 2 Na+(aq)

HARD WATER SOFT WATER

 Ion-Exchange by Zeolites

pH control water softening

Capture of toxic or radioactive ions

e.g. 137Cs+ and 90Sr2+

Porosity of
Zeolites
Higher
aromatics

4 5 6 7

Critical Molecular Dimension / Å

A FER ZSM-5 MOR X,Y

4 5 6 7

Average Channel Size / Å

Diffusion of Molecules through Zeolites
Diffusion of Aromatics Through FAU

FAU
 Activation Energy of Diffusion in ZSM-5

Diffusion coefficient / cm2s-1

1/T (K-1)
Activation energies for diffusion (kJ mol-1):
2-methyl 2-methyl benzene 2,3 dimethyl cyclohexane 2,2 dimethyl
butane pentane butane butane
31.9 36.0 40.6 60.3 64.9 69.8
 CH3F0: Advanced Inorganic Chemistry

Fundamentals of catalysis and metal-centred reactions

Professor Richard Walton

Segment 12: Binding of molecules in zeolites

 Problem 2 for Workshop
Explain the diffusion coefficients of hydrocarbons through ZSM-5
Diffusion coefficient / cm2s-1

Critical molecular diameter / Å

 Problem 3 for Workshop
Explain the trends in diffusion coefficients of hydrocarbons through mordenite (400 K)

Molecule Diffusion Coefficient/ 10 -10cm2 s-1

Methane 154
n-butane 16
iso-butane 7.6
perfluorobutane 6.9
 Strong Binding Sites in Zeolites

pyridine in zeolite K-L

drying agent/
capture of pollutant molecules
capture of odorous
molecules
 Strong Binding Sites in Zeolites
Non-crygenic air separation (Pressure Swing Adsorption)

PRESSURE
Cu+ [zeolite](s) + N2/O2 Cu+ [zeolite] [N2](s) + O2

N2 and O2 have very similar critical radius 95 %

separation
NN is quadrupolar and binds strongly to Cu+
Molecular Seives in Industry
 Problem 4 for Workshop
Explain the following graph showing uptake of hydrocarbons by cation-exchanged LTA
 Summary of Adsorption by Zeolites
(1) Cations present provide ion-exchange properties
but fill space, limiting porosity

(2) Si:Al ratio defines framework charge.

High Si content means fewer extra-framework cations

(3) Size/shape of molecules vs zeolite pore size affects

their diffusivity

(4) Temperature enhances diffusivity via thermal motion

of molecules and zeolite framework

(5) Polarity of molecules with close size match to zeolite pores

slows their diffusion

(6) Strong binding sites in large cages leads to highly selective

adsorption at equilibrium
 CH3F0: Advanced Inorganic Chemistry

Fundamentals of catalysis and metal-centred reactions

Professor Richard Walton

Segment 13: Zeolites as catalysts

 Zeolites as Solid-Acid Catalysts
Na+ Na+ Na+
O O - O O - O O - O
Si Al Si Al Si Al
O O O O O O O O O O O O

Ion-exchange

NH4+ NH4+ NH4+

O O - O O - O O - O
Si Al Si Al Si Al
O O O O O O O O O O O O
Heat
-NH3

H+ H+ H+
O O - O O - O O - O
Si Al Si Al Si Al
O O O O O O O O O O O O
Zeolites as Solid-Acid Catalysts
 Transition-Metal Zeolite Catalysts

Framework

Mn+ Mn+
O O - O O - O O - O
Si Al Si Al Si Al
O O O O
Extra-Framework O O O O O O O O
Shape-Selectivity in Zeolite Catalysis-1
 Shape-Selectivity in Zeolite Catalysis-2

CH3OH
Shape-Selectivity in Zeolite Catalysis-3

2
Examples of Zeolites in Industrial Catalysis
Petroleum Cracking
FAU
Zeolite

'Fluid Catalytic Cracking'

 Petroleum Cracking in Context

In 2018, the global refining catalyst market

was estimated at $2.9 billion USD

~ 4 million tonnes per year synthesised

0.16 kg of FCC catalysts are used for the

conversion of a barrel of feedstock

La2O3/zeolite Y catalyst
 FCC catalyst is multicomponent

Vogt and Weckhuysen Chem. Soc. Rev., 44 (2015) 7342-7370

 Problem 5 for Workshop
The aluminosilicate zeolite mordenite (Si:Al = 200:1) was used as a catalyst for the
isopropylation of isopropyl-naphthalene (IPN) isomers using propene at 250 °C. Mordenite is
a Lewis acid that has a structure with channels limited by 12-ring windows. The table below
contains information concerning its catalytic activity.

Reactant Conversion to Major Product(s)

diisopropyl-
naphthalenes
2,6-DIPN (60 %)
2-IPN > 80 %

2,7-DIPN (30 %)

1-IPN < 5%
-

(1) Rationalise the data in the table.

(2) Explain why use of a high aluminium mordenite was used for the same catalytic
transformation gives low conversion and a complex mixture of products containing isomers
such as 2,5-DIPN.
 CH3F0: Advanced Inorganic Chemistry

Fundamentals of catalysis and metal-centred reactions

Professor Richard Walton

Segment 14: Zeotypes

 Porous (Nanoporous) Materials: A Time-Line
1756 Crönstedt zeolite = “boiling stone”

1862 St Claire Deville zeolite synthesis

1930-40s Systematic zeolite synthesis (Barrer, London)

1948 Zeolite A novel framework (Milton USA)

1970s Siliceous zeolites e.g. silicalite

1982 Aluminium phosphates (AlPOs)

1990s Microporous oxides, fluorides, sulfides …

Transition metals, Groups 2, 13 -16, actinides …

1990s Mesoporous silicas

2000s Metal-Organic Frameworks (MOFs)

2010s Covelant Organic Frameworks (COFs)

 Zeotypes

analogue of silicate zeolite with other chemical elements

Zeolite: MxDy[Al(x+2y)Si(n-(x+2y))O2n].mH2O

Siliceous Zeolite: [SiO2][NR4F]

Si(IV)O2 = Si(IV)2O4 = Al(III)P(V)O4

New microporous materials?
“AlPO-5” [Al12P12O48](C12H28N+)(OH-)(H2O)x

Wilson et al. 1982 (patent)

Tetrapropylammonium SDA
12-ring channels
No silicate analogue
 AlPOs: templating effect?

Computer design of SDA to fit desired zeolite structure:

‘Zeolites by evolutionary de novo design’ = ZEBEDEE

Lewis et al. Nature, 382 (1996) 604

 AlPOs: no unique template

Lok et al. Zeolites 3 (1983) 282

Gallium Phosphates: Greater Structural Variety

10-ring channels 20-ring windows

pyridinium template solely octahedral gallium
[C5H5NH]+[CoGa2P3O12]- Ga4(HPO4)2(PO4)3F3.[H3N(CH2)4NH3]2.4H2O

(1994) (2000)
 Applications of Phosphates?
(Co,Mn)AlPO-18 (AEI type)

selective
terminal
oxidation

“Molecular-sieve catalysts for the selective oxidation of linear alkanes by

molecular oxygen”
Thomas et al. Nature 398 (1999) 227
ND-1 zinc phosphate with 24-ring windows (1999)

porosity
with
organic
SDA
present

1,2-diaminocyclohexane template
Channel Sizes of Microporous Materials (1998)
 Giant Pores in Zinc-Gallium Phosphite Materials

Lin et al. Science 15 Feb 2013: Vol. 339, Issue 6121, pp. 811-813
 CH3F0: Advanced Inorganic Chemistry

Fundamentals of catalysis and metal-centred reactions

Professor Richard Walton

Segment 15: Mesoporous materials

Larger SDAs : Self-Assembled Molecules

a, Cone-shaped surfactant resulting in b, normal

micelles. c, Champagne cork shaped surfactant
resulting in d, reverse micelles with control of their size
by the water content. e, Interconnected cylinders. f,
Planar lamellar phase. g, Onion-like lamellar phase.
 Mesoporous Silicas
Proposed mechanism for the templating of a silica using surfactants

(1)

(2)/(3)

1: formation of template array

2: hydrolysis of TEOS to form silicate TEOS = Si(OEt)4
3: calcination: removal of template
 Surfactants
Surfactant Templating conditions
Cationic Alkaline
e.g. hexadecyltrimethylammonium bromide
Acidic

Anionic Alkaline
e.g. sodium dodecylsulfate
O Acidic
O
S
O
O Na
Neutral Neutral
e.g. Dodecylamine

Non-ionic Acidic
e.g. alkyl-polyoxyethylene ether

Neutral

triblock copolymers (e.g. Pluronic®)

 Characteristics of Mesoporous Silicas

Electron Microscopy of ‘MCM-41’

Amorphous SiO2 walls : ordered porosity

Pore diameter = 2 - 9 nm Surface area > 1000 m2g-1
Pore Structures of Mesoporous Silicas

hexagonal cubic

disordered
Mesoporous Silicas as Catalyst Supports

Internal surface is terminated

by silanol groups: Si-OH
Mesoporous Silicas as Catalyst Supports

FePt nanoparticles inside ordered

mesoporous silica SBA-15
 CH3F0: Advanced Inorganic Chemistry

Fundamentals of catalysis and metal-centred reactions

Professor Richard Walton

Segment 16: Metal-Organic Frameworks

Metal-organic framework materials (MOFs)
Hybrid organic-inorganic solids

‘coordination polymers’

metal polyhedra or clusters: ‘building units’

polydentate organic linkers: carboxylates / amines

 Metal-organic framework materials (MOFs)
Definitions (IUPAC 2013)

(1) ‘coordination polymer’ = a coordination compound with

repeating coordination entities extending in 1, 2 or 3 dimensions

(2) 'coordination network' = coordination compounds that

extend through repeating coordination entities with cross links
between two or more individual coordination entities

(3) 'metal-organic framework' = a coordination network with

organic ligands containing potential voids.’

www. iupac.org/web/ins/2009-012-2-200
 MOF Example 1

Cu-BTC (HKUST-1)

Connected in 3 dimensions by organic links (metal oxide clusters)

I0O3
MOF Example 2

MIL-53

Connected in 2 dimensions by
organic links

Metal oxide chains in third direction

I1O2
 Structural Flexibility of MIL-53

temperature ~14 Å
~7 Å pressure
solvent

‘hinge’

‘wine-rack’ mechanism
Common Ligands for MOF Synthesis

squaric muconic
acid acid (trans, trans)

Polydentate carboxylates / carboxylic acids

Azoles Multi-Functional Ligands

POLYDENTATE LIGANDS
Example of Synthesis: MOF-5

I0O3
 ‘Isoreticular’ MOFs

MOF-5
IRMOF-16
 Important Examples of MOF Chemistry
Ultrahigh Porosity

~10 nm

Yaghi and co-workers

Science July 2012
SURFACE AREA > 10,000 m2g-1!
 Catalysis by MOFs
(1) Lewis Acidity (2) Brønsted Acidity

MIL-101-SO3H
Cu-BTC (HKUST-1)

Schlichte et al. Microporous and Mesoporous

Materials, 73 (2004) 81 Zhou et al. Chem. Eur. J., 20 (2014) 14976
 Catalysis by MOFs
(3) Oxidation Catalysis

Liu et al. J. Phys. Chem. C, 114 (2010) 13362

 Catalysis by MOFs
(4) Chiral Catalysis

[Zn4(μ4-O)(L2)3]

Song et al. J. Am. Chem. Soc. 132 (2010) 15390

 Comparison of MOFs and zeolites
Zeolites (& zeotypes) MOFs

corner-shared tetrahedral oxide networks metal-centred polyhedra + organic linkers

~240 unique structures ~ infinite variety

microporous: surface areas ~ 100s m2g-1 microporous–mesoporous > 10,000 m2g-1

limited structural flexibility: unprecedented flexibility:

< 1 Å atom displacement reversible displacement of several Ås

high thermal stability: up to 800 oC low thermal stability < 400 oC

‘designed’ uniform site catalysts?

 Hexameric Yb6 building unit:
A Hydrothermally Stable chemically robust
Dual Acid MOF

Loosely-bound water:
Lewis acidic Yb3+ ?

[Yb6(BDC)7(OH)4(H2O)4]
Bridging hydroxyls:
Brønsted acid sites ?

water at 140 C gives 64.5 % 5-HMF

Burnett et al. (2019)
 CH3F0: Advanced Inorganic Chemistry

Fundamentals of catalysis and metal-centred reactions

Professor Richard Walton

Segment 17: Heterogeneous vs homogeneous

 Fischer- Tropsch Catalysis
A Heterogeneous Organometallic Reaction
Reliance on hydrocarbons: need for an alternative route
(not via crude oil)
Fischer- Tropsch discovered 1925

Developed by Ruhrchemie and Sasol

No reliance on oil reserves: “gas-to-liquids

technology” (GTL)

NOW – crude oil limited, politics, CH4

reserves, US coal reserves – F-T likely to
be more important

can also use biomass to produce

‘syngas’
Fischer- Tropsch Catalysis

Catalysts Fe, Co and Ru

Adsorption of Hydrogen
Adsorption of CO
Reaction
H2 & CO adsorption modes and oxide reducibility

Perego et al. Catalysis Today 2009, 142, 9–16

Carbide mechanism: Propagation & Termination
Comparison with Homogeneous Catalysis
In homogeneous hydrogenation reactions H2 is often ‘activated’ by oxidative
addition, cf. heterogeneous dissociative adsorption

In homogenous M-CO bonds, CO often ‘activated’ by ligand addition

cf. non-dissociative heterogeneous adsorption

Envia’s GTL plant, Oklahoma City, USA