Study Unit 5:

Homogeneous Catalysis

Part B: Catalysis by
organometallic complexes

ISY417P
Dr LF Mabena

Faculty of Science
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Homogeneous Catalysis- The reactants and catalyst are
present in a single phase (usually in the liquid phase)

Types of homogeneous Catalysis:

 Acid/base
 Metal-ion
 Electron transfer
 Organometallic
 Macromolecules
 Phase transfer (PTC)
 Micelles
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 Learning Outcomes...

PART 1:

 Predict complex stability using the

eighteen electron rule.
 Interpret and understand the stability
and reactivity of simple organometallic
complexes.
 Catalysis by organometallic complexes

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Organometallic
complexes
 Organometallic complexes
 Organometallic complex consist of a central transition metal ion bonded to
organic ligands such as R2C=CR2, RCO, R3P, R3N, CO etc.
 They involve soft ligands, and soft metal ions in low oxidation states.
 C-containing groups may be: carbonyls, alkenes, alkynes, aromatic, cyclic or
heterocyclic.
 C≡O The carbonyl ligand, PR3 The phosphines, where R is, for example –CH 3 or -
C6H5 (trimethyl phosphine and triphenylphosphine), ethylenes, butadiene,
cyclooctadiene, cycopentadienyl anion:
 Many organometallic compounds are thermodynamically unstable and
spontaneously flammable.
 Examples of some of the first organometallic compounds are: [PtCl2(CO)]2 in
1868 and ferrocene - Fe(C5H5)2 in 1951.
 Organometallic catalysts play major role in homogeneous catalysis.
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 Organometallic complexes

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 Organometallic complexes
 Catalysis occurs through dissociation of ligands followed by co-ordination of
reactant molecule to the metal ion.
 The transition metal ions react through exchange of d-electrons.
 Organometallic complexes usually have octahedral or tetrahedral geometry.
 Both the metal and the large variety of ligands determine the properties of
the catalyst.
 The success of organometallic catalysts lies in the relative ease of catalyst
modification by changing the ligand environment.
 Crucial properties to be influenced are the rate of the reaction and the
selectivity to certain products.

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 18 Electron rule: How to count electrons
The rule states that thermodynamically stable transition metal organometallic
compounds are formed when the sum of the metal d electrons and the electrons
conventionally considered as being supplied by the surrounding ligands equals
18.

In general, the conditions favouring adherence to the 18 electron rule are, an electron
rich metal (one that is in a low oxidation state) and ligands that are good Π-
acceptors

1. Neutral ligand method/Covalent Method

2. Donor pair Method/Ionic Method

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 Hapto (h) Number (hapticity)

 For some molecules the molecular formula provides

insufficient information with which to classify the metal
carbon interactions

 The hapto number (h) gives the number of carbon

(conjugated) atoms bound to the metal, For example,
 η2 describes a ligand that coordinates through 2 atoms.

 It normally, but not necessarily, gives the number of

electrons contributed by the ligand.

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 Different numbers of atoms of the organometallic ligand may be involved in bond and
is called the “Hapticity” of the ligand

(h5-C5H5)Fe(CO)2Cl
Total charge on ligands = X,
Fe = dX
(h5-C5H5- = X) + (2CO x 2 = 4) + (Cl- = X) = X electrons
Total of X electrons
Coordination

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 Neutral Ligand Method…

 All ligands are treated as neutral and are categorized according to how many electrons
they are considered to donate.
 All valence electrons of the metal atom and all the electrons donated by the ligands are
included.
 If the complex is charged, we simply add or subtract the appropriate number of electrons
to the total.
 Ligands are defined as L type if they are neutral two-electron donors (like CO, PMe3) and
X type if, when they are considered to be neutral, they are one-electron radical donors
(like halogen atoms, H, CH3).

For example, Fe(CO)5 acquires 18 electrons from the eight valence electrons on the Fe atom
and the 10 electrons donated by the five CO ligands.

Total valence electrons = Metal group + electrons donated by all even- and odd-electron
ligands - Overall charge on the complex
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Methods of counting: Neutral atom method and oxidation state methods

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 Carbonyl complexes and 18e- rule
A very simple rule allows us to predict the numbers of donor groups
attached to metal ions in organometallic complexes, called the eighteen
electron rule. The latter rule states that the sum of the d-electrons possessed
by the metal plus those donated by the ligands (2 per C≡O) must total
eighteen:

[Ni(CO)4] [Fe(CO)5] [Cr(CO)6]

Ni(0) = d10 Fe(0) = d8 Cr(0) = d6

4 x CO = 8 5 x CO = 10 6 x CO = 12

18 e 18e 18e
`Formal oxidation states are all zero.

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 Carbonyl complexes and 18e- rule
To obey the 18-electron rule, many carbonyl complexes are
anions or cations, as in:

[V(CO)6]- [Mn(CO)6]+ [Fe(CO)4]2-

V(0) = d5 Mn(0) = d7 Fe(0) = d8

6 CO = 12e 6 CO = 12e 4 CO = 8e

1- = +1e 1+ = -1e 2- = 2e

= 18e
Formal oxidation = 18
Formal e
oxidation Formal= oxidation
18e
state = V(-I) state = Mn(I) state = Fe(-II)
[NOTE: In applying the 18-electron rule, metal ions are always
considered to be zero-valent, not the formal oxidn. state]
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 Charged ligands and 18e- rule

The formally charged ligands that are important in organometallic

chemistry are mainly soft ligands such as Cl-, Br-, and I-, with CN- also
occurring. Hydride (H-) is also very important. These mono-anionic ligands
all contribute one electron for the 18-electron rule, as in the following
examples:

[Mn(CO)5Cl] [H2Fe(CO)4] [HCo(CO)4]

Mn(0) = d7 Fe(0) = d8 Co(0) = d9
5 CO’s = 10 4 CO’s = 8 4 CO’s = 8
1 Cl = 1 2H = 2 1H = 1
18 e 18 e 18 e

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 Metal-Metal bonding in Carbonyl complexes

A species such as [Mn(CO)5] would have only 17 e. The 18e rule

can be obeyed by two such entities forming a Mn-Mn bond, where each
Mn contributes one electron to the valence shell of the other Mn, giving
the metal-metal bonded species [(CO)5Mn-Mn(CO)5]. To check on the 18e
rule, we look at one metal at a time:

Mn-Mn Mn(0) = d7
bond 5 C≡O = 10
Mn Mn-Mn = 1
Mn
18 e
[Mn2(CO)10]
 Metal-Metal bonded clusters in Carbonyl complexes

Here we see a Rhodium tetramer

where each Rh forms three Rh-Rh
bonds to the other Rh atoms.
18-electron rule: Focus on one Rh
atom:

Rh(0) = d9
3 CO per Rh = 6
3 Rh-Rh bonds: = 3

18e
[Rh4(CO)12]

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 Bridging Carbonyls in Carbonyl complexes
bridging Carbonyls may form bridges
carbonyls between two metals, where they donate one
electron to each metal in working out the 18
electron rule. In [Co2(CO)8] at left each Co
has three terminal CO’s, two bridging CO’s,
Co Co and a Co-Co bond:
Co(0) = d9
3 CO’s = 6
Co-Co 2 bridge CO’s = 2
bond Co-Co bond = 1
18 e
No new concepts are required to understand bridging ligands
other than that the Greek letter µ (mu) is used to indicate how
[Co2(CO)8] many atoms the ligand bridges.
Thus a µ2-CO is a carbonyl group that bridges two metal
atoms and a µ3-CO bridges?
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 Bridging Carbonyls in Fe2(CO)9

Fe2(CO)9 has each Fe with three

bridging terminal CO’s, three bridging CO’s,
carbonyls and an Fe­Fe bond. The 18 electron
rule holds for each Fe atom as:

Fe(0) = d8
3 CO’s = 6
3 bridge CO’s = 3
Fe-Fe bond = 1

18 e
Fe-Fe
bond
[Fe2(CO)9]

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 Examples of using neutral-ligand method…
 Do (a) [IrBr2(CH3)(CO)(PPh3)2] and (b) [Cr(η5-C5H5)(η6-C6H6)] obey the 18-electron rule?

 (a) 1. Start with the Ir atom (Group 9) which has nine valence electrons.
 2. Then add in the electrons from the two Br atoms and the CH3 group (each is a one-
electron donor).
 3. Finally add in the electrons from the CO and PPh3 (both are two-electron donors).
 4. Thus, the number of valence electrons on the metal atom is 9 + (3 x 1) + (3 x 2) = 18.

 (b) 1. The Cr atom (Group 6) has six valence electrons.

 2. The η5-C5H5 ligand donates five electrons, and the η6-C6H6 ligand donates six.
 3. So the number of metal valence electrons is 6 + 5 + 6 = 17.
 This complex does not obey the 18-electron rule and is not stable.

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 Donor-pair Method …
 Ligands are considered to donate electrons in pairs, resulting in the need to treat
some ligands as neutral and others as charged.
 The donor-pair method requires a calculation of the oxidation number.
 The rules for calculating the oxidation number of an element in an organometallic
compound are the same as for conventional coordination compounds.
 Neutral ligands, such as CO and phosphine, are considered to be two-electron
donors and are formally assigned an oxidation number of 0.
 Ligands such as halides, H, and CH3 are formally considered to take an electron from

the metal atom, and are treated as Cl-, H- and CH3- (and hence are assigned
oxidation number -1).
 In this anionic state they are considered to be two-electron donors.

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 Ionic method- donor pair method

1.Determine the total charge of the ligand set and the number of electrons donated by

ligands

2.Determine the oxidation states of the metal

3.Determine the d-electron count of the metal

4.Determine the total number of electrons by summing the number of d-electrons and the

total number of electrons donated by the ligands

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 Donor-pair Method …

 The cyclopentadienyl ligand, C5H5 (Cp), is treated as C5H5- (it is assigned an oxidation number of -1).
 In this anionic state it is considered to be a six-electron donor.

Then:
 The oxidation number of the metal atom is the total charge of the complex minus the charges of any
ligands.
 The number of electrons the metal provides is its group number minus its oxidation number.
 The total electron count is the sum of the number of electrons on the metal atom and the number of
electrons provided by the ligands.

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 Donor-pair Method…

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 Examples of using donor-pair method…

 Assign the oxidation number and count the valence electrons on the metal atom in (a) [IrBr 2(CH3)(CO)

(PPh3)2], (b) [Cr(η5-C5H5)(η6-C6H6)], and (c) [Mn(CO)5]-.

 (a) We treat the two Br groups and the CH3 as three singly negatively charged two-electron donors

 and the CO and the two PPh3 ligands as three two-electron donors, providing 12 electrons in all.
 Because the complex is neutral overall, the Group 9 Ir atom must have a charge of +3 (that is, have
oxidation number +3) to balance the charge of the three anionic ligands, and thus contributes 9 – 3 = 6
electrons.
 This analysis gives a total of 18 electrons for the Ir(III) complex.

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 Examples of using donor-pair method…
 Assign the oxidation number and count the valence electrons on the metal atom in (a) [IrBr 2(CH3)

(CO)(PPh3)2], (b) [Cr(η5-C5H5)(η6-C6H6)], and (c) [Mn(CO)5]-.

 (b) We treat the η5-C5H5 ligand as C5H5- and thus it donates six electrons, with the η6-C6H6 ligand
donating a further six.
 To maintain neutrality, the Group 6 Cr atom must have a charge of +1 (and an oxidation number of
+1) and contributes 6 – 1 = 5 electrons.
 The total number of metal electrons is 12 + 5 = 17 for a Cr(I) complex.
 As noted before, this complex does not obey the 18-electron rule and is unlikely to be stable.

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 Examples of using donor-pair method…
 Assign the oxidation number and count the valence electrons on the metal atom in (a)
[IrBr2(CH3)(CO)(PPh3)2], (b) [Cr(η5-C5H5)(η6-C6H6)], and (c) [Mn(CO)5]-.

 (c) We treat each CO ligand as neutral and contributing two electrons, giving 10 electrons.
 The overall charge of the complex is -1; because all the ligands are neutral, we consider this
charge to reside formally on the metal atom, giving it an oxidation number -1.
 The Group 7 Mn atom thus contributes 7 + 1 electrons, giving a total of 18 for a Mn(-1) complex.

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Methods of counting: Neutral atom method and oxidation state methods

Neutral atom method: Metal is taken as in zero oxidation state for counting purpose

Oxidation state method: We first arrive at the oxidation state of the metal by
considering the number
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 The two methods compared:
some examples

Some ligands donate the same

number of electrons

Number of d-electrons and

donation of the other ligands
can differ

Now we will look at practical

examples on the black board

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Catalytic cycles
 Unique reactions in organometallic Chemistry

 Oxidative Addition
 Reductive Elimination
 Migratory Insertion
 Hydrogen Elimination

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 Oxidative Addition
When addition of ligands is accompanied by oxidation of the metal, it is called an
oxidative addition reaction

Oxidation state of metal increases by 2 units

Coordination number increases by 2 units
2 new anionic ligands are added to the metal
Requirements for oxidative addition
 availability of nonbonded electron density
on the metal,
 two vacant coordination sites on the reacting complex (LnM), that is, the complex
must be coordinatively unsaturated,
 a metal with stable
Department oxidation states separated by two units; the higher oxidation
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state must be energetically accessible and stable.
 Reductive Elimination (Reverse of oxidative addition)

 Oxidation state of metal decreases by 2 units

 Coordination number decreases by 2 units
 2 cis oriented anionic ligands form a stable σ-bond and leave the metal

Factors which facilitate reductive elimination

 a high formal positive charge on the metal,
 the presence of bulky groups on the metal, and
 an electronically stable organic product.

Cis orientation of the groups taking part in reductive elimination is a MUST.

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 Migratory insertion

 No change in the formal oxidation state of the metal

 A vacant coordination site is generated during a migratory insertion (which gets
occupied by the incoming ligand)
 The groups undergoing migratory insertion must be cis to one another

These reactions are enthalpy driven and although the reaction is entropy
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the large enthalpy term dominates
 Type of Migratory insertion

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 β-Hydride Elimination
 Beta-hydride elimination is a reaction in which an alkyl group having a β-hydrogen,
σ-bonded to a metal centre is converted into the corresponding metal-bonded
hydrideand a Π-bonded alkene.
 The alkyl must have hydrogens on the beta carbon. For instance butyl groups can
undergo this reaction but methyl groups cannot. The metal complex must have an
empty (or vacant) site cis to the alkyl group for this reaction to occur.

No change in the formal oxidation state of the metal

Mechanism

DepartmentCan either be
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Organometallic
complexes
Terminology
Catalytic cycles: a circular path meant to show productive reactions, in order, that lead
from the catalytically active species and its reaction with a substrate through to product
elimination and regeneration of the catalyst.
Turnover number: number of times a cycle is completed before the catalyst dies. Typically
this is > 1000; a stoichiometric reaction has a TON of 1.
Turnover rate or frequency: the rate at which a cycle is completed. This can be reported
in many ways but it is usually in mol product per mol catalyst per time. Eg. a good ethylene
polymerization catalyst might have a turnover rate of 5000 kg polyethylene per mol of
catalyst per hour.
Resting State: this is the stable, and usually inactive, form of the catalyst when no
substrate is provided or when it has been used up. Eg. with a coordinated solvent molecule
occupying the active coordination site.
Pre-catalyst: the stable compound put into the reactor; it must be transformed in situ into
the active species.
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Catalysis by organometallic complexes
The selectivity can be changed by altering the ligands, allowing synthesis
of products not formed in the un‐catalyzed process.
Chemoselectivity, when two chemically Regioselectivity, as in the example shown for
different functionalities are present such as the hydroformylation reaction, the formyl
an alkene and an aldehyde which both can be group can be attached to either the primary,
hydrogenated. terminal carbon atom or the secondary,
The chemoselectivity tells us whether the internal carbon atom, which leads respectively
aldehyde or the alkene is being to the linear and the branched product.
hydrogenated; or when more than one
reaction can take place for the same
substrate e.g. hydrogenation or
hydroformylation.

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Catalysis by organometallic complexes
Diastereoselectivity, the substrate contains a Enantioselectivity, the substrate is achiral in
stereogenic centre and this together with the this instance, but the enantiopure or enantio-
catalyst can direct the addition of dihydrogen enriched catalyst may give rise to the
in the example to give two diastereomers, the formation of one specific product enantiomer.
selectivity for either one is called the
diastereoselectivity;

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 Hard and Soft Catalysis

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 Catalysis by organometallic complexes

Reactions catalyzed by organometallic complexes include:

 Oxidation reactions
 Hydrogenation reactions
 Carbonylation reaction (Monsanto Process)
 Glycol synthesis
 Alkene oligomerization (SHOP) and polymerization (Ziegler Natta)
 C-C and C-X coupling
 Hydroformylation
 Epoxidation
 Hydrocyanation
 Hydrosilylation
 metathesis
 C-H Department
functionalization
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 Mechanisms
 Homogeneous catalysis mechanism is often represented by catalytic cycles.
 In catalytic cycles, usually catalysts are shown as member of cycle and all
reactants and products are placed outside the cycle and connected to it by arrows.
 For example, the cycle of a catalytic reaction where A+ B → P
having intermediates K and L can be represented as

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 Reaction and Mechanisms
 The stable metal complex added to the reaction at the beginning is called catalyst
precursor or precatalyst.
 The intermediates species can be studied using various spectroscopic studies such as
FTIR, NMR, UV-Vis etc.
 homogeneous organometallic complex catalysts, the reaction begins with the
reactant molecule getting attached to a metal centre in the catalyst. Hence, the
metallic centers must have vacant coordination sites. However, it is difficult to
maintain vacant sites on the metallic center as the molecules are always in
solvated conditions.
 Over all, the mechanism can be described as removal of ligand from the metallic
center and addition of reactant to the vacant site. This mechanism is similar to
substitution reaction. There is always competition for vacant sites between
ligand, reactant or solvent molecules. The process is proposed to occur by
associative or dissociative mechanism.

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Mechanisms: Dissociative Mechanism
 In dissociative ligand exchange mechanism, initially there is breaking of bond
between the metal and leaving ligand.
 This is the slowest and rate controlling step. A solvent molecule occupies
the open site. Subsequently, the solvent is replaced by reactant in a fast step.

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 Mechanisms: Associative
In associative ligand exchange process, bond breaking of ligand from metal
and bond formation between metal and reactant occurs simultaneously as
shown below.

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Mechanisms: Insertion

Elementary steps
Insertion: In insertion mechanism an unsaturated molecule inserts
into a metal- anion bond. In the shown example, the CO inserts
into the metal (Pt)-methyl bond and acyl bond formed (R-CO) takes
position of methyl group. The vacant position on metal is filled in
solvent (S) molecule.

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 Mechanisms: Migration
 In migration mechanism, atom or group of atoms migrates from
metal to hydrocarbon.
 In the shown example, hydride migrates from metal atom to
ethene. The vacant position on metal is filled in by ligand (L)
molecule.

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 Mechanisms: ß-elimination

 This reaction is reverse of migration.

 The ß-elimination requires a vacant site at the complex.

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 Mechanisms: Oxidative Addition

In this reaction, a compound XY adds to a metal complex during

which the XY bond is broken and two new bonds MX and MY are
formed

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 Mechanisms: Reductive elimination

It is reverse of oxidative addition

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 Mechanisms

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WC
IN
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 Mechanisms

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Hydrogenation reaction: Oxidative Addition of H2 to an alkene
 H2 adds to the catalyst before the olefin.
 The last step of the catalytic cycle is irreversible. This is very useful because a
kinetic product ratio can be obtained

Simplistically, the relative rates

suggest that the rate-determining
step is OA of H2.

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 Carbonylation Reaction: Monsanto

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 Carbonylation Reaction: Monsanto

Acetic acid for industrial uses: vinyl

acetate, cellulose acetate,
pharmaceuticals, dyes and
pesticides.

Monsanto process dominates the

market but older methods such as
the oxidation of ethylene via
acetaldehyde are still practiced.

conditions: 180ºC / 30-40 atm /

10-3 M catalyst

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 Carbonylation Reaction: CATIVA Process

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Hydroformylation (Oxo) Catalysis
 Formally addition of formaldehyde across a double bond
 Discovered by BASF by Otto Roelen using Co catalysts
 Worldwide scale: about 7 BILLION kgs per year
 Largest homogeneous catalytic process. > 15 billion pounds of aldehydes (alcohols) per year
 Commercial catalysts are complexes of Co or Rh
 Selectivity to linear (normal) or branched (iso) products is important

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Hydroformylation (Oxo) Catalysis-Phosphine modified cobalt

HRh(CO)(PPh3)2 allows lower T

(100ºC) and P (6 atm)
linear to branched ratio: > 10:1
hydrogenation is much slower
under the conditions used and does
not compete as a side reaction.

Phosphine modified Cobalt catalysed

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 Alkene Oxidation-Wacker Process
Characteristics of the Wacker process:
 The oxygen in the product derives from water, not directly from the oxygen used
as oxidant
 higher olefins yield ketones, not aldehydes
 large amounts of halides required: corrosive
 side products resulting from nucleophilic attack of halide on olefin
Several variations (with more complicated nucleophiles) used in organic synthesis

Used to prepare acetaldehyde for conversion to acetic acid

 replaced dangerous hydration of acetylene in 1950’s
 now largely superceded by Monsanto process
 ultimate oxygen source is air although the reaction chemistry occurs solely at
Pd
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 Alkene Oxidation-Wacker Process

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