CHM102A: General Chemistry

Inorganic Chemistry: Lecture 7

Sabuj Kundu
sabuj@iitk.ac.in
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 Oxidative Addition
❑ Oxidative addition (OA) is a process that adds two anionic
ligands e. g. A and B, that originally are a part of a A-B molecule,
like in H2 or Me−I, on to a metal center and is of significant
importance from the perspective of both synthesis and catalysis.

❑ The exact reverse of the same process, in which the two ligands,
A and B, are eliminated from the metal center forming back the
A−B molecule, is called the reductive elimination (RA).

•  OS = +2
•  EC = +2
•  CN = +2 2
 Factors affecting the Oxidative Addition

❑ Metal typically needs to be electron rich (and in a relatively low oxidation state).
As during oxidative addition, the metal formally loses two d electrons.

❑ The metal needs to bear two open coordination sites for oxidative addition to
occur, because two new ligands enter the metal’s coordination sphere. Since the
new ligands need space, steric hindrance tends to discourage oxidative addition.

❑ Oftentimes ligand dissociation is required before oxidative addition can occur; in

many of these cases, the rate of dissociation influences the overall rate of the
reaction. 3
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 Oxidative Addition: Mechanisms
❑Concerted Oxidative Addition: when A-B (substrate) is a non-
polar molecule; such as hydrogen and hydrocarbons

σ-complex
The resulting ligands will
be mutually cis,
❑Concerted oxidative addition: although subsequent
σ complex formation followed isomerization may occur
by bond braking.
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 Oxidative Addition: Mechanisms
❑SN2-type Oxidative Addition: when A-B (substrate) is a polar
molecule; such as alkyl halides and halogens

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 Reductive Elimination
❑ Reductive elimination (RE) is the microscopic reverse of oxidative
addition. It is literally oxidative addition run in reverse
❑ Reductive elimination and oxidative addition share the same
reaction coordinate. Thus, their mechanisms depend on one
another, and trends in the speed and extent of oxidative additions
correspond to opposite trends in reductive eliminations.

❑ Reductive elimination is an intramolecular

reaction and favored by low electron density •  OS = -2
of the metal center. Ligands must be in a cis •  EC = -2
position in order to undergo reductive •  CN = -26
elimination.
 Reductive Elimination

❑ In several cases that a ligand dissociates from octahedral complexes before

concerted reductive elimination occurs. Presumably, dissociation to form a
distorted TBP geometry brings the eliminating groups closer to one another to
facilitate elimination.

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 Reductive Elimination
❑ Reductive elimination is an important step in many catalytic
cycles—it usually comes near the “end” of catalytic mechanisms,
just before product formation.

❑ For some catalytic cycles it’s the turnover-limiting step, making it

very important to consider! Hydrocyanation is a classic example; in
the mechanism of this reaction, reductive elimination of C–CN is
the slow step.

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 β-Hydride elimination
❑ in which an alkyl group bonded to a metal centre is converted into
the corresponding metal-bonded hydride and an alkene.

❑ The alkyl must have hydrogens on the β-carbon.

❑ The metal complex must have an empty (or vacant) site cis to the
alkyl group for this reaction to occur.

-Hydride elimination

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 Insertion Reactions
❑Oxidative addition and substitution allow us to assemble ligands
on the metal. With insertion, and elimination we can now combine
and transform these ligands within the coordination sphere, and
ultimately expel these transformed ligands to form free organic
compounds.

❑An insertion reaction involves the formal insertion of one ligand

(usually unsaturated) into another metal-ligand bond on the same
complex. The generic reaction is shown below, where U = an
unsaturated ligand:

U = CO, C2H4, C2R2, NO, CR2, CNR, RCN, O2, CO2

X = H, alkyl, aryl, OR, NR2
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 Types of Insertion Reactions
❑There are two main types of insertion—1,1 and 1,2.

❑1,1 insertion:

❑The metal and the X ligand end up bound to the same

(1,1) atoms of an L-type ligand.

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 Types of Insertion Reactions
❑1,2 insertion:

❑The metal and the X ligand end up bound to the

adjacent (1,2) atoms of an L-type ligand.

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 Types of Insertion Reactions
❑The type of insertion observed in any given case depends on the
nature of the 2e inserting ligand.

❑For example, CO gives only 1,1 insertion: that is, both the M and
the X group end up attached to the CO carbon.

❑On the other hand, ethylene gives only 1,2 insertion, in which the
M and the X end up on adjacent atoms of what was the 2e ligand.

❑In general, η1 ligands tend to give 1,1 insertion and η2 ligands give
1,2 insertion.

❑SO2 is the only common ligand that can give both types of
insertion; as a ligand, SO2 can be η1 (S) or η2 (S, O).

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 Insertion Reactions
❑The insertion requires a cis arrangement of the ligands,
and the elimination reaction also need cis arrangement of
these ligands.

❑The formal oxidation state does not change during

insertion reaction.

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 Insertion Involving Alkenes
❑The insertion of coordinated alkenes into M−H bonds is a very
important reaction because it gives alkyls and constitutes a key step
in a variety of catalytic reactions including alkene polymerization.

❑As η2-ligands, alkenes give 1,2 insertion. This is the reverse of the
familiar β-elimination reaction.

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 Insertion Involving Alkenes
❑The position of equilibrium is decided by the thermodynamics of
the particular system and depends strongly on the alkene.

❑For ethylene the equilibrium tends to lie to the left (i.e., the alkyl
β-eliminates).

❑ But for alkenes with electron-withdrawing ligands (e.g., C2F4), the

alkyl is particularly stable, and the equilibrium lies entirely to the
right; alkyls such as LnMCF2CF2H.

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 Catalysis
❑Catalysts are substances that increase the reaction rate of a
chemical reaction without being consumed in the process.
❑ A catalyst, does not appear in the overall stoichiometry of the
reaction it catalyzes, but it must appear in at least one of the
elementary reactions in the mechanism for the catalyzed reaction.
Catalysis is a kinetic phenomenon
❑ Homogeneous: the catalyst
and substrates for the reaction
are in the same phase.

❑ Heterogeneous: the catalyst

and substrates for the reaction
are NOT in the same phase.

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 Catalytic Cycle
❑The catalytic cycle is the main method for describing the role of
catalysts.
❑It is a multistep reaction mechanism that involves a catalyst.
❑Since catalysts are regenerated, catalytic cycles are usually written
as a sequence of chemical reactions in the form of a loop.

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 TON and TOF
❑ Each time the complete catalyst cycle occurs, we consider one
catalytic turnover (one mole of product formed per mole of
catalyst) to have been completed.

❑ The catalytic rate can be conveniently given in terms of the

turnover frequency (TOF) measured in turnovers per unit time
(often per hour); the lifetime of the catalyst before deactivation is
measured in terms of total turnovers number (TON).

❑ TON: the number of moles of substrate that a mole of catalyst

can convert before becoming inactivated.

❑ Example: If 0.1 mole of catalyst converts 100 moles of substrates

in 10 minutes (100% yield) then
❑ TON = 100/0.1 = 1000
❑ TOF = TON/time = 100 min-1
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 Wilkinson's catalyst

The stereochemistry of addition is cis-

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 Hydroformylation/Oxo Process

catalysts

❑ It is an industrial process to produce aldehydes from alkenes.

❑ Both cobalt and rhodium complexes are used as catalysts.

❑ Alkene isomerization, alkene hydrogenation and formation of

branched aldehydes are the possible side reactions.
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Hydroformylation/Oxo Process

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 Monsanto process
❑ The Monsanto acetic acid process is the major commercial production
method for acetic acid.
❑ Methanol, which can be generated from synthesis gas ("syn gas", a CO/H2
mixture), is reacted with carbon monoxide in the presence of a catalyst
to afford acetic acid.

❑ Mid 1960s: BASF cobalt catalyst used for methanol carbonylation;

Reaction conditions: 250 oC and 680 bar
❑ Late 1960s: Monsanto rhodium catalyst discovered;
Reaction conditions: 150-200 oC and 30-60 bar

❑ Replaced by an Iridium catalyst in the late 1990s by BP Chemicals.

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 Monsanto process

2 = Oxidative Addition
3 = Migratory Insertion
4 = CO Addition
5 = Reductive Elimination 24
 Metalloenzymes
❑ Metalloenzymes all have
one feature in common,
Metalloenzyme active site are
namely that the metal ion
finely tuned to do selective job
is bound to the protein
with one labile
coordination site.

❑ Shape of the active site is

crucial.
❑ The metal ion is usually
located in a pocket whose
shape fits the substrate.
❑ It catalyzes reactions that
are difficult to achieve in
organic chemistry.
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 Myoglobin and Hemoglobin
❑ O2 is only marginally soluble (< 0.0001 M) in blood plasma at
physiological pH.
❑ Our blood stream contains about 150 g/L of hemoglobin (Hb),
which is an effective oxygen-carrier.

❑ Once the Hb-O2 complex reaches the tissue that consumes oxygen,
the O2 molecules are transferred to another protein -- myoglobin
(Mb) -- which transports oxygen through the muscle tissue.

❑ Hemoglobin:
• Found in red blood cells
• Promotes diffusion of O2 throughout the body (binds O2 at lungs, releases at
tissues)

❑ Myoglobin:
• Found in muscle cells
• Promotes diffusion of O2 into and throughout muscle cell 26
 Myoglobin and Hemoglobin
❑ The O2-binding curve of hemoglobin is S
shaped, sigmoid curve.

❑ at low oxygen pressures, the affinity of

deoxyhemoglobin for O2 is substantially
lower than that of myoglobin, whereas at
high O2 pressures the two proteins have
comparable O2 affinities.

❑ In the lungs, where O2 pressure is highest, the high oxygen affinity of

deoxyhemoglobin allows it to be completely loaded with O2, giving four O2
molecules per hemoglobin.
❑ In the tissues, where the oxygen pressure is much lower, the decreased oxygen
affinity of hemoglobin allows it to release O2, resulting in a net transfer of
oxygen to myoglobin.

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 Myoglobin and Hemoglobin
❑ Hemoglobin is a heterotetramer (contains four subunit proteins) with two α- &
two β-subunits, non-covalently bound, each made of 141 and 146 amino acid
residues, respectively.

❑ Each subunit has a molecular weight of about 16,000 daltons, total molecular
weight of the tetramer of about 64,000 daltons.

❑ Myoglobin belongs to the globin superfamily of proteins, consists of eight alpha

helices connected by loops. Myoglobin is a single-subunit, α-helical protein,
contains 154 amino acids.

Myoglobin Hemoglobin 28
 Myoglobin and Hemoglobin
❑ In the deoxymyoglobin, the iron (ferrous) is five-coordinate and high spin.
Because high-spin Fe2+ is too large to fit into the “hole” in the center of the
porphyrin, it is about 60 pm above the plane of the porphyrin.

❑ When O2 binds to deoxymyoglobin to form oxymyoglobin, the iron is converted

to six-coordinate (low spin). Because low-spin Fe3+ is smaller than high-spin Fe2+,
the iron atom moves into the plane of the porphyrin ring to form an octahedral
complex.

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