CHM 113M: General Inorganic Chemistry

Lecture 5

Apparao Draksharapu
appud@iitk.ac.in
 Recap of Lecture IV
1. Magnetism (systems with unpaired electrons)
 Metalloenzymes

X. Huang, J. T. Groves,
Chem. Rev. 2018, 118, 2491.
 Inspiration from nature
Photosystem II Methane Monooxygenase
− 4e−, 4H+ O2, sMMO
2H2O O2 CH4 CH3OH
BDE = 105 kcal mol-1

“OEC”

“Q”
Science 2006, 314, 821 Chem. Rev. 2018, 118, 2554 9
 The Magic of Dioxygen
O2

O2-

O22-
“The dark side of molecular oxygen encompasses deleterious reactions of
species derived from O2 that can lead to damage of cellular components.
These reactive oxygen species (ROS) have historically been perceived almost
exclusively as agents of the dark side, but it has more recently become clear
that they play beneficial roles as well.” Chem. Rev. 2018, 118, 2491.
Common Ligands

Oxygen based
(O2-●, O22- & O2-)
H2O, OH-
HCO3-, CO32-,
S2-, Cl-, Br-, NO, CO, CH3-
11
 Myo/Hemo-globin – Oxygen Transporter

O2
Hemoglobin

Myoglobin
Chem. Rev. 2018, 118, 2491.
 Oxygen Binding to Myoglobin
• O2 binds to only available coordination site on iron atom.
• His 93 (proximal his) binds directly to iron.
Distal Histidine
• His 64 (distal his) stabilizes the O2 binding site.

Proximal Histidine
Myoglobin
Structural Changes in Myoglobin Upon O2 Binding
• Oxygen binding changes the Mb conformation
• Without oxygen bound, Fe is out of heme plane
• Oxygen binding pulls the Fe into the heme plane
• O2 binds to only available coordination site on iron atom.
• Fe pulls its His F8 ligand along with it
• This change means little to Mb, but lots to Hb!
Structural Changes in Hemoglobin Upon O2 Binding
Deoxyhemoglobin Oxyhemoglobin

Total unpaired electrons = 1, S = 1/2

Total unpaired electrons = 4, S = 2 Oxygenated form is low-spin
Deoxygenated form is high-spin The magnetic moment of Fe3+ and the superoxide
and paramagnetic radical anion involves in anti-ferromagnetic coupling
and the oxygenated complex is not paramagnetic
Oxygen Binding Curve for Hemoglobin

.
 CO binding to Mb and Hb
➢ Carbon monoxide is produced continuously in the body by degradation of the porphyrin
ligand.
➢ Under normal conditions, CO occupies approximately 1% of the heme sites in hemoglobin and
myoglobin.
➢ Although CO has a much greater affinity for a ferrous heme than
does O2 (by a factor of about 25,000), the affinity of CO for
deoxyhemoglobin is only about 200 times greater than that of O2,
which suggests that something in the protein is decreasing its
affinity for CO by a factor of about 100

➢ Both CO and NO bind to

ferrous hemes in a linear
fashion.
➢ In Mb and Hb, distal His forces
bent binding of both, weakens
CO binding.
 Why Horseshoe crab blood is blue?

O2

1 L 11.5 lakhs

Deoxy-Hc (A) and oxy-Hc (B) from Li. polyphemus shows a large
geometric change at the active site upon oxygen binding (the
Cu●●●Cu distance decreases by 1.0 Å) 18
Why Study Organometallic Chemistry?
 Why Study Organometallic Chemistry?
• Fundamental Science: Understanding the nature of the interesting and useful complexes.

• Organic Synthesis: Organometallic Complexes allow many powerful synthetic organic

transformations that can not be accomplished without metals, including Heck, Suzuki,
asymmetric hydrogenation reactions.

• Bulk Chemical Synthesis and Catalysis: Huge industrial importance to organometallic

processes, including commodity chemicals, plastics, petroleum, etc.

• Material Science: Chemical vapor deposition for depositing thin-films of metals. Complex
organometallics for advanced materials, such as organic light emitting diodes.

• Bioinorganic Chemistry: Some overlap, such as with Vit. B12, hydrogenase, carbonylase, etc.

• Energy Science: Emerging subfield of catalysis.

 Organometallic Compounds in Nature
➢ Organometallic chemistry has
really been around for
millions of years

Naturally occurring cobalamins

Hydrogenase
contain Co—C bonds
 Organometallic Compounds
• An Organometallic Complex contains at least one M—C bond
• Common ligands in organometallic compound: CO, NO, N2, PR3, H2
• Both s and p bonding between M and C occur

• History
• Zeise’s Salt synthesized
in 1827 = K[Pt(C2H4)Cl3] • H2O

• Confirmed to
have H2C=CH2 as
a ligand in 1868.
 Organometallic Compounds - History
• Ni(CO)4 synthesized in 1890 (Ludwig Mond of Brunner Mond & Co.)

• 1893: Alfred Werner develops the modern ideas of coordination chemistry.

• Grignard Reagents (X-Mg-R) synthesized about 1900. 1912

• Accidentally produced while trying to make other compounds

• Utility to organic synthesis recognized early on.
 Organometallic Compounds - History
• 1951: Ferrocene discovered (serendipity synthesis by Keally and Pauson, and Miller and co-
workers), correct structure proposed by Wilkinson and Fischer) that led to metallocene chemistry
and eventually awarded Nobel Prize in 1973 (Wilkinson and Fischer).
II

• Wilkinson and Woodward (1952)

Historical importance: First example of a robust organometallic

complex, and demonstrated that ligands design can effect the stability.
 Cyclopentadienyl Anion
➢ Why is the pKa of cyclopentadiene so much
lower?

➢ The conjugate base is aromatic

Common Organic Ligands
 Terminology: Hapticity (η)
h x “eta-x” was originally developed to indicate how many contiguous donor atoms of a π-system
were coordinated to a metal center. Hapticity is another word used to describe the bonding mode of
a ligand to a metal center. An η5-cyclopentadienyl ligand, for example, has all five carbons of the ring
bonding to the transition metal center.
hx values for all-carbon based ligands where the x value is odd usually indicate anionic carbon
ligands (e.g., η5-Cp, η1-CH3, η1-allyl or η3-allyl, η1-CH=CH2). The # of electrons donated (ionic method
of electron counting) by the ligand is usually equal to x + 1. Even ηx values usually indicate neutral
carbon π-system ligands (e.g., η6-C6H6, η2-CH2=CH2, η4-butadiene, η4-cyclooctadiene). The # of
electrons donated by the ligand in the even (neutral) case is usually just equal to x.

Ferrocene
 Electron Counting: The 18 Electron Rule
➢ Electron counting is an important tool to judge whether a given compound is stable or not.

➢ You are familiar with the octet rule for the second-row elements. The 18-electron rule is
analogous formulation for transition elements (with many exceptions!).

➢ For thermodynamically stable complexes, the number of ligands attached to a metal will be
such that the sum of the number of electron donated by the ligands plus the valence electrons
on the metal will be 18.

➢ Why 18? It is the maximum number of electrons that can be accommodated by One {ns}, three
{np}, and five {(n-1)d} orbitals.

➢ Structures which have this preferred count are called electron-precise.

➢ Structures which have less than 18 electrons are termed as “coordinatively unsaturated” (they
have room for more ligand(s))
 Applicability of the 18 Electron Rule
❑For early transition metals, 18e- is often unattainable for steric reasons

➢ The required number of ligands would not fit.

❑For later transition metals, 16e- is often quite stable

➢ In particular for square-planar d8 complexes.

While there are many exceptions, we will focus on systems where

the 18-electron rule can be applied to understand
structure/reactivity.

NOTE: 18e– “rule” is more of a suggestion. Many of the most interesting,

i.e., reactive, complexes do not follow this “rule”.
How to count electrons?
 Methods for Counting Electrons
• First method is called “ionic method” which considers charges on the metal
ion and ligands in order to calculate the number of electrons.

• Second method is called “neutral atom method”.

We will follow only the ionic method to avoid any confusion

• Determine the oxidation state of the transition metal center(s) and the metal
centers resulting d-electron count. To do this one must: [Ni(CO)4]
• a) Note any overall charge on the metal complex
• b) Know the charges of the ligands bound to the metal
center (ionic ligand method)
• c) know the number of electrons being donated to the metal Ni
center from each ligand (ionic ligand method)

• Add up the electron counts for the metal center and ligands.
 Common Ligands and Electrons Contributed
• Electron Counting

a) Common ligands are assigned an

electron count and charge; those that are
commonly ions are treated as such.

b) The overall charge on the complex

must equal the total charge on ligands
plus the charge on the metal; this helps
determine d-electron count of metal.

c) Add up all electrons from metal d

orbitals and ligands to find total electron
count.
Varying Hapticity = Varying Electron Contribution

2 electron donor

4 electron donor

6 electron donor
The allyl anion has similar attributes

A molecule can have the

Same ligand in different
hapticities.

4 electron donor 2 electron donor

 Metal-Carbonyl Complexes
• The carbonyl ligand forms a huge number of complexes with metal ions, most
commonly in low oxidation states, where it binds to the metal through its
C-donor, as in the complexes below, where all the metal ions are zero-valent:

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

Ni(0), d10 = 10e- Fe(0), d8 = 8e- Cr(0), d6 = 6e-
4 x CO = 8e- 5 x CO = 10e- 6 x CO = 12e-
18 e- 18 e- 18 e-
 Example: A Simple Case
• There is no overall charge on the complex
• There is one anionic ligand (CH3-, methyl group)
• The Re metal atom must have a +1 charge to
compensate for the one negatively charged
ligand. So the Re is the in the +1 oxidation state.
We denote this three different ways: Re(+1),
Re(I), or ReI.
Exceptions to the 18-Electron “Rule”
Re(+1), d6 6e-
2 PR3 4e-
2 CO 4e-
CH3- 2e-
CH2=CH2 2e-
Total: 18e-
Early Transition Middle Transition Late Transition
Metals Metals Metals
 Example: Somewhat Tricky! Exceptions to the 18-Electron “Rule”

1) There is no overall charge on the

complex

2) There is one anionic ligand (C3H5-, allyl)

3) The top ligand is NOT a MeCp-!

It is a neutral diene that has a H Early Transition
Metals
Middle Transition
Metals
Late Transition
Metals
attached to the methyl- 16e- and sub-16e-
configurations are
18e- configurations
are common
16e- and sub-16e-
configurations are
substituted ring carbon. This is common common
Coordination Coordination Coordination
a neutral 4e- donor. geometries higher geometries of 6 are geometries of 5 and
than 6 relatively common lower are common:
common d 8 = square planar

4) Because the complex is neutral and there is one

Rh(+1), d8 d 6 8e-
anionic ligand present, the Rh atom must have a PR3 2e-
+1 charge to compensate for the one negatively η4-C5H5Me 4e-
charged ligand. So the Rh atom is in the +1 η3-C3H5- 4e-
oxidation state.
Total: 18e-
18 Electron Rule Explains Some Observations
• The compound Mn2(CO)10 exists but Mn(CO)5 does not.
• A species such as [Mn(CO)5] would have only 17 e-.
• 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 18-electron rule,
we look at one metal at a time:

[Mn2(CO)10]
Mn(0), d7 = 7 e-
Mn-Mn
bond 5 C≡O = 10 e-
Mn Mn-Mn = 1 e-
Mn
18 e-
 Bridging Carbonyl Ligands
bridging • Carbonyls may form bridges between
[Co2(CO)8] carbonyls two metals, where they donate one
electron to each metal in working out the
18 electron rule.
• In [Co2(CO)8] , each Co has three terminal
CO’s, two bridging CO’s, and a Co-Co
Co Co bond:

Co(0), d9 = 9e-
Co-Co 3 CO’s = 6e-
bond 2 bridged μ-CO’s = 2e-
Co-Co bond = 1e-
18e-
Four Clˉ ligands are missing in each of the given skeletons of dimeric compounds (A), (B) and (C). Given that all of them obey the
18-electron rule and no additional metal-metal bonds are present, attach the missing Clˉ ligands on the complexes in the most
appropriate manner. (6 marks)

2 cp- + 2 Ru + 4 Cl- =0
(A)
2 x (-1) + 2 Ru + 4 x (-1) = 0

(B) Ru Oxidation state = +3

Ru(III), d5 = 5e-
1 Cp- = 6e-
Ru-Ru bond = 1e-
12e-
(C)
CHM 113M: General Inorganic Chemistry

Lecture 6

Apparao Draksharapu
appud@iitk.ac.in
 Recap of Lecture V

oxy-Hc
 Bonding in Metal Carbonyls
• M-CO:
➢ σ-donation strengthens M-C bond
➢ π-back donation strengthens M-C bond and weakens C≡O

M C O M C O

As back bonding would increase, we would expect the C=O bond strength to decrease
Infrared (IR) Spectroscopy and C=O Bond Strength
• IR spectra provides information about the stretching frequency of a bond. Recall that the stronger
a bond gets, the higher its stretching frequency.

• The υCO stretching frequency of the coordinated CO is very informative as to the nature of the
bonding.

• Thus, the more important the M=C=O (C=O is a double bond) canonical structure, the lower the υCO
stretching frequency as compared to the M-C≡O structure (C≡O is a triple bond): (Note: υCO for free
C≡O is 2143 cm-1).

-2 -1 0 0
[Ti(CO)6 ]2- [V(CO)6 ]- [Cr(CO)6] [Mn(CO)6]+

υCO 1748 1858 1984 2094 cm-1

increasing M=C double decreasing M=C double
bonding bonding
IR Spectra: Bridging vs Terminal Carbonyls
• Bridging CO groups can be regarded as having a double bond C=O group, as
compared to a terminal C≡O, which is more like a triple bond:

~ triple bond ~ double bond

M The C=O group in a bridging
M-C≡O C=O carbonyl is more like the C=O in
a ketone, which typically has
M
υC=O = 1750 cm-1.
terminal carbonyl bridging carbonyl
(~ 1850-2125 cm-1) (~1700-1860 cm-1)

• One can thus use the CO stretching

frequencies around 1700-2200 cm-1 to
detect the presence of bridging CO groups.
C=O υC=O = 1750 cm-1
Bridging vs Terminal CO
 Exceptions to 18 Electron Rule
xceptions to the 18-Electron “Rule”

MeTiCl3, 8e-;
Me2NbCl3, 10e-;
WMe6, 12e-;
Pt(PCy3)2, 14e-;
[M(H2O)6]2+ (M = V, 15e-; Cr,
16e-; Mn, 17e-; Fe, 18e-),
Early Transition Middle Transition Late Transition
Metals Metals Metals CoCp2, 19e-;
16e- and sub-16e- 18e- configurations 16e- and sub-16e-
configurations are are common configurations are NiCp2, 20e-;
common common
Coordination Coordination Coordination
geometries higher geometries of 6 are geometries of 5 and
than 6 relatively common lower are common:
common d 8 = square planar
d6
 The Elementary Steps in TM Catalysis
B
atco rdinatedligand
Elementary Organometallic Reactions
Nu
[M] L [M]n
+ [M] Nu+ L
oxidative coupling
ligand exchange
nucleophilic addition
[M] n+2
[M] [M] at coordinated ligand

[M] n X + RM' [M] R A + M' X oxidative addition __>

transmetallation
[M] [M] n+2
+ A B reductive elimination <__
B
The Elementary Steps in TM Catalysis
R
E
migratory insertion __>
electrophilic addition
(carbo-, hydro-metalation)
[M] [M]
[M] E
R oxidative coupling
-elimination <__
[M]n
[M] n+2 [M] at coordinated ligand
(decarbo-, dehydro-metalation)

R O
[M] [M] R (CO) insertion
transmetallation
[M] X + RM' [M] + R M' X
C
O
 1. Oxidative Addition
Pd(0) is electron rich and has a nucleophilic character. This transformation often
represents the first step of a catalytic cycle and its mechanism depends on the nature o
• A reaction in which (usually) a neutral ligand adds to a metal center and in doing so
the metaloxidizes
as welltheas on typically
metal, the substrate
by 2e-. involved. An increase of 2 in the formal oxidation
The metal
• the
state of transferring
and of the
thetwo electrons from
coordination the metal
number to the incoming ligand breaks a
is observed.
bond in that ligand forming two new anionic ligands. At least one of these new anionic
ligands ends up bonded to the metal center.

A
n
[M] + A B [M] n+2
B

• The new M-A and M-B bonds are formed using:

➢ the electron pair of the A-B bond
The most lone
➢ one metal-centered commonly
pair encountered systems:
• The metal goes up in oxidation state (+2).
(d10 / d8): Ni(0) / Ni(II), Pd(0) / Pd(II)
• A-B formally gets reduced to A-, and B-.
8 6
 Types of Substrates (X-Y)
• Depending on the nature of the substrate (X-Y), the mechanism of the oxidative addition may
differ .
• There are three main classes of molecules (substrates) that can perform oxidative additions
to metal centers: Non-Electrophillic; Non-Electrophillic “Intact”; Electrophillic.

• Non-electrophillic: These molecules do NOT contain electronegative atoms and/or are not
good oxidizing agents. These molecules usually require the presence of an empty orbital on
the metal in order for them to pre-coordinate prior to being activated for the oxidative
addition reaction.
”
 Non Electrophilic Substrates that Do Not Fragment
• Non-electrophillic “Intact”: These molecules have a double or triple bond present. One also
needs a metal center with an empty orbital (16e- or lower count) in order to pre-coordinate the
ligand before the oxidative addition occurs.

• Alkenes and alkynes are typical “intact” ligands that can perform an oxidative addition without
fragmenting apart.

metallocyclopropene
R
R R PMe3
PMe3
Me3P Pt Pt
PMe3
e Transition
Metals
-PMe3 PMe3
- and sub-16e- R
igurations are
common
oordination
metries of 5 and
 Electrophilic Substrates
Electrophillic: These molecules do contain electronegative atoms and are good oxidizing agents.
They are often considered to be “reactive” substrates.
These molecules do NOT require the presence of an empty orbital (18e- is OK) on the metal center in
order to perform the oxidative addition reaction. Examples: X2 (X = Cl, Br, I), R-X, Ar-X, H-X, O2, etc.
e”

Late Transition
Metals
16e- and sub-16e-
configurations are
common
Coordination
geometries of 5 and
lower are common:
d 8 = square planar
 Oxidative Addition: Electrophilic Substrates
• In the case of a starting 18e- complex (shown below) only one of the two anionic ligands
(usually the strongest binding) generated from the oxidative addition will end up coordinated
to the metal unless a separate substitution reaction occurs.

ctron “Rule”

ddle Transition Late Transition

 2. Reductive Elimination
• A reductive elimination reaction is the reverse of an oxidative addition. It is a reaction in which
two cisoidal anionic ligands on a metal center couple together. Each anionic ligand pushes one
electron back onto the metal center (in the case of a monometallic complex) to reduce it by
Exceptions to the 18-Electron “Rule” 2e -.

The coupled anionic ligands then usually fall off the metal center as a neutral molecule.

Early Transition Middle Transition Late Tran

Metals Metals Meta
16e- and sub-16e- 18e- configurations 16e- and s
configurations are are common configurat
common comm
Coordination Coordination Coordin
geometries higher geometries of 6 are geometries
than 6 relatively common lower are c
common d 8 = squar
d6
 Reductive Elimination: Effect of Ligand Dissociation
• Sometimes, more than one reductive elimination possibilities arise from saturated 18e-
complexes (so long as the two ligands that you want to reductively eliminate are cisoidal to one
another).
• An understanding of the electronic requirements can facilitate reaction engineering to favour
one option over the other.

e Transition
Metals
and sub-16e-
gurations are
common
ordination
etries of 5 and
are common:
square planar Both pathways occurred; reaction was slow (~ many hours)
Reductive Elimination: Effect of Ligand Dissociation
• It has been shown that reductive elimination can be promoted by a ligand dissociation
generating an unsaturated and more electron-deficient metal center.

Exceptions to the 18-Electron “Rule”

Early Transition Middle Transition Late Transition

 3. Migratory Insertion
• A migratory insertion reaction is when a cisoidal anionic and neutral ligand on a metal
complex couple together to generate a new coordinated anionic ligand. This new anionic
ligand is composed of the original neutral and anionic ligands now bonded to one
another.

• There is NO change in the oxidation state or d electron-count of the metal center.

ctron “Rule”

ddle Transition Late Transition

ns to the 18-Electron “Rule”
Migratory Insertion of Alkenes

Early Transition Middle Transition Late Transition

Metals Metals Metals
16e- and sub-16e- 18e- configurations 16e- and sub-16e-
onfigurations are are common configurations are
common common
Coordination Coordination Coordination
geometries higher geometries of 6 are geometries of 5 and
than 6 relatively common lower are common:
common d 8 = square planar
d6

• Successive migratory insertions can lead to chain elongation

 4. Elimination Reaction
• The most common elimination is β-hydride elimination. It can be thought of as
the opposite of migratory insertion.

• No change in formal oxidation state

• You must have an empty orbital that is cisoidal to the group that you are doing an
elimination reaction on. Alternatively, a cisoidal labile ligand that can easily
dissociate to open up an empty orbital.
 Other Eliminations
• α-hydride elimination.

• Carbonyl elimination or decarbonylation.

• No change in formal oxidation state

• You must have an empty orbital that is cisoidal to the group that you are
doing an elimination reaction on. Alternatively, a cisoidal labile ligand that
can easily dissociate to open up an empty orbital.
 Applications of Organometallic Complexes
Catalyzed rxn
proceeding through
an intermediate

Ea
A catalyst is a substance that changes the rate of a
Ea
chemical reaction without itself appearing into the catalyzed
G
products.
Reactants
G

Products

• A catalyst
• Speeds up a reaction Reaction Coordinate
• Enables a reaction to proceed that otherwise does not without it
• Typically added in non-stoichiometric amounts
• Remains unchanged at the end of the reaction

• Catalysis is a kinetic phenomenon.

Homogeneous And Heterogeneous Catalysis

• Homogeneous catalysis: Catalyst and reactants are in the same phase.

• Heterogeneous catalysis: Catalyst and reactants are in the different phase (the
catalyst is usually insoluble; reaction occurs on its surface).
Homogeneous and Heterogeneous Catalysis
• Most catalytic reactions in industry use heterogeneous catalysis

Homogeneous catalysts:
Advantages generally far more selective for a single product
far more active
far more easily studied from chemical & mechanistic aspects
far more easily modified for optimizing selectivity
Disadvantages far more sensitive to permanent deactivation
far more difficult for achieving product/catalyst separations
 Terminologies in Catalysis : TON and TOF
• TON: The number of moles of substrate that a mole of catalyst can convert before becoming
inactivated.

• How many cycles that a catalyst can do TON

• TOF: 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 turnover number (TON).

Example: If 0.1 mole of catalyst converts 100 moles of substrates in 5 minutes (100% yield) then

TON = 100/0.1 = 1000

TOF = TON/time = 1000/5 min = 200 min-1

 Hydrogenation of Alkenes

Wilkinson’s catalyst
• The most commonly used catalyst is the Wilkinson’s Catalyst

• Many alkenes are hydrogenated with hydrogen at 1 atm pressure or less.to the 18-Electron “Rule”
Exceptions

• Wilkinson’s catalyst is highly sensitive to the nature of the phosphine ligand and the
alkene substrate.
• Analogous catalysts with alkyl phosphine ligands are inactive
• Highly hindered alkenes and ethylene are not hydrogenated by the catalyst

Early Transition Middle Transition Late Tra

Metals Metals Met
e”
Wilkinson’s Catalyst - Mechanism
I

Reductive Elimination 16e- Oxidative Addition

III III

18e- 18e-
Ligand Dissociation
Ligand Association
Late Transition
Metals
16e- and sub-16e-
III
configurations are III
common
Coordination
geometries of 5 and 16e- 16e-
lower are common:
d 8 = square planar III
Migratory Insertion
Alkene Coordination
18e-
 Hydroformylation

• A less common, but more appropriate name is hydrocarbonylation

• Both cobalt and rhodium complexes are used as catalysts.Exceptions to the 18-Electron “Rule”
• Alkene isomerization, alkene hydrogenation and formation of branched aldehydes are
the possible side reactions.

• Cobalt catalysts operate at 150 ºC and 250 atm, whereas RhodiumEarly

catalysts
Transition operate
Metals
at
Middle Transition
Metals
Late Transi
Metals
moderate temperatures and 1 atm. 16e- and sub-16e- 18e- configurations 16e- and sub
configurations are are common configuration
• Rhodium catalysts promotes the formation of linear aldehydes. Cobalt catalystsCoordination
common
Coordination
do so if common
Coordinati
modified with alkylphosphine ligands. geometries higher
than 6 relatively
geometries of 6 are
common
geometries of
lower are com
 Hydroformylation Exceptions to the 18-Electron “Rule”

Ligand Dissociation
I

Reductive Elimination
18e-
III I

16e -
Early Transition Middle Transition Late Tra
18e- Metals
16e- and sub-16e-
Metals
18e- configurations
Met
16e- and
Oxidative Addition configurations are are common configura
common comm
Alkene Coordination
CoordinationCoordination
geometries higher
geometries of 6 are
Coordi
geometries
than 6 relatively common lower are
I common d 8 = squa
I
d6
18e- 18e-
Ligand Association I
Migratory Insertion Ligand Association
Migratory Insertion
18e-
 Monsanto Acetic Acid Synthesis Exceptions to the 18-Electron “Rule”

• All three members of the group 9 (Co, Rh and Ir) can catalyze this reaction.
• A cobalt complex was initially used, which was replaced with the rhodium complex later on.

• Methanol initially reacts with hydroiodic acid to give methyliodideEarly

and H2O. Methyliodide
Transition Middle Transition Late Tra
reacts with the 16e- catalyst, which is the rate-determining step. Metals
16e- and sub-16e-
Metals
18e- configurations
Me
16e- and
configurations are are common configura
common com
Coordination Coordination Coord
geometries higher geometries of 6 are geometrie
than 6 relatively common lower are
common d 8 = squa
d6
• The final product formed after the catalytic cycle is acetyl iodide, which is hydrolyzed by
water to acetic acid and HI.
 Monsanto Acetic Acid Synthesis
I

Reductive Elimination 16e-

Oxidative Addition

“Rule”

III III

18e- 18e-

ansition Late Transition

Migratory Insertion
III
als Metals
urations 16e- and sub-16e- Ligand Association
mmon configurations are
common
nation
of 6 are
Coordination
geometries of 5 and 18e-
 Alkene Polymerization
ns to the 18-Electron “Rule”

If only a few monomers couple together, the short chains formed are called oligomers.

Early Transition Middle Transition Late Transition

Metals Metals Metals
16e- and sub-16e- 18e- configurations 16e- and sub-16e-
configurations are are common configurations are
common common
Coordination Coordination Coordination
geometries higher geometries of 6 are geometries of 5 and
than 6 relatively common lower are common:
common d 8 = square planar
d6

The commonly used catalyst has a tetrahydrofuran molecule occupying the fourth
coordination site of zirconium.
 Ziegler-Natta Catalyst
• Karl Ziegler in 1953, discovered a catalyst based
on TiCl3 and AlCl3 for the polymerization of
ethylene.

• Giulio Natta extended the method for the

polymerization of other olefins like propylene
and made a number of different variations.

• The Ziegler-Natta catalyst family includes Exceptions to the

halides of titanium, chromium, vanadium and
zirconium, typically activated by aluminum
halide compounds.

• Ziegler and Natta received the Nobel Prize in

Chemistry in the year 1963. Ziegler-Natta

Early Transiti
 Recap of Lecture 1
1. Importance of transition metal complexes 2. Ligands and their denticity

3. Werner theory for transition metal complexes 4. Isomerism

71
Recap of Lecture II
 Recap of Lecture III
1. John-Teller Distortion
2. CFT in Spinels
Normal Spinels : (AII)tet(BIII2)octO4
Z-out Z-in
Inverse Spinels : (BIII)tet(AIIBIII)octO4

3. Magnetism (systems with unpaired e-)

“Any non-linear molecular system in a degenerate

electronic state is unstable and will undergo distortion
to form a system of lower symmetry and lower energy
thereby removing the degeneracy”
 Recap of Lecture IV
1. Magnetism (systems with unpaired electrons)
 Recap of Lecture V

oxy-Hc