Dr. Paul Mushonga: Course Title: Inorganic Systems and Metal Clusters

Course code: HCH416
Course Title: INORGANIC SYSTEMS AND METAL

CLUSTERS
Part A: Heterocyclic Inorganic Systems
Dr. Paul Mushonga.

Rm 205, Chemistry New Wing
Department of Chemistry
UNIVERSITY OF ZIMBWE
Email: [email protected]
Office Hours: Tue 14:00-15:30;

Thu 14:30-15:30
or by appointment.
Paul
MUSH
ISOLOBAL ANALOGY - 1
• An important contribution to the understanding of parallels
between organic and inorganic chemistry has been the
concept of ISOLOBAL MOLECULAR FRAGMENTS, described by
Roald Hoffmann
• According to Hoffmann, molecular fragments are said to be

isolobal if
– the number, symmetry properties, approximate energy and
shape of the frontier orbitals [HOMO and LUMO]
– and the number of electrons in them
are similar—not identical, but similar
• Hoffmann’s symbol to designate groups as isolobal,
2
Paul
MUSH
• It is known in chemistry that both the electronic and molecular
structure of a compound influence its chemical reactivity.
• Using a concept known as the ISOLOBAL ANALOGY, Hoffmann

has argued that if
– the symmetry, shape, and relative energy of the frontier
molecular orbitals (FMOs) for two different chemical
species are the same
– AND they have the same number of valence electrons
occupying those orbitals,
they can be considered as isolobal and should possess similar
chemical properties
•
3
Paul
MUSH
• It is known in chemistry that electronic and molecular
structure of a compound influences its chemical reactivity.
• Using a concept known as the isolobal analogy, Hoffmann has

argued that if
– the symmetry, shape, and relative energy of the frontier
molecular orbitals (FMOs) for two different chemical
species are the same
– AND they have the same number of valence electrons
occupying those orbitals,
they can be considered as isolobal and should possess similar
chemical properties.
• The ISOLOBAL CONCEPT can be used to draw parallels

between organometallic and main group reaction chemistry
4
Paul
MUSH
• While the FMOs of the main group elements follow the octet
rule, those of the organometallics obey the effective atomic
number (EAN) rule.
• Thus, it is reasonable to assume that a saturated metal

carbonyl compound such as [Cr(CO)6], which contains 18
valence electrons, should be isolobal with CH4, which has a
completely filled octet.
• Extending this analogy, the 17-electron species [Mn(CO)5]

should be isolobal with the 7-electron CH3 radical
• Indeed, the chemical reactivities of the two species are similar,

as shown below
5
Paul
MUSH
The isolobal fragments CH3.

and [Mn(CO)5] have similar
reactivity
• The isolobal relationship is indicated by the Hoffmann symbol,

a double-headed arrow with a loop:
6
Paul
MUSH
Examples of molecules which are Isolobal
• Now, the carbonyl ligands in [Mn(CO)5] can be replaced with

any two-electron donor ligands, so that [MnH5]−, [Mn(PR3)5],
[MnCl5]5− and [Mn(NCR)5] are all isolobal with [Mn(CO)5].
7
Paul
MUSH
• Thus isolobal analogy can apply to any molecular fragment
where the FMOs have the same size, shape, energy, and
occupancy.
• The species do not necessarily have to have the same number

of electrons missing from their valence shells
• Thus, for example, [Au(PPh3)], which has only 13 valence

electrons, and the 17-electron species [Mn(CO)5] are isolobal
8
Paul
MUSH
Example 1
For each of the organometallic compounds listed below, provide a main
group fragment that is isolobal with the species:
(a) [Fe(CO)2(PPh3)]−, (b) [Re(CO)5],
(c) [(𝜂6-C6H6)Cr(CO)2], and (d) [(𝜂5-Cp)Fe(CO)]
• Solution.
(a) This species has 15 valence electrons, three short
of the 18-electron rule, which makes it isolobal with
the CH fragment.
(b) This 17-electron fragment is missing a single
electron and is therefore isolobal with CH3.
(c) There are 16 valence electrons in this
organometallic compound, making it two short of a
closed shell. The main group analog would be the CH2
fragment.
(d) This species has 16 valence electrons, making it
isolobal with CH2.
9
Paul
MUSH
Intercalation CHEMISTRY - 1
• The term ‘INTERCALATION’ refers to a process whereby a
guest molecule or ion is inserted into a host lattice
• The structure of the guest–host or intercalation compound is

only slightly perturbed from the host structure
• The reaction used to form the compound is either chemically

or thermally reversible
10
Paul
MUSH
• Intercalation reactions are particularly important for a number
of reasons:
– they can be utilised to dramatically change the chemical,

electronic, optical, and magnetic properties of a host lattice
– Intercalation reactions can be used as a low temperature

(chimie douche) method to prepare novel materials which
may not be accessible by other techniques
• Intercalation reactions leave the structure of the host lattice

largely unchanged
• Thus they are different from normal solid-state reactions that

involve extensive bond breaking and structural reorganization.
11
Paul
MUSH
• Intercalation of the guest species occurs in parts of the
structure that contain a connected network of vacant lattice
sites or of mobile ionic species
• Intercalation of a mobile guest species (G) into a host lattice

(H) with interconnected vacant lattice sites ( ) can be
represented by equation (1)
• Exchange reactions where the host lattice contains a

connected network of mobile ions by equation (2)
12
Paul
MUSH
• As indicated before, intercalation reactions are usually
reversible
• In many cases, reactions occur near ambient temperature, but

in general the reaction temperature should be
– high enough to ensure mobility of the guest species
– but not so high that the strong bonds are broken and the
structure of the host lattice is rearranged
• Given the constraints of the intercalation processes, 2D-

materials are the most common hosts
• Materials with 1D-motifs can facilitate exit and entry of guest

species but also undergo major re-organization upon
13
intercalation.
Paul
MUSH
• Conversely, 3D-materials retain their structural integrity but
impede facile intercalation of guests
• Classic inorganic solids in the 2D category include layered

materials such as
– Graphite
– Graphite oxide and
– Montmorillonite (a silicate clay)
– Layered transition metal dichalcogenides
14
Paul
MUSH
Intercalation in LAYERED TRANSITION METAL CHALCOGENIDES
• Layered transition metal dichalcogenides can be considered as
molecular crystals consisting of two dimensionally infinite MX2
units (M = TMs e.g. Ti, Zr Hf, V, Nb, Ta, Mo, W and X = S, Se, Te)
held together by weak Van de Waals forces
• The general preparation methods for the synthesis

of dichalcogenide intercalation compounds are:
– Exchange reactions guest/guest
– Electrochemical intercalation by discharge of guest cations

from electrolytes on dichalcogenide cathodes
15
Paul
MUSH
– Direct thermal reaction of the host lattice with the guest
phase either pure or dissolved in an appropriate fluid phase
– Indirect reaction via an associated chemical process

providing a negative free enthalpy for the overall reaction
e.g.
(this type of reaction is used e.g. in the preparation of

LixMX2 from MX2 and C4H9Li (8))
– Co-intercalation
16
Paul
MUSH
• The guest species which have been found to intercalate into
dichalcogenide lattices may be divided into the following
categories:
– Monoatomic species: electropositive metals (alkali and
alkaline earth, Eu, Yb), post transition metals (Cu, Ag, TI, Sn)
– Lewis base molecular compounds: inorganic and organic

compounds with functional groups of Lewis base character
(e.g. NH3, heterocycles etc.)
– Cation/solvent complexes: polar molecular compounds

solvating intercalated cations (main group and transition
metal cations, organic and inorganic metal complex cations,
organic cations etc.)
17
Paul
MUSH
GRAPHITE INTERCALATION CHEMISTRY
• Graphite is a layered material and because its sheets are held

together by weak Van de Waals forces, many substances can
be intercalated between the sheets
18
Paul
MUSH
• Graphite intercalation is often accompanied by oxidation
reduction chemistry
• For example, when graphite is intercalated with potassium, the

black graphite converts to a gold lustrous metallic-looking
compound as a result of the graphite host being reduced:
• Intercalated compounds are often written with the host first,

so KC8 is usually written C8K even though the graphite is
reduced
19
Paul
MUSH
• Conversely, when graphite is intercalated with nitric acid the
host graphite is oxidized:
MECHANISM OF INTERCALATION
• Intercalation is a complex process which involves

– adsorption of guest species on host crystals,
– exchange or insertion at the host surface
– the formation of intermediate stages in layered
compounds, and
– transport within the host lattice
20
Paul
MUSH
MECHANISM OF INTERCALATION
• For a given guest species, there is a series of stoichiometric

compositions obtainable each corresponding to a STAGE.
• For a stage n compound, every nth layer contains guest

molecules so that the highest concentration of guests occurs in
the stage 1 compound
The continuous line represents the host layer, the dashed line a
21 guest layer
Paul
MUSH
• Macroscopic effects that can strongly influence the kinetics of

intercalation include
o Variations in crystal size
o Dislocations
o Stacking faults
o Pore mouth blockage can
22

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Course code: HCH416

Course Title: INORGANIC SYSTEMS AND METAL

Dr. Paul Mushonga.

Office Hours: Tue 14:00-15:30;

• According to Hoffmann, molecular fragments are said to be

• Hoffmann’s symbol to designate groups as isolobal,

• Using a concept known as the ISOLOBAL ANALOGY, Hoffmann

• Using a concept known as the isolobal analogy, Hoffmann has

• The ISOLOBAL CONCEPT can be used to draw parallels

• Thus, it is reasonable to assume that a saturated metal

• Extending this analogy, the 17-electron species [Mn(CO)5]

• Indeed, the chemical reactivities of the two species are similar,

The isolobal fragments CH3.

• The isolobal relationship is indicated by the Hoffmann symbol,

Examples of molecules which are Isolobal

• Now, the carbonyl ligands in [Mn(CO)5] can be replaced with

• The species do not necessarily have to have the same number

• Thus, for example, [Au(PPh3)], which has only 13 valence

• The structure of the guest–host or intercalation compound is

• The reaction used to form the compound is either chemically

– they can be utilised to dramatically change the chemical,

– Intercalation reactions can be used as a low temperature

• Intercalation reactions leave the structure of the host lattice

• Thus they are different from normal solid-state reactions that

• Intercalation of a mobile guest species (G) into a host lattice

• Exchange reactions where the host lattice contains a

• In many cases, reactions occur near ambient temperature, but

• Given the constraints of the intercalation processes, 2D-

• Materials with 1D-motifs can facilitate exit and entry of guest

• Classic inorganic solids in the 2D category include layered

• The general preparation methods for the synthesis

– Exchange reactions guest/guest

– Electrochemical intercalation by discharge of guest cations

– Indirect reaction via an associated chemical process

(this type of reaction is used e.g. in the preparation of

– Lewis base molecular compounds: inorganic and organic

– Cation/solvent complexes: polar molecular compounds

• Graphite is a layered material and because its sheets are held

• For example, when graphite is intercalated with potassium, the

• Intercalated compounds are often written with the host first,

• Intercalation is a complex process which involves

• For a given guest species, there is a series of stoichiometric

• For a stage n compound, every nth layer contains guest

• Macroscopic effects that can strongly influence the kinetics of

o Pore mouth blockage can

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