Structure and Bonding of Methyl Lithium (CH₃Li)

Structure:
Methyl lithium (CH₃Li) is an organolithium compound that features a simple structure. It consists of a
methyl group (CH₃) bonded to a lithium (Li) atom. The bonding is characterized by the following:
1. C-Li Bonding: The lithium atom in CH₃Li has a low electronegativity and readily donates its
electron to the carbon atom of the methyl group. This creates a highly polarized bond where the
carbon atom carries a partial negative charge and the lithium atom carries a partial positive
charge.
2. Ionic Nature: The C-Li bond in CH₃Li is considered ionic. This is because lithium is
electropositive, and it readily dissociates from the methyl group, resulting in a lithium cation
(Li⁺) and a methyl anion (CH₃⁻). The methyl anion (CH₃⁻) is highly reactive and acts as a
nucleophile in reactions.
3. Structure in Solid State: In the solid state, methyl lithium exists as a polymeric structure in
which the lithium cations are coordinated by the methyl anions. The lithium atoms are
surrounded by methyl groups in a polymeric arrangement that stabilizes the compound.
Bonding:
The bonding in CH₃Li is mainly ionic, though it exhibits some covalent character due to the overlap
of the orbitals. The interaction between the carbon and lithium atoms leads to a polarized bond, but
because of lithium's electropositivity, the bond remains predominantly ionic.

Structure and Bonding of Ferrocene (Fe(C₅H₅)₂)

Structure:
Ferrocene is an organometallic compound consisting of a central iron (Fe²⁺) cation sandwiched
between two cyclopentadienyl anions (C₅H₅⁻). The structure can be described as:
1. Sandwich Structure: The iron atom is located between two planar C₅H₅ rings, each with five
carbon atoms. The structure resembles a "sandwich," with the iron in the center and the two
cyclopentadienyl rings acting as "bread."
2. Planar Geometry: The cyclopentadienyl anions (C₅H₅⁻) are coordinated to the iron center in a
parallel, staggered arrangement. The bond between the iron and the carbon atoms in the
cyclopentadienyl rings is delocalized.
Bonding:
The bonding in ferrocene involves both ionic and covalent contributions:
1. Covalent Bonding: The iron atom forms a coordinate covalent bond with each of the five
carbon atoms in the cyclopentadienyl anion. This bonding is through the overlap of the iron d-
orbitals with the π-electrons of the C₅H₅⁻ rings, forming a stable complex.
2. Delocalized π-Bonding: The cyclopentadienyl rings have a delocalized system of π-electrons
over the five carbon atoms. This electron cloud interacts with the iron atom, stabilizing the
complex.
 3. Charge Transfer: The iron (Fe²⁺) is a cation, and the cyclopentadienyl anion (C₅H₅⁻) donates
electrons to the iron center. The bond formation is largely due to the transfer of electron density
from the cyclopentadienyl ring to the metal center, stabilizing the structure.

Structure and Bonding of Zeise's Salt ([PtCl₃(C₂H₄)]⁻)

Structure:
Zeise’s salt is a platinum-containing organometallic compound with the formula [PtCl₃(C₂H₄)]⁻,
where platinum (Pt) is in the +2 oxidation state and is coordinated with three chloride ions and one
ethene (C₂H₄) ligand. The structure can be described as:
1. Square Planar Geometry: The platinum atom is centrally located in a square planar
arrangement, coordinated to three chloride ions and one ethene molecule.
2. Coordination with Ethene: The ethene molecule (C₂H₄) forms a coordinate bond with the
platinum center, with the π-electrons of the C=C double bond interacting with the platinum d-
orbitals.
3. Anionic Complex: The complex carries a negative charge, which is associated with the
chloride ligands.
Bonding:
The bonding in Zeise’s salt involves both coordination bonding and π-complexation:
1. Coordination Bonding: The platinum atom forms coordinate covalent bonds with the chloride
ions (Cl⁻). These are typical ionic interactions where chloride ligands donate lone pairs of
electrons to the platinum.
2. π-Back Donation: The platinum ion in the +2 oxidation state has low-lying d-orbitals. These
orbitals are available for π-back donation, where platinum donates electron density from its d-
orbitals back into the π* anti-bonding orbitals of the ethene ligand. This back donation
strengthens the bond between platinum and ethene and is an example of π-acceptance by the
metal.
3. Ethene as a Ligand: The ethene molecule interacts with the platinum center through its π-
electrons, forming a π-complex. The interaction of the platinum’s d-orbitals with the ethene’s
π-system is crucial in stabilizing the complex.

Summary Comparison:
Compound Structure Bonding Type

Methyl
Ionic, with Li⁺ and CH₃⁻ ions Ionic, with some covalent character
Lithium

Sandwich structure with two C₅H₅

Ferrocene Covalent (coordinate), Delocalized π-bonding
rings
Compound Structure Bonding Type

Coordination, π-complexation (π-back

Zeise's Salt Square planar, Pt²⁺ with Cl⁻ and C₂H₄
donation)
Each of these compounds showcases a different type of bonding: ionic in methyl lithium, covalent
with delocalized electrons in ferrocene, and coordination with π-back donation in Zeise’s salt.
π-Acceptor Behavior of CO (Carbon Monoxide)
Carbon monoxide (CO) is well-known for its π-acceptor behavior, which plays a significant role in
its interactions with transition metals in coordination complexes. CO acts as a π-acceptor ligand
because it can both donate electron density to a metal center through its lone pair (in the σ-donor
mode) and accept electron density back from the metal center into its π (anti-bonding) orbitals*.
To understand this in detail, let’s discuss the Molecular Orbital Diagram for CO and the concept of
π-acceptance in the context of its interaction with transition metals.

Molecular Orbitals of CO
The molecular orbitals of CO are derived from the atomic orbitals of carbon and oxygen. Carbon has
an sp hybridization, and oxygen has sp² hybridization, contributing to the bonding and anti-bonding
interactions between the two atoms.
Here’s a breakdown of the Molecular Orbitals in CO:
1. σ-Orbital (from Carbon and Oxygen overlap):
o This is the bonding molecular orbital formed by the overlap of the sp hybrid orbital of
carbon with the sp² hybrid orbital of oxygen.
o It’s the lowest energy orbital and is fully occupied in CO.
2. π-Orbitals (from Carbon and Oxygen p-orbitals overlap):
o There are two degenerate π-bonding orbitals formed by the overlap of the p-orbitals of
carbon and oxygen.
o These orbitals contribute to the bonding between the two atoms in CO.
3. *π-Anti-bonding Orbitals (from Carbon and Oxygen p-orbitals overlap)**:
o These are the anti-bonding orbitals that arise from the interaction of the p-orbitals of
carbon and oxygen.
o They are higher in energy and are empty in CO.
4. σ-Anti-bonding Orbital*:
o This is the anti-bonding molecular orbital resulting from the overlap of the sp hybrid
orbital of carbon with the sp² hybrid orbital of oxygen.
o It is also empty in CO.

CO as a π-Acceptor Ligand
CO’s ability to act as a π-acceptor ligand is due to the availability of empty π anti-bonding orbitals*
on the CO molecule. These empty orbitals allow CO to accept electron density from the metal center
into its π* orbitals. This interaction strengthens the bond between CO and the metal, especially in
complexes with transition metals.
Let’s break this down:
1. σ-Donation:
o CO donates electron density from its lone pair (in the σ orbital) on the carbon atom to the
metal center. This is a typical σ-donor behavior.
o The interaction is based on the overlap between the carbon’s lone pair (in an sp hybrid
orbital) and the metal’s empty orbitals.
2. π-Acceptance (Back-Donation):
o In addition to donating electron density via the σ bond, CO can also accept electron
density from the metal center through π-back donation.
o This occurs when the metal has a low-lying d-orbital (often d₈ or d₁⁰) that can overlap
with the empty π anti-bonding orbitals* of CO.
o The metal donates electron density from its d-orbitals into the empty π orbitals of CO*.
This is called π-back donation, and it weakens the C-O bond in CO but strengthens the
overall metal-ligand interaction.

Molecular Orbital Diagram for CO in Metal Complexes (with π-Acceptor Behavior)

Let's now look at the Molecular Orbital diagram of CO when it interacts with a transition metal
center.
Energy Levels:
1. Metal d-orbitals: The metal’s d-orbitals (especially the low-energy dₓᵧ, dᵧ², and dₓ²₋ᵧ² orbitals)
are important for both σ-donation and π-back donation.
2. CO σ-orbital: The lone pair of electrons on carbon (in the sp hybrid orbital) donates electron
density to the metal.
3. CO π-orbital*: The empty π orbitals* on CO accept electron density from the metal's d-orbitals
in π-back donation.
Diagram for CO (as a ligand):

Interaction in a Metal-CO Complex:

 σ-Donation: The lone pair of electrons from the carbon atom of CO fills one of the metal's
empty orbitals (usually an empty d- or p-orbital).
 π-Back Donation: The metal’s low-lying d-orbitals donate electron density into the π-anti-
bonding orbitals* of CO, which weakens the C-O bond and strengthens the metal-ligand bond.
Significance of π-Back Donation:
1. Stabilization of Complex: The π-back donation interaction results in a stronger overall
bonding between the metal and CO, making CO a strong field ligand in many transition metal
complexes (like in carbonyl complexes such as [Ni(CO)₄] or [Fe(CO)₅]).
2. Weakened C-O Bond: The π-back donation from the metal causes the C-O bond in CO to
weaken, which makes CO a better ligand. This is evident from the red-shift in the C-O
stretching frequency in the IR spectrum when CO binds to a metal center.
3. Binding to Low Oxidation States: CO is particularly effective as a ligand when the metal is in
a low oxidation state (like in d⁸ or d¹⁰ metal complexes), where the metal has available low-
lying d-orbitals for π-back donation.

Conclusion:
CO's ability to act as a π-acceptor ligand is a result of its electronic structure, where the empty π anti-
bonding orbitals* can accept electron density from the low-lying d-orbitals of a transition metal.
This π-back donation strengthens the metal-ligand bond and weakens the C-O bond, making CO an
effective ligand in a variety of coordination complexes, particularly in those with transition metals in
lower oxidation states. The interaction of CO with the metal can be understood through a combination
of σ-donation and π-back donation mechanisms, both of which are critical for the stability and
reactivity of CO-metal complexes.
Synergic Effect and Use of IR Data to Explain the Extent of Back Bonding in Metal-Carbonyl
Complexes
Synergic Effect in Metal-Carbonyl Complexes
The synergic effect in metal-carbonyl complexes refers to the combined contribution of two types
of bonding interactions between the metal and the carbonyl ligands:
1. σ-Donation from the carbonyl ligand to the metal.
2. π-back donation from the metal to the carbonyl ligand.
Together, these interactions lead to a stronger metal-ligand bond than would be expected if only one
of the interactions (either σ-donation or π-back donation) were present. This combined bonding
stabilizes the complex and affects its reactivity and properties.
 σ-donation occurs when the carbonyl ligand donates electron density from its lone pair on the
carbon atom to an empty orbital of the metal. This interaction is typical for many ligands and is
the primary method through which the ligand interacts with the metal center in metal-carbonyl
complexes.
 π-back donation occurs when the metal, particularly one with available low-lying d-orbitals
(like transition metals), donates electron density from these d-orbitals to the π anti-bonding
orbitals* of the carbonyl ligand. This creates an additional stabilizing interaction, but also
weakens the C-O bond in CO.
The synergic effect in metal-carbonyl complexes arises because:
 The σ-donation strengthens the M-C bond, increasing the electron density on the metal.
  The π-back donation weakens the C-O bond in CO, but simultaneously strengthens the overall
metal-ligand interaction by creating a strong bonding interaction between the metal and CO.
This synergistic interaction leads to enhanced stability of the complex and often results in unique
electronic properties such as changes in the C-O stretching frequency in the IR spectrum.
π-Acceptor Behavior of CO (Carbon Monoxide) with Molecular Orbital Theory (MOT)
Carbon monoxide (CO) is a well-known ligand that can act as both a σ-donor and a π-acceptor in
coordination complexes. This dual behavior plays a significant role in the bonding interactions in
metal-ligand systems, especially in transition metal complexes. Understanding this behavior requires
an application of Molecular Orbital Theory (MOT) to describe how CO interacts with metal
centers.
1. CO as a σ-Donor Ligand:
 In the σ-donor role, the carbon of the CO molecule donates electron density from its lone pair
in the sp hybridized orbital into an empty d-orbital or s-orbital of the metal center.
 This donation results in the formation of a σ-bond between the carbon atom of CO and the
metal center.
2. CO as a π-Acceptor Ligand:
In addition to its σ-donor behavior, CO can also behave as a π-acceptor ligand, primarily due to the
empty π antibonding orbitals* present in CO. The π-acceptor behavior of CO is a key feature in its
bonding with transition metals, particularly in complexes where the metal is in a low oxidation state.
Molecular Orbital (MO) Theory Explanation:
To understand the π-acceptor behavior, we examine the interaction between CO and a transition
metal ion using Molecular Orbital Theory (MOT).
1. Bonding Interaction:
o In the CO molecule, the C–O bond consists of a σ-bond formed from the overlap of the
sp hybrid orbital of carbon with the sp hybrid orbital of oxygen, and a π-bond from
the overlap of p-orbitals on carbon and oxygen.
o The CO molecule has two main types of orbitals involved in the interaction with the
metal center:
 A σ-orbital from the lone pair on carbon (acting as a donor).
 A π antibonding orbital* on the oxygen atom (acting as an acceptor).
2. Interaction with the Metal:
o The metal provides empty orbitals that can overlap with the π antibonding orbital* on
oxygen, allowing the metal to accept electron density from the π orbital of CO*.
o This interaction leads to the formation of a π-back bond from the metal into the π
antibonding orbital* of CO.
o The overall bonding interaction is described as follows:
 σ-donation: The lone pair on carbon donates electron density to the metal’s empty
orbital.
  π-back donation: The metal donates electron density from its d-orbitals into the
π antibonding orbital* of CO (primarily on oxygen).
3. The Resulting Molecular Orbitals:
o The bonding interaction between CO and the metal is a combination of σ-donation and
π-back donation. The σ-donation strengthens the bond between the metal and the
carbon, while the π-back donation weakens the C–O bond in CO.
o This is why CO is often described as a ligand that strengthens the metal-ligand bond
by back donation and weakens the C–O bond simultaneously.
Energy Diagram for CO as a π-Acceptor Ligand:
1. Metal d-Orbitals: The metal provides a set of d-orbitals, some of which are empty and can
participate in π-back donation.
2. CO Orbitals: CO has a σ-donor orbital (the lone pair on carbon) and π antibonding orbitals*
(mainly on oxygen) that can accept electron density.
The interaction can be illustrated in the following energy diagram:

In the diagram:
 σ-donation occurs between the CO lone pair and the metal's empty orbital.
 π-back donation occurs from the metal’s filled d-orbitals into the CO π antibonding orbital*.
π-Acceptor Behavior and Its Consequences:
1. Bonding Strength:
o The σ-donation strengthens the bond between the metal and the carbon atom of CO.
o The π-back donation weakens the bond between carbon and oxygen, leading to a
weaker C–O bond.
2. Spectroscopic Observations:
o The C–O stretching frequency in the IR spectrum is often observed to shift to a lower
frequency due to π-back donation. This shift indicates a weakening of the C–O bond.
o The extent of the back donation can be inferred from the IR spectra of the CO-ligated
complexes. A larger shift corresponds to more back donation.
3. Influence of Metal Oxidation State:
o The π-back donation is more significant when the metal is in a low oxidation state.
This is because metals in lower oxidation states have more electrons in their d-orbitals,
making them more capable of π-back donation.
o As the oxidation state of the metal increases, its ability to donate electrons into the π
orbital of CO* decreases.
4. Color and Magnetism:
 o The π-acceptor behavior of CO can also affect the color and magnetic properties of
metal complexes. The extent of back donation can alter the electronic configuration of
the metal, influencing the d-d transitions and magnetic behavior (such as whether the
complex is paramagnetic or diamagnetic).
Summary of π-Acceptor Behavior of CO:
 CO acts as both a σ-donor (donating electron density from its lone pair on carbon) and a π-
acceptor (accepting electron density into its π antibonding orbital* on oxygen).
 This dual interaction leads to a stronger metal-ligand bond due to σ-donation and a weaker
C–O bond due to π-back donation.
 The degree of back donation can be inferred from IR spectra, where a shift in the C–O
stretching frequency to lower values indicates more π-back donation.
 π-acceptor behavior is more pronounced in low oxidation state metals and plays a key role in
the bonding and stability of metal-carbonyl complexes.
In summary, the π-acceptor behavior of CO significantly influences the bonding, stability, and
electronic properties of metal-carbonyl complexes and is a crucial feature of many transition metal
complexes.

Using IR Data to Explain the Extent of Back Bonding

Infrared (IR) spectroscopy is an essential tool to study the nature and extent of back bonding in
metal-carbonyl complexes. The key feature of CO’s interaction with the metal is the C-O stretching
vibration, which is sensitive to both σ-donation and π-back donation.
Here’s how IR data is used to explain back bonding:
1. C-O Stretching Frequency:
o In free CO (gas phase or unbound), the C-O stretching frequency typically occurs at
around 2143 cm⁻¹.
o When CO coordinates to a metal center, the C-O stretching frequency shifts. The
extent of the shift provides valuable information about the strength of the metal-ligand
interaction, especially the degree of back bonding.
 If back donation is weak (i.e., little π-back donation), the C-O bond is only
weakly weakened, and the stretching frequency remains relatively high (closer to
the unbound CO frequency).
 If back donation is strong, the C-O bond is significantly weakened, and the C-
O stretching frequency shifts to lower values (typically in the range of 1900-2000
cm⁻¹). This shift indicates that the metal has effectively donated electron density
into the empty π orbitals* of the CO, weakening the C-O bond.
2. Correlation with Metal’s Electronic Properties:
o Metals in low oxidation states (such as Ni(0), Fe(0), and Cr(0)) have more available d-
electrons for π-back donation, leading to a lower C-O stretching frequency.
 o High oxidation state metals (such as Fe(III) or Mn(VI)) are less able to back-donate to
CO due to the lack of available d-orbitals. As a result, the C-O stretching frequency
remains relatively high.
o For example:
 In Ni(CO)₄ (Nickel Tetracarbonyl), the C-O stretching frequency is around 2000
cm⁻¹, indicating significant back donation from the Ni(0) center.
 In [Fe(CO)₅] (Iron Pentacarbonyl), the stretching frequency of CO is slightly
lower than 2000 cm⁻¹, suggesting some π-back donation from the Fe(0) center.
3. Comparing Carbonyls of Different Metals:
o The extent of back donation can also be inferred by comparing C-O stretching
frequencies in metal carbonyls of different metals. For instance:
 [Cr(CO)₆]: Chromium in the 0 oxidation state, with a low d-electron count, shows
a strong π-back donation, and the C-O stretching frequency is significantly
lowered.
 [Fe(CO)₅]: Iron also in the 0 oxidation state shows noticeable back donation, but
the C-O stretch is higher than that of chromium carbonyls, indicating less back
donation compared to chromium.
 [Ni(CO)₄]: Nickel exhibits strong back donation, but not as much as chromium, so
its C-O stretching frequency falls in between.
4. Effect of Ligand Environment:
o Additional ligands can affect the extent of back donation. For example, ligands that
donate electron density to the metal (like phosphines) can increase the electron density
on the metal and enhance back donation. Conversely, electron-withdrawing ligands
(like halides) can reduce the metal’s ability to back-donate, thus keeping the C-O
stretching frequency higher.
Summary of IR Data Interpretation:
 C-O Stretching Frequency Higher than 2000 cm⁻¹: Indicates weak or no back donation. The
metal is in a higher oxidation state or does not have available low-lying d-orbitals for back
donation.
 C-O Stretching Frequency Lower than 2000 cm⁻¹: Indicates significant back donation. The
metal is in a low oxidation state (typically 0) and has available d-orbitals for back donation into
the π* orbitals of CO.
 Comparison Across Different Metal Carbonyls: Comparing the C-O stretching frequencies
of carbonyls of different metals allows the extent of back donation to be inferred. Transition
metals in lower oxidation states show stronger back donation and thus lower C-O stretching
frequencies.

Conclusion
The synergic effect of σ-donation and π-back donation significantly influences the stability of metal-
carbonyl complexes, and the extent of back donation can be clearly assessed using IR spectroscopy.
A lower C-O stretching frequency indicates stronger π-back donation, which is typically associated
with metals in low oxidation states with available low-lying d-orbitals. By examining the C-O
stretching frequency in IR spectra, one can determine the extent of back bonding and gain insights
into the electronic structure of the metal-carbonyl complex.
18-Electron Rule as Applied to Carbonyl Complexes
The 18-electron rule is a guiding principle in organometallic chemistry that helps predict the stability
and structure of transition metal complexes, particularly those involving π-acceptor ligands like
carbon monoxide (CO). According to this rule, transition metal complexes tend to be most stable
when the total number of valence electrons (from both the metal and the ligands) equals 18.
This rule is most applicable to transition metals in their lowest oxidation states (typically 0 or +1),
which allow for the fullest use of their available d-electrons, s-electrons, and p-electrons.
In the case of metal-carbonyl complexes, the 18-electron rule provides a useful framework to
determine the stability and structure of metal carbonyls, where CO acts as a ligand that donates
electron density to the metal and also accepts electron density from the metal (through π-back
donation).
How the 18-Electron Rule Works
For a transition metal complex, the total number of valence electrons can be calculated by
considering:
1. Electrons from the metal center: The metal’s oxidation state and the number of d-electrons
it contributes.
2. Electrons from the ligands: Each CO ligand donates 2 electrons to the metal (via σ-
donation), and in cases of π-back donation, the metal may also contribute to the bonding with
the ligand.
The 18-electron configuration is achieved by summing the valence electrons from the metal and the
ligands until the total equals 18 electrons.
Application of the 18-Electron Rule to Metal-Carbonyl Complexes
1. Determining the Electron Count in Metal-Carbonyl Complexes:
Each CO ligand contributes 2 electrons to the metal center through σ-donation. For carbonyl
complexes, the electron count is determined as follows:
 The number of electrons contributed by the metal depends on its oxidation state.
 The number of electrons donated by the CO ligands is determined by the number of CO
ligands attached to the metal.
For example, in the case of a metal-carbonyl complex, the electron count can be calculated like this:
Electron Count=(Electrons from metal)+(Electrons from CO ligands)\text{Electron Count} =
(\text{Electrons from metal}) + (\text{Electrons from CO ligands})
2. Example: [Fe(CO)₅] (Iron Pentacarbonyl)
  Iron (Fe) in [Fe(CO)₅] is in the 0 oxidation state, so it contributes its full 8 valence electrons
from its 3d, 4s, and 4p orbitals.
 Each CO ligand contributes 2 electrons, and there are 5 CO ligands.
o Electrons from CO ligands: 5×2=105 \times 2 = 10 electrons.
So, the total electron count is:
Electron Count=8(from Fe)+10(from CO)=18 electrons\text{Electron Count} = 8 (\text{from Fe}) +
10 (\text{from CO}) = 18 \text{ electrons}
Thus, [Fe(CO)₅] satisfies the 18-electron rule and is stable because the metal achieves the stable
electron configuration of 18 electrons.
3. Example: [Ni(CO)₄] (Nickel Tetracarbonyl)
 Nickel (Ni) in [Ni(CO)₄] is in the 0 oxidation state, so it contributes 10 valence electrons
(from its 3d, 4s, and 4p orbitals).
 Each CO ligand contributes 2 electrons, and there are 4 CO ligands.
o Electrons from CO ligands: 4×2=84 \times 2 = 8 electrons.
So, the total electron count is:
Electron Count=10(from Ni)+8(from CO)=18 electrons\text{Electron Count} = 10 (\text{from Ni}) +
8 (\text{from CO}) = 18 \text{ electrons}
Thus, [Ni(CO)₄] also satisfies the 18-electron rule and is stable.
4. Example: [Cr(CO)₆] (Chromium Hexacarbonyl)
 Chromium (Cr) in [Cr(CO)₆] is in the 0 oxidation state, contributing 6 valence electrons.
 Each CO ligand contributes 2 electrons, and there are 6 CO ligands.
o Electrons from CO ligands: 6×2=126 \times 2 = 12 electrons.
So, the total electron count is:
Electron Count=6(from Cr)+12(from CO)=18 electrons\text{Electron Count} = 6 (\text{from Cr}) +
12 (\text{from CO}) = 18 \text{ electrons}
Thus, [Cr(CO)₆] satisfies the 18-electron rule and is stable.
Exceptions to the 18-Electron Rule
While the 18-electron rule is a valuable tool for predicting the stability of transition metal
complexes, there are some important exceptions:
1. Low Oxidation State Complexes:
o Transition metal complexes in low oxidation states (e.g., 0 or +1) with large numbers of
ligands may violate the 18-electron rule due to the steric bulk of the ligands or the
availability of low-lying d-orbitals for π-back donation.
2. Clusters and Metal-Metal Bonds:
 o Polynuclear metal carbonyl complexes (metal clusters) may have electron counts that
do not conform to the 18-electron rule but are stable due to the presence of metal-metal
bonds and additional bonding interactions between the metal atoms, such as in
[Fe₄(CO)₁₂]²⁻.
3. Metal Carbonyls with Multiple Ligands:
o Some complexes, like [Mo(CO)₆], can be stable even if they do not have exactly 18
electrons. For instance, in some cases, metal-carbonyl complexes with 16 electrons (e.g.,
[Mo(CO)₄]) can be stable due to π-back donation from the metal, which stabilizes the
electron configuration.
Conclusion
The 18-electron rule is an essential concept in the study of metal-carbonyl complexes, as it
provides a simple framework to predict the stability of such complexes. In general, transition metal
complexes with 18 valence electrons (including both the metal's electrons and those donated by the
ligands) tend to be stable. For metal-carbonyl complexes, the σ-donation from CO ligands combined
with π-back donation from the metal contributes to achieving this stable configuration. While the
rule applies to many common metal-carbonyl complexes (like Fe(CO)₅, Ni(CO)₄, and Cr(CO)₆), it is
not universal, and exceptions exist based on specific bonding scenarios.
Mononuclear and Polynuclear Carbonyls of 3d Metals
Carbonyl complexes are a significant class of coordination compounds where carbon monoxide
(CO) acts as a ligand. The CO ligand is a π-acceptor ligand that can donate electron density to the
metal center (via its lone pair in the σ-donation mode) and also accept electron density back from the
metal into its empty π orbitals* (via π-back donation). The chemistry of carbonyl complexes is rich
and diverse, especially when considering the mononuclear (single metal center) and polynuclear
(multiple metal centers) complexes of 3d transition metals.
Mononuclear Carbonyls of 3d Metals
Mononuclear carbonyl complexes involve a single metal atom coordinated to one or more CO
ligands. These complexes are often characterized by their geometry, oxidation state of the metal,
and the number of CO ligands bound to the metal.
Key Features of Mononuclear Carbonyls:
1. Geometry: Mononuclear carbonyl complexes of transition metals often adopt octahedral or
square planar geometries, depending on the metal’s oxidation state and the number of CO
ligands.
o For example, complexes like [Fe(CO)₅] adopt a trigonal bipyramidal geometry, while
[Ni(CO)₄] has a tetrahedral geometry.
2. Oxidation States: Transition metals in mononuclear carbonyls generally exist in lower
oxidation states (like +1, +2, or 0), where they have available d-orbitals for interaction with
CO ligands.
o For instance, Fe(CO)₅ has Fe in the 0 oxidation state, and Ni(CO)₄ has Ni in the 0
oxidation state.
3. Examples of Mononuclear Carbonyls:
 o Iron (Fe) Carbonyls:
 Fe(CO)₅: A classic example where iron in the 0 oxidation state is bound to five
CO ligands. The complex adopts a trigonal bipyramidal structure.
 [Fe(CO)₄]²⁻: A reduced form where iron is in the -2 oxidation state and is
coordinated with four CO ligands.
o Nickel (Ni) Carbonyls:
 Ni(CO)₄: Nickel in the 0 oxidation state, coordinated with four CO ligands, adopts
a tetrahedral structure.
o Chromium (Cr) Carbonyls:
 Cr(CO)₆: Chromium in the 0 oxidation state, coordinated with six CO ligands,
adopting an octahedral structure.
4. Bonding:
o The bonding in mononuclear carbonyls is characterized by σ-donation from CO to the
metal and π-back donation from the metal to the CO ligand. This synergistic bonding
interaction stabilizes the complex.
5. Stability: The stability of mononuclear carbonyls is influenced by the metal’s d-electron
count, which affects the availability of low-lying d-orbitals for π-back donation. For
instance, transition metals with d⁸ or d¹⁰ configurations (such as Ni and Fe) are more stable
in carbonyl complexes due to the availability of these orbitals for π-back donation.
Examples of Mononuclear 3d Metal Carbonyls:
 [Fe(CO)₅] (Iron Pentacarbonyl)
 [Ni(CO)₄] (Nickel Tetracarbonyl)
 [Cr(CO)₆] (Chromium Hexacarbonyl)
Polynuclear Carbonyls of 3d Metals
Polynuclear carbonyl complexes involve more than one metal center, and the carbonyl ligands can
bridge between multiple metal atoms. These complexes often exhibit interesting metal-metal
interactions and are a source of cluster chemistry.
Key Features of Polynuclear Carbonyls:
1. Metal-Metal Bonding: In polynuclear carbonyls, the metal atoms can interact directly through
metal-metal bonds, in addition to the metal-ligand bonding through the CO ligands. These
interactions can result in cluster complexes where metal atoms are linked by bridging
carbonyls.
2. Cluster Geometries: These complexes can adopt various geometries, such as cubane-like
(e.g., in [Mn₄(CO)₁₂]²⁻) or icosahedral-like arrangements depending on the number of metal
centers and the nature of the bonding.
3. Examples of Polynuclear Carbonyls:
o [Fe₄(CO)₁₂]²⁻ (Iron Tetra-Carbonyl Cluster): A tetrahedral complex of four iron atoms
bridged by CO ligands, each metal center also bound to CO.
 o [Ni₄(CO)₁₂]²⁻ (Nickel Tetra-Carbonyl Cluster): This complex contains four nickel centers
with bridging CO ligands.
o [Mn₄(CO)₁₂]²⁻: A manganese carbonyl cluster with Mn-Mn bonds between the metal
centers, coordinated by CO ligands.
4. Bonding:
o The bonding in polynuclear carbonyls involves both metal-metal bonding (through
direct overlaps of metal d-orbitals) and metal-ligand bonding (via CO σ-donation and
π-back donation).
o In these complexes, CO can act as a bridge between metal atoms, with some carbonyls
binding to multiple metal centers simultaneously. This results in bridging CO ligands
and metal-metal interactions.
5. Examples of Polynuclear 3d Metal Carbonyls:
o [Fe₄(CO)₁₂]²⁻: This complex features four iron atoms in a tetrahedral arrangement, with
CO bridging between the metal centers.
o [Mn₄(CO)₁₂]²⁻: Manganese in a tetrahedral arrangement, each metal center linked by CO
ligands.
o [Ni₆(CO)₁₈]: A hexanuclear nickel carbonyl complex, where CO acts as a bridge between
the metal centers.

Bonding in Mononuclear and Polynuclear Carbonyls

The bonding in both mononuclear and polynuclear carbonyls is based on two key mechanisms:
1. σ-Donation: The lone pair of electrons on the carbon atom of CO donates electron density to
the metal center. This happens through the overlap of the CO's carbon atomic orbital with an
empty orbital of the metal (typically a d- or p-orbital).
2. π-Back Donation: The metal donates electron density from its filled d-orbitals to the empty π
anti-bonding orbitals* of CO. This interaction is critical in stabilizing the complex, particularly
for metals in low oxidation states, which have readily available d-orbitals for back donation.
3. Metal-Metal Interactions in Polynuclear Carbonyls: In addition to CO-metal interactions,
polynuclear carbonyls also exhibit metal-metal bonding, where metal atoms share electron
density between them through metal-metal bonds, which are often supported by bridging
carbonyl ligands.

Conclusion
 Mononuclear carbonyls of 3d metals like Fe, Ni, and Cr are typically stable in lower
oxidation states, with carbon monoxide acting as both a σ-donor and π-acceptor ligand.
 Polynuclear carbonyls involve multiple metal centers and may exhibit metal-metal bonding
in addition to metal-ligand bonding, leading to more complex cluster geometries.
  The bonding in both types of carbonyls involves σ-donation from CO to the metal and π-back
donation from the metal to CO, with metal-metal bonds playing a key role in polynuclear
systems.
These carbonyl complexes of 3d metals play an essential role in organometallic chemistry and are
widely studied for their structure, bonding, and reactivity.