Q.Using crystal field theory, draw energy level diagram, write electronic configuration of the central metal atom/ion and determine the magnetic moment value in the following:
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🔒 Start your 14-day free trial to unlock the full solution →Concept understanding — Crystal Field Splitting
Crystal Field Splitting: From Intuition to Precision
Imagine you are a negatively charged electron sitting on a metal ion. All around you, the space is perfectly spherical — every direction feels the same. Your energy depends only on how far you are from the nucleus, not on which way you face.
Now imagine that six negative ions (or the negative ends of polar molecules) march in from the x, y, and z axes and stop close to you. Suddenly, the space around you is no longer uniform. If you try to move straight toward one of these approaching ions, you feel a strong repulsion — that path costs extra energy. If you move between the axes (say, along a diagonal), you feel less repulsion because you are farther from the incoming charges.
This is the core intuition: when ligands approach a metal ion, they break the spherical symmetry of the space around the metal. Different directions in space are no longer equivalent. Electrons in orbitals that point directly at the ligands get pushed up in energy; electrons in orbitals that point between the ligands stay lower.
The Precise Statement
Crystal Field Splitting is the splitting of degenerate d orbitals of a transition metal ion into two or more sets of different energies, caused by the electrostatic repulsion between the metal's d electrons and the negative charge (or dipole) of surrounding ligands.
For the most common geometry — octahedral — here is what happens:
- Six ligands sit at the corners of an octahedron, along the +x, −x, +y, −y, +z, −z axes.
- The dx2−y2 and dz2 orbitals point their lobes directly along these axes. These are the eg set. They feel maximum repulsion → higher energy.
- The dxy, dxz, and dyz orbitals point their lobes between the axes (into the octahedral faces). These are the t2g set. They feel less repulsion → lower energy.
The energy gap between these two sets is denoted by Δo (or 10Dq). The t2g set drops by 0.4Δo and the eg set rises by 0.6Δo, keeping the average energy unchanged (the "barycentre" rule).
The labels eg and t2g come from group theory — they describe how the orbitals transform under the symmetry operations of an octahedron. You do not need to memorise the derivation, but the notation is standard in every exam.
Why This Matters
Crystal field splitting explains three things you will see repeatedly:
- Colour — electrons can jump from t2g to eg by absorbing visible light. The gap Δo determines the colour you see.
- Magnetism — if Δo is large, electrons pair up in the lower t2g set (low spin). If Δo is small, electrons spread out (high spin). This changes the number of unpaired electrons. …
Why this formula?
Crystal Field Splitting: Why the Energy Splitting Occurs
Crystal Field Theory (CFT) explains how the d-orbitals of a transition metal ion split in energy when placed in an electrostatic field created by surrounding ligands (anions or polar molecules). The key result is that five degenerate d-orbitals split into two or more sets with different energies. Let's understand why this happens.
1. The Starting Point: Degenerate d-Orbitals
In a free transition metal ion (no ligands), all five d-orbitals have the same energy (degenerate). Their shapes are:
- dxy, dxz, dyz — lobes lie between the x, y, z axes (called t2g set in octahedral symmetry)
- dx2−y2, dz2 — lobes point directly along the x, y, z axes (called eg set)
Key idea: The spatial orientation of each orbital determines how it interacts with approaching ligands.
2. The Octahedral Case: Why eg Orbitals Are Higher in Energy
Imagine six ligands approaching along the +x, –x, +y, –y, +z, –z axes (octahedral geometry).
What happens to dx2−y2 and dz2?
- Their lobes point directly at the ligands.
- The negatively charged ligands repel the electron density in these orbitals.
- This repulsion raises the energy of these orbitals — they become less stable (higher energy).
What happens to dxy, dxz, dyz?
- Their lobes point between the axes (e.g., dxy lobes lie in the xy-plane but at 45° to x and y).
- They avoid the ligands — less repulsion.
- Their energy is lower than the eg set.
The Splitting Pattern
Δoct=E(eg)−E(t2g)
Where:
- E(eg) = energy of dx2−y2 and dz2 (higher)
- E(t2g) = energy of dxy, dxz, dyz (lower)
- Δoct is called the crystal field splitting energy (CFSE)
Why the name? The eg orbitals are "doubly degenerate" (2 orbitals), t2g are "triply degenerate" (3 orbitals). The letters come from group theory symmetry labels.
3. The Energy Conservation Rule
The total energy of all five d-orbitals must remain constant (no energy is created or destroyed). So:
- The center of gravity (average energy) of the split set equals the original degenerate energy.
- For octahedral splitting:
- 2 eg orbitals go up by +0.6Δoct each
- 3 t2g orbitals go down by −0.4Δoct each
Check:
2×(+0.6Δ)+3×(−0.4Δ)=1.2Δ−1.2Δ=0
This conservation of energy is a fundamental constraint — the splitting is not arbitrary.
4. The Tetrahedral Case: Why It's Opposite and Smaller
In a tetrahedral complex, four ligands approach from alternate corners of a cube. The axes are different:
- The dxy, dxz, dyz orbitals now point closer to the ligands (more repulsion).
- The dx2−y2 and dz2 orbitals point away from ligands (less repulsion).
Result:
- e set ( dx2−y2, dz2 ) — lower energy
- t2 set ( dxy, dxz, dyz ) — higher energy
The splitting is inverted compared to octahedral.
Magnitude:
Δtet≈94Δoct
Why smaller?
- Only 4 ligands (vs. 6) → less total repulsion.
- Ligands are not directly along axes → weaker interaction. …
Concept: Crystal Field Splitting — the d-orbitals split into t2g (lower energy) and eg (higher energy) in an octahedral field. The magnitude of Δo depends on the ligand: weak field (small Δo, high-spin) vs strong field (large Δo, low-spin).
(i) [CoF6]3−
Co3+: 3d6. F− is a weak field ligand → small Δo, high-spin.
Configuration: t2g4eg2 (4 unpaired electrons).
Magnetic moment: μ=n(n+2)=4×6=24≈4.90 BM.
(i) [Co(H2O)6]2+
Co2+: 3d7. H2O is intermediate but usually weak field for Co2+ → high-spin.
Configuration: t2g5eg2 (3 unpaired electrons).
μ=3×5=15≈3.87 BM.
(i) [Co(CN)6]3−
Co3+: 3d6. CN− is a strong field ligand → large Δo, low-spin.
Configuration: t2g6eg0 (0 unpaired electrons).
μ=0 BM (diamagnetic).
(ii) [FeF6]3−
Fe3+: 3d5. F− is weak field → high-spin.
Configuration: t2g3eg2 (5 unpaired electrons).
μ=5×7=35≈5.92 BM.
(ii) [Fe(H2O)6]2+
Fe2+: 3d6. H2O is weak field → high-spin. …
Crystal field theory explains how ligand field strength splits d-orbital energies, determining whether a complex is high-spin or low-spin. For each complex, we identify the metal ion's d-count, the ligand's field strength, fill the t2g and eg orbitals accordingly, and compute the magnetic moment using μ=n(n+2) BM, where n is the number of unpaired electrons.
Let’s work through each complex step by step. The key idea: ligands like CN⁻ are strong-field (large Δo, causing pairing), while F⁻ and H₂O are weak-field (small Δo, favouring high-spin). The geometry is octahedral for all.
(i) [CoF6]3−, [Co(H2O)6]2+, [Co(CN)6]3−
1. [CoF6]3−
- Cobalt in +3 oxidation state: Co atomic number 27, so Co³⁺ has [Ar]3d6 configuration.
- F⁻ is a weak-field ligand → small Δo. Electrons fill according to Hund's rule: high-spin.
- In octahedral field, the six d-electrons occupy: t2g4eg2 (four in t2g, two in eg).
- Number of unpaired electrons: n=4 (two in eg are unpaired, and two of the t2g electrons are unpaired because of the fourth electron pairing one).
- Magnetic moment: μ=4(4+2)=24≈4.90 BM.
A common mistake is to think Co³⁺ with weak field gives t2g3eg3 — that would be 3 unpaired, but the actual filling for d⁶ high-spin is t2g4eg2 with 4 unpaired electrons. Always apply Hund's rule to the t2g set first.
2. [Co(H2O)6]2+
- Cobalt in +2: Co²⁺ has [Ar]3d7.
- H₂O is intermediate but generally weak-field for Co²⁺ (it is borderline; for Co²⁺, H₂O acts as weak field). So high-spin.
- d⁷ high-spin octahedral: t2g5eg2.
- Unpaired electrons: n=3 (the eg has two unpaired, and the t2g has one unpaired because five electrons in three orbitals give one unpaired).
- μ=3(3+2)=15≈3.87 BM.
3. [Co(CN)6]3−
- Again Co³⁺, d⁶.
- CN⁻ is a strong-field ligand → large Δo, electrons pair up in t2g before occupying eg.
- Configuration: t2g6eg0 (all six electrons paired in the three t2g orbitals).
- Unpaired electrons: n=0.
- μ=0 BM (diamagnetic).
For d⁶, strong field gives t2g6 (low-spin, 0 unpaired), weak field gives t2g4eg2 (high-spin, 4 unpaired). The difference is dramatic — magnetic moment changes from 0 to ~4.9 BM.
(ii) [FeF6]3−, [Fe(H2O)6]2+, [Fe(CN)6]4−
4. [FeF6]3−
- Iron in +3: Fe³⁺ has [Ar]3d5.
- F⁻ is weak-field → high-spin.
- d⁵ high-spin octahedral: t2g3eg2 (Hund's rule: all five orbitals singly occupied).
- Unpaired electrons: n=5.
- μ=5(5+2)=35≈5.92 BM.
5. [Fe(H2O)6]2+
- Iron in +2: Fe²⁺ has [Ar]3d6.
- H₂O is weak-field for Fe²⁺ (it is borderline but generally considered weak for Fe²⁺). So high-spin. …
Method: Crystal Field Theory (CFT) for Octahedral Complexes
This method uses the electrostatic approach to explain how ligands split the d-orbital energies of the central metal ion.
Core Idea
In an octahedral field, the five d-orbitals split into:
- Higher energy: eg set (dx2−y2, dz2) — point directly at ligands
- Lower energy: t2g set (dxy, dyz, dzx) — point between ligands
The energy gap is Δo (or 10Dq).
Steps for Any Complex
- Determine oxidation state of the central metal ion.
- Write the dn configuration of the metal ion.
- Identify ligand strength:
- Strong field (e.g., CN⁻) → low spin (electrons pair in t2g first)
- Weak field (e.g., F⁻, H₂O) → high spin (electrons fill all orbitals singly before pairing)
- Draw the energy level diagram (split t2g and eg levels).
- Fill electrons according to Hund’s rule and spin state.
- Calculate magnetic moment using:
μ=n(n+2)BM
where n = number of unpaired electrons.
(i) Cobalt Complexes
1. [CoF6]3−
- Oxidation state: Co is +3 (since F⁻ is -1 each, total charge -3)
- Electronic config of Co³⁺: [Ar]3d6
- Ligand: F⁻ is weak field → high spin
- Filling: t2g4eg2 (4 electrons in t2g, 2 in eg)
- Unpaired electrons: n=4
- Magnetic moment:
μ=4(4+2)=24≈4.90BM
2. [Co(H2O)6]2+
- Oxidation state: Co is +2 (H₂O is neutral)
- Electronic config of Co²⁺: [Ar]3d7
- Ligand: H₂O is weak field → high spin
- Filling: t2g5eg2
- Unpaired electrons: n=3
- Magnetic moment:
μ=3(3+2)=15≈3.87BM
3. [Co(CN)6]3−
- Oxidation state: Co is +3 (CN⁻ is -1 each, total charge -3)
- Electronic config of Co³⁺: [Ar]3d6
- Ligand: CN⁻ is strong field → low spin
- Filling: t2g6eg0 (all 6 electrons paired in t2g)
- Unpaired electrons: n=0
- Magnetic moment:
μ=0BM(diamagnetic)
(ii) Iron Complexes
1. [FeF6]3−
- Oxidation state: Fe is +3 (F⁻ is -1 each)
- Electronic config of Fe³⁺: [Ar]3d5
- Ligand: F⁻ is weak field → high spin
- Filling: t2g3eg2 (Hund’s rule — all 5 orbitals singly occupied)
- Unpaired electrons: n=5
- Magnetic moment:
μ=5(5+2)=35≈5.92BM
2. [Fe(H2O)6]2+
- Oxidation state: Fe is +2 (H₂O neutral)
- Electronic config of Fe²⁺: [Ar]3d6
- Ligand: H₂O is weak field → high spin …
Common Mistakes in Crystal Field Splitting Problems
Students frequently lose marks on these exact complexes. Here are the most common errors and how to avoid each.
Mistake 1: Wrong Oxidation State of the Central Metal
The error: Students often take the given complex ion's charge as the metal's oxidation state directly.
Example: In [CoF6]3−, writing Co as +3 without calculation.
How to avoid: Always calculate systematically:
- Let oxidation state of metal = x
- Ligand charge: F⁻ = -1 each, CN⁻ = -1 each, H₂O = 0
- Complex charge = sum of charges
For [CoF6]3−:
x+6(−1)=−3⟹x=+3
For [Co(H2O)6]2+:
x+6(0)=+2⟹x=+2
Mistake 2: Confusing Strong vs Weak Field Ligands
The error: Treating H₂O as a strong field ligand or F⁻ as a strong field ligand.
The truth:
- Strong field ligands: CN⁻, CO, NH₃ (cause pairing, low spin)
- Weak field ligands: F⁻, Cl⁻, Br⁻, I⁻, H₂O (no pairing, high spin)
How to avoid: Memorise the spectrochemical series partially:
I−<Br−<Cl−<F−<OH−<H2O<NH3<en<NO2−<CN−<CO
- Left of H₂O → weak field (high spin)
- Right of H₂O → strong field (low spin)
- H₂O itself → borderline, but for 3d metals, usually weak field
Mistake 3: Wrong d-Orbital Splitting Diagram for Octahedral
The error: Drawing t2g above eg or incorrect labelling.
Correct diagram for octahedral:
- Lower energy: t2g (3 orbitals: dxy,dyz,dzx)
- Higher energy: eg (2 orbitals: dx2−y2,dz2)
How to avoid: Remember: "t₂g below, e₉ above" — the energy gap is Δo (or 10Dq).
Mistake 4: Wrong d-Electron Count
The error: Using the wrong number of d-electrons for the metal ion.
Example: For Fe³⁺ (atomic number 26), students write 5 d-electrons incorrectly.
How to avoid: Use the periodic table:
- Fe (Z=26): [Ar]3d64s2
- Fe³⁺: remove 3 electrons → 3d5
- Co (Z=27): [Ar]3d74s2
- Co³⁺: remove 3 electrons → 3d6
- Co²⁺: remove 2 electrons → 3d7
Mistake 5: Filling Electrons Incorrectly in the Diagram
The error: For weak field (high spin), students pair electrons before filling all orbitals singly.
Correct filling rules:
- Weak field (small Δo): Hund's rule — fill all 5 orbitals singly first, then pair
- Strong field (large Δo): Fill t2g completely first (pairing), then eg
Example — [CoF6]3− (Co³⁺, d6, weak field):
- Correct: t2g4eg2 (4 in t₂g: 3 singly + 1 paired; 2 in e₉ singly)
- Wrong: t2g6eg0 (that's low spin — wrong for F⁻)
Example — [Co(CN)6]3− (Co³⁺, d6, strong field):
- Correct: t2g6eg0 (all paired in t₂g)
- Wrong: t2g4eg2 (that's high spin — wrong for CN⁻)
Mistake 6: Wrong Magnetic Moment Formula
The error: Using μ=n(n+2) where n is wrong.
How to avoid:
- n = number of unpaired electrons
- Formula: μ=n(n+2) BM (Bohr magnetons) …
Showing the 12 most recent of 20 on this concept.
- CBSE 2026Set ANNUAL1 markQ.Write any one example of low spin complex.
›Reveal solutionSolution
A low-spin complex forms when a strong-field ligand causes the d electrons to pair up in the lower-energy t2g set rather than spreading into eg, reducing the number of unpaired electrons.
…
- CBSE 2026Set ANNUAL1 markMCQQ.Assertion [A]: [Ni(CN)4]2- is a square-planar and diamagnetic. Reason [R]: It has no unpaired electrons due to presence of strong field.(a) Both [A] and [R] are true and [R] is the correct explanation of [A].(b) Both [A] and [R] are true, but [R] is not the correct explanation of [A].(c) [A] is true, but [R] is false.(d) [A] is false, but [R] is true.
›Reveal solutionSolution
[Ni(CN)4]2− is indeed square planar and diamagnetic, and this is correctly explained by CN⁻ being a strong field ligand that forces electron pairing, leaving no unpaired electrons.
In [Ni(CN)4]2−, nickel is in the +2 oxidation state: Ni2+ has configuration 3d8 (8 electrons: t2g6eg2 in a free-ion sense, or 3d8=↑↓↑↓↑↓↑ ↑).
…
- CBSE 2026Set ANNUAL1 markQ.Which one is an inner-orbital complex? [Co(NH3)6]3+ or [CoF6]3−
›Reveal solutionSolution
Because NH3 is a strong-field ligand, Co3+'s d-electrons pair up and the complex uses the inner (n−1)d orbitals for hybridisation — making [Co(NH3)6]3+ the inner-orbital complex, unlike [CoF6]3−.
Analysis
Co3+ has the configuration 3d6 in both complexes; the difference lies in the field strength of the ligand.
- In [Co(NH3)6]3+: NH3 is a strong-field ligand. It forces all 6 d-electrons to pair up within three 3d orbitals (t2g6), freeing the other two 3d orbitals for hybridisation. Cobalt then hybridises as d2sp3, using inner (n−1)d, i.e. 3d, orbitals — this is an inner-orbital (low-spin) complex, diamagnetic. …
- CBSE 2025Set 56/5/11 markMCQQ.In which of the following groups are both ions coloured in aqueous solution ? I. Cu+ II. Ti4+ III. Co2+ IV. Fe2+ [Atomic number : Cu = 29, Ti = 22, Co = 27, Fe = 26] (A) I and II (B) II and III (C) III and IV (D) I and IV
›Reveal solutionSolution
The colour of a transition metal ion in aqueous solution depends on the presence of unpaired d-electrons, which allow d-d transitions. Both Co2+ and Fe2+ have unpaired d-electrons and are coloured, while Cu+ and Ti4+ have fully filled or empty d-subshells and are colourless. The correct pair is III and IV, i.e., option (C).
The question asks which two ions among the given four are coloured in aqueous solution. Colour in transition metal ions arises from the absorption of visible light due to electronic transitions between split d-orbitals — the famous d-d transition. But this only happens if the d-subshell is partially filled (i.e., has at least one unpaired electron and at least one vacant orbital). If the d-subshell is completely empty (d0) or completely filled (d10), no d-d transition is possible, and the ion is colourless (or white) in solution.
Let’s examine each ion one by one.
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Cu+ (Copper(I))
Atomic number of Cu = 29. Neutral Cu has configuration [Ar]3d104s1.
Cu+ loses the 4s electron, so its configuration becomes [Ar]3d10.
The d-subshell is completely filled. No d-d transitions possible.
Result: Colourless in aqueous solution.
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Ti4+ (Titanium(IV))
Atomic number of Ti = 22. Neutral Ti has [Ar]3d24s2.
Ti4+ loses all four valence electrons (two from 4s and two from 3d), so its configuration becomes [Ar]3d0.
The d-subshell is completely empty. No d-d transitions possible.
Result: Colourless in aqueous solution.
-
Co2+ (Cobalt(II))
Atomic number of Co = 27. Neutral Co has [Ar]3d74s2.
Co2+ loses the two 4s electrons, giving [Ar]3d7.
The d-subshell is partially filled (7 electrons in 5 orbitals — there are unpaired electrons). In aqueous solution, Co2+ forms the pink [Co(H2O)6]2+ complex.
Result: Coloured (pink) in aqueous solution. …
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- CBSE 2025Set D1 markMCQQ.The structure of complex ion [Ni(CN)4]2- is(a) Linear(b) Tetrahedral(c) Square planar(d) Octahedral
›Reveal solutionSolution
Ni2+ (d8) with strong-field CN- gives dsp2 hybridisation -> square planar [Ni(CN)4]2-.
Step 1 - oxidation state: In [Ni(CN)4]2-, four CN- (each -1) give -4; overall charge -2, so Ni is +2.
Step 2 - configuration: Ni2+ is 3d8.
Step 3 - ligand strength: CN- is a strong-field ligand. It pairs up the d electrons, freeing one 3d orbital. …
- CBSE 2025Set ANNUAL1 markQ.CO is stronger ligand than Cl⁻¹. (True / False)
›Reveal solutionSolution
True — CO lies far above Cl⁻ in the spectrochemical series, so it is a much stronger field ligand.
The spectrochemical series arranges ligands in order of increasing crystal-field splitting (Δo) they cause:
I−<Br−<S2−<SCN−<Cl−<...<NH3<en<CN−<CO
…
- CBSE 2025Set ANNUAL1 markQ.Draw a figure to show the splitting of d-orbitals in an octahedral crystal field.
›Reveal solutionSolution
Figure — The stem 'Draw a figure to show the splitting of d-orbitals in an octahedral crystal field' needs the t2g/eg e Ligands approaching along the axes in an octahedral complex raise the energy of orbitals pointing along the axes more than those pointing between the axes, splitting the 5 degenerate d-orbitals into two sets separated by Δo.
Description of the splitting (energy-level diagram in words)
In a free (gaseous) metal ion, all five d-orbitals (dxy,dyz,dzx,dx2−y2,dz2) are degenerate (equal energy). When 6 ligands approach the metal ion symmetrically along the ±x,±y,±z axes to form an octahedral complex, the orbitals lying along the axes experience more electrostatic repulsion from the approaching ligand electron pairs than the orbitals lying between the axes. This splits the 5 orbitals into two sets:
- eg set (higher energy): dx2−y2 and dz2 — these point directly at the ligands along the axes, so they are raised in energy above the mean (barycentre) by +0.6Δo (i.e. +53Δo).
- t2g set (lower energy): dxy,dyz,dzx — these point between the axes (away from the ligand directions), so they are lowered below the barycentre by −0.4Δo (i.e. −52Δo).
Schematically (energy increasing upward):
____ ____ <- e_g (d(x2-y2), d(z2)) +0.6(Delta_o) … - CBSE 2024Set 56/3/11 markMCQQ.Which of the following is diamagnetic in nature ? (A) Co3+, octahedral complex with strong field ligand (B) Co3+, octahedral complex with weak field ligand (C) Co3+, in a square planar complex (D) Co3+, in a tetrahedral complex [ Atomic number : Co = 27 ]
›Reveal solutionSolution
The key is to determine the number of unpaired electrons in Co3+ (3d6) under each geometry and ligand field. Only the octahedral strong-field (low-spin) case gives zero unpaired electrons, making it diamagnetic. The correct option is (A).
Let’s start with the core idea. A substance is diamagnetic when all its electrons are paired — no unpaired electrons means no net magnetic moment. For transition metal complexes, this depends entirely on how the d-orbitals split in energy under the influence of the surrounding ligands (Crystal Field Splitting) and how electrons fill those orbitals.
Cobalt has atomic number 27. Its ground state electron configuration is [Ar]3d74s2. When it forms Co3+, it loses three electrons — typically the two 4s electrons and one 3d electron. So Co3+ has a 3d6 configuration.
Now, six d-electrons can arrange themselves in different ways depending on the geometry of the complex and the strength of the ligand field. The geometry determines the splitting pattern of the d-orbitals, and the ligand field strength decides whether electrons pair up in lower orbitals or spread out (Hund’s rule) into higher ones.
Let’s examine each option one by one.
-
Option (A): Octahedral complex with strong field ligand
In an octahedral field, the five d-orbitals split into two sets: the lower-energy t2g (three orbitals) and the higher-energy eg (two orbitals). The energy gap Δo is large when the ligand is strong (like CN⁻, CO).
For 3d6, a strong field forces electrons to pair up in the t2g set before any electron goes to eg. So the filling is: t2g6 — all six electrons paired in three orbitals. That gives zero unpaired electrons.
TipStrong field = low spin = maximum pairing. For d6, low-spin octahedral is always diamagnetic.
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Option (B): Octahedral complex with weak field ligand
Here Δo is small. Electrons follow Hund’s rule: they occupy all five orbitals singly before pairing. For d6, the first five electrons go one each into t2g and eg (actually t2g3eg2), and the sixth electron must pair in a t2g orbital. So the configuration is t2g4eg2 — that’s four electrons in t2g (one pair, two unpaired) and two unpaired in eg. Total unpaired electrons = 4. Hence paramagnetic.
-
Option (C): Square planar complex …
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- CBSE 2024Set ANNUAL1 markQ.What is crystal field splitting energy?
›Reveal solutionSolution
When ligands approach a metal ion, electrostatic repulsion splits the previously degenerate d-orbitals into two energy sets; the gap between them is the crystal field splitting energy, Δ.
In an isolated (gas-phase) transition-metal ion, all five d-orbitals are degenerate (equal energy). When ligands approach to form a complex, their electron pairs create an electric field that repels electrons in the d-orbitals unequally, depending on each orbital's spatial orientation relative to the ligand positions.
In an octahedral field, the d-orbitals split into two sets:
- t2g (dxy,dyz,dxz) — lower energy, point between the ligand axes
- eg (dx2−y2,dz2) — higher energy, point directly at the ligands …
- CBSE 2024Set ANNUAL1 markMCQQ.A coordination compound is colourless due to –(a) the absence of ligand(b) loss of water molecules(c) d-d transition of the electron(d) energy of crystal field splitting energy
›Reveal solutionSolution
A coordination compound is colourless when it cannot undergo d-d electronic transitions — either because it has no d electrons or a completely filled d-subshell.
Colour in most coordination compounds arises from d–d transitions, where an electron is excited from a lower-energy d-orbital (t2g) to a higher-energy one (eg) after crystal field splitting, absorbing a specific wavelength of visible light (and transmitting/reflecting the complementary colour).
…
- CBSE 2023Set 56/1/11 markMCQQ.Assertion (A) : Low spin tetrahedral complexes are rarely observed. Reason (R) : Crystal field splitting energy is less than pairing energy for tetrahedral complexes. (A) Both Assertion (A) and Reason (R) are true and Reason (R) is the correct explanation of the Assertion (A). (B) Both Assertion (A) and Reason (R) are true, but Reason (R) is not the correct explanation of the Assertion (A). (C) Assertion (A) is true, but Reason (R) is false. (D) Assertion (A) is false, but Reason (R) is true.
›Reveal solutionSolution
The assertion is true — low-spin tetrahedral complexes are rare — and the reason is also true: for tetrahedral complexes, the crystal field splitting energy Δt is much smaller than the pairing energy P, making low-spin configurations energetically unfavourable. The reason correctly explains the assertion, so option (A) is correct.
Why this question hinges on crystal field splitting
In coordination chemistry, the spin state of a complex (high-spin vs low-spin) depends on a tug-of-war between two energies: the crystal field splitting energy (Δ) and the pairing energy (P). If Δ>P, electrons prefer to pair up in the lower-energy orbitals (low-spin). If Δ<P, electrons spread out to avoid pairing (high-spin).
For tetrahedral complexes, the splitting pattern is the inverse of octahedral — the dxy,dyz,dzx orbitals (called t2) are higher in energy, and the dx2−y2,dz2 orbitals (called e) are lower. But the key number is the magnitude of Δt (tetrahedral splitting).
Δt≈94Δo
For the same metal ion and ligands, tetrahedral splitting is only about 44% of octahedral splitting.
Since Δo itself is often comparable to or smaller than P for many metal ions (especially first-row transition metals), Δt ends up being much smaller than P in almost all cases. That means the energy cost of pairing electrons is never recovered by the splitting — so electrons always occupy orbitals singly before pairing, giving high-spin configurations.
Watch outA common mistake is to think that low-spin tetrahedral complexes are impossible. They are not — they are just rare. With very strong-field ligands (like CN⁻) and heavy metals (where Δ is larger), a few examples exist. But for typical exam contexts (first-row transition metals, common ligands), the statement holds.
Step-by-step reasoning
- Understand the assertion: "Low spin tetrahedral complexes are rarely observed." This is a factual statement about coordination chemistry. For a tetrahedral complex to be low-spin, the splitting Δt must exceed the pairing energy P. But because Δt is inherently small (about 4/9 of Δo), this condition is seldom met. …
- CBSE 2023Set 56/3/11 markMCQQ.Which of the following is the most stable complex species? (A) [Fe(C2O4)3]3− (B) [Fe(CN)6]3− (C) [Fe(CO)5] (D) [Fe(H2O)6]3+
›Reveal solutionSolution
The stability of a complex is primarily determined by the nature of the ligand (denticity and field strength) and the oxidation state of the central metal. Metal carbonyls, like [Fe(CO)5], exhibit exceptional stability due to synergistic bonding and often obey the 18-electron rule. The most stable complex species is (C) [Fe(CO)5].
The stability of a complex species refers to its tendency to remain intact in solution or under various conditions. Several factors influence this stability, primarily the nature of the ligand and the central metal ion. We will analyze each option based on these factors.
Concept and Intuition: Factors Affecting Complex Stability
The stability of a coordination complex is governed by the strength of the metal-ligand bonds. This strength is influenced by:
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Nature of the Ligand:
- Ligand Field Strength: Strong field ligands (e.g., CN−, CO) cause a larger crystal field splitting and generally form more stable complexes than weak field ligands (e.g., H2O). This is because stronger interactions lead to more energy required to break the bonds.
- Chelate Effect: Polydentate (chelating) ligands, which bind to the metal ion through multiple donor atoms, form significantly more stable complexes than monodentate ligands. This enhanced stability, known as the chelate effect, is primarily an entropic effect. When a chelating ligand replaces several monodentate ligands, the number of species in solution often increases, leading to a favorable increase in entropy. For example, replacing two monodentate ligands with one bidentate ligand increases the number of free species.
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Nature of the Central Metal Ion:
- Oxidation State: Generally, a higher positive oxidation state of the metal ion leads to greater stability. A higher positive charge on the metal ion results in stronger electrostatic attraction between the metal and the electron-donating ligands.
- Size: Smaller metal ions tend to form more stable complexes due to higher charge density, leading to stronger electrostatic interactions.
- Electronic Configuration: The d-electron configuration can also play a role, especially in terms of crystal field stabilization energy (CFSE).
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Synergistic Bonding (for Metal Carbonyls): In metal carbonyls, a unique type of bonding occurs where the ligand (CO) donates electrons to the metal (sigma bond) and the metal simultaneously donates electrons back to the ligand's empty antibonding orbitals (pi back-bond). This synergistic bonding greatly strengthens the metal-ligand bond, leading to exceptionally stable complexes. Many stable metal carbonyls also obey the 18-electron rule, which is a good indicator of kinetic stability.
Let's apply these concepts to the given options.
Step-by-Step Analysis
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Identify the central metal ion and its oxidation state in each complex.
- (A) [Fe(C2O4)3]3−: The central metal is Iron (Fe). Oxalate (C2O42−) is a bidentate ligand with a −2 charge. Let the oxidation state of Fe be x. x+3(−2)=−3 x−6=−3 x=+3. So, the metal ion is Fe3+.
- (B) [Fe(CN)6]3−: The central metal is Iron (Fe). Cyanide (CN−) is a monodentate ligand with a −1 charge. Let the oxidation state of Fe be x. x+6(−1)=−3 x−6=−3 x=+3. So, the metal ion is Fe3+.
- (C) [Fe(CO)5]: The central metal is Iron (Fe). Carbonyl (CO) is a neutral monodentate ligand. Let the oxidation state of Fe be x. x+5(0)=0 x=0. So, the metal is in the zero oxidation state, Fe0.
- (D) [Fe(H2O)6]3+: The central metal is Iron (Fe). Water (H2O) is a neutral monodentate ligand. Let the oxidation state of Fe be x. x+6(0)=+3 x=+3. So, the metal ion is Fe3+.
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Compare the ligands based on their denticity and field strength.
- Denticity:
- C2O42− (oxalate) is a bidentate ligand. It forms a chelate ring.
- CN− (cyanide) is a monodentate ligand.
- CO (carbonyl) is a monodentate ligand.
- H2O (aqua) is a monodentate ligand.
- Ligand Field Strength (from the spectrochemical series, weakest to strongest):
H2O<C2O42−<CN−<CO
- H2O is a weak field ligand.
- C2O42− is a moderately strong field ligand.
- CN− is a strong field ligand.
- CO is a very strong field ligand.
- Denticity:
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Evaluate the stability of each complex. …
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