DTM
الامتياز في الكيمياء
by Emtiazche · 10 questions ·
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#1
1) In coordination chemistry, what does the term 'الامتياز' (ligand field splitting) primarily refer to?
- The energy separation of d-orbitals in a transition metal due to ligand interactions
- The bond dissociation energy of metal–ligand bonds
- The difference in electronegativity between metal and ligand atoms
- The energy difference between sigma and pi bonds formed with ligands
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The energy separation of d-orbitals in a transition metal due to ligand interactions
#2
2) Which factor most directly increases the magnitude of d-orbital splitting (Δ) in an octahedral complex?
- Using strong-field ligands such as CN− or CO
- Using ligands lower in the spectrochemical series
- Decreasing the oxidation state of the central metal
- Increasing the metal–ligand bond distance
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Using strong-field ligands such as CN− or CO
#3
3) For a d6 metal ion in an octahedral field, which situation favors a low-spin configuration?
- High temperature and high spin–orbit coupling
- Small Δ and weak-field ligands, leading to high pairing energy
- Presence of paramagnetic ligands that donate unpaired electrons
- Large Δ relative to pairing energy, causing electrons to pair in lower orbitals
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Large Δ relative to pairing energy, causing electrons to pair in lower orbitals
#4
4) How does a tetrahedral ligand field splitting (Δt) generally compare numerically to the octahedral splitting (Δo) for the same metal–ligand combination?
- Δt is always larger than Δo due to increased electrostatic interactions
- Δt is generally smaller, roughly 4/9 of Δo
- Δt is approximately equal to 2 × Δo
- Δt is zero because tetrahedral fields do not split d-orbitals
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Δt is generally smaller, roughly 4/9 of Δo
#5
5) Which experimental technique directly measures the ligand field splitting energy in many transition-metal complexes?
- Nuclear magnetic resonance (NMR) chemical shifts
- UV-Vis (electronic) spectroscopy observing d–d transitions
- Mass spectrometry of the intact complex
- Infrared spectroscopy of ligand vibrations
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UV-Vis (electronic) spectroscopy observing d–d transitions
#6
6) In crystal field theory, which set of d-orbitals is higher in energy in an octahedral field?
- Core s and p orbitals are higher than d-orbitals
- eg (dz2, dx2−y2)
- All five d-orbitals remain degenerate
- t2g (dxy, dxz, dyz)
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eg (dz2, dx2−y2)
#7
7) Which of the following modifications to a complex would most likely decrease the observed ligand field splitting Δo?
- Substituting strong σ-donor/π-acceptor ligands with weak σ-donors
- Increasing the oxidation state of the metal center
- Replacing H2O ligands with CN− ligands
- Replacing a 3d metal with a 4d or 5d metal of similar charge
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Substituting strong σ-donor/π-acceptor ligands with weak σ-donors
#8
8) What role does π-backbonding play in modifying ligand field splitting for complexes with π-acceptor ligands?
- It increases splitting by withdrawing electron density from metal eg orbitals only
- It reduces splitting by donating electron density into metal t2g orbitals
- It has no effect because π-backbonding involves only ligand-centered orbitals
- It can increase Δ by stabilizing t2g orbitals through back-donation into ligand π* orbitals
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It can increase Δ by stabilizing t2g orbitals through back-donation into ligand π* orbitals
#9
9) Which statement best distinguishes crystal field theory (CFT) from ligand field theory (LFT)?
- LFT includes covalent metal–ligand interactions and orbital mixing; CFT is purely electrostatic
- They are identical theories with different names
- CFT accounts for covalency while LFT treats ligands as point charges exclusively
- CFT is a quantum mechanical method while LFT is a classical model
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LFT includes covalent metal–ligand interactions and orbital mixing; CFT is purely electrostatic
#10
10) For a complex showing an intense absorption band due to charge-transfer rather than a weak d–d transition, what does this imply about ligand field splitting and selection rules?
- Δ is very large so that d–d transitions are forbidden by spin selection only
- Charge-transfer transitions often have higher intensity and can overshadow weak parity-forbidden d–d bands
- d–d transitions are always more intense than charge-transfer bands
- It implies the complex has no unpaired electrons
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Charge-transfer transitions often have higher intensity and can overshadow weak parity-forbidden d–d bands
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