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Question
Draw figure to show the splitting of d orbitals in an octahedral crystal field.
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Solution
- Let the six ligands be symmetrically located along the Cartesian axes and the metal atom is at the origin.
- On approaching the ligand, the energy of the d-orbitals increases as expected compared to the free ions. As is the case in a spherical crystal field.
- The orbitals along the axes (`d_(z^2)` and `d_(x^2 - y^2)`) repel more strongly than the dxy, dyz and dzx orbitals and have lobes directed between the axes.
- In the spherical crystal field, the `d_(Z^2)` and `d_(x^2 - y^2)` orbitals increase in energy and the dxy, dyz, dzx orbitals decrease in energy compared to the average energy.
d orbital splitting in an octahedral crystal field - Therefore, the degenerate set of d-orbitals splits into two groups: the low energy orbital group t2g and the high energy orbital group eg separated by energy Δo.
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(ii) \[\ce{[Mn(CN)6]^{3-}}\]
(iii) \[\ce{[Fe(CN)6]^{4-}}\]
(iv) \[\ce{[Fe(CN)6]^{3-}}\]
Atomic number of \[\ce{Mn, Fe, Co}\] and Ni are 25, 26, 27 and 28 respectively. Which of the following outer orbital octahedral complexes have same number of unpaired electrons?
(i) \[\ce{[MnCl6]^{3-}}\]
(ii) \[\ce{[FeF6]^{3-}}\]
(iii) \[\ce{[CoF6]^{3-}}\]
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Arrange following complex ions in increasing order of crystal field splitting energy (∆O):
\[\ce{[Cr(Cl)6]^{3-}, [Cr(CN)6]^{3-}, [Cr(NH3)6]^{3+}}\].
\[\ce{CuSO4 . 5H2O}\] is blue in colour while \[\ce{CuSO4}\] is colourless. Why?
Match the complex ions given in Column I with the hybridisation and number of unpaired electrons given in Column II and assign the correct code:
| Column I (Complex ion) | Column II (Hybridisation, number of unpaired electrons) |
| A. \[\ce{[Cr(H2O)6]^{3+}}\] | 1. dsp2, 1 |
| B. \[\ce{[Co(CN)4]^{2-}}\] | 2. sp3d2, 5 |
| C. \[\ce{[Ni(NH3)6]^{2+}}\] | 3. d2sp3, 3 |
| D. \[\ce{[MnF6]^{4-}}\] | 4. sp3, 4 |
| 5. sp3d2, 2 |
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:
\[\ce{[FeF6]^{3-}, [Fe(H2O)6]^{2+}, [Fe(CN)6]^{4-}}\]
What is the spectrochemical series?
What is crystal field splitting energy?
Read the passage carefully and answer the questions that follow.
|
Crystal field splitting by various ligands Metal complexes show different colours due to d-d transitions. The complex absorbs light of specific wavelength to promote the electron from t2g to eg level. The colour of the complex is due to the transmitted light, which is complementary of the colour absorbed. The wave number of light absorbed by different complexes of Cr ion are given below:
|
Answer the following questions:
(a) Out of ligands "A", "B", "C" and "D", which ligand causes maximum crystal field splitting? Why?
OR
Which of the two, “A” or “D” will be a weak field ligand? Why?
(b) Which of the complexes will be violet in colour? [CrA6]3- or [CrB6]3+ and why?
(Given: If 560 - 570 nm of light is absorbed, the colour of the complex observed is violet.)
(c) If the ligands attached to Cr3+ ion in the complexes given in the table above are water, cyanide ion, chloride ion, and ammonia (not in this order).
Identify the ligand, write the formula and IUPAC name of the following:
- [CrA6]3-
- [CrC6]3+
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