Inorganic Tutorial-1 (Feb-2024)

Q1. Interpret the variation, including the overall trend across the 3d series, of the following values of
oxide lattice enthalpies (in kJ mol−1). All the compounds have the rock-salt structure:
CaO (3460), TiO (3878), VO (3913), MnO (3810), FeO (3921), CoO (3988), NiO (4071).

Q2. Write down the d-orbital splitting diagram for [NiCl4]2− and [Ni(CN)4]4−. Will these complexes be
paramagnetic or diamagnetic?
Q3. The complexes [NiCl2(PPh3)2] and [PdCl2(PPh3)2] are paramagnetic and diamagnetic respectively.
What does this tell you about their structures?
Q4. Calculate the CFSE values for [NiCl4]2−, [Mn(H2O)6]2+, [Co(NCS)6]4− and [Fe(CN)6]4−.
Q5. An iron(III) complex, Fe(Me3P)2Cl3, revealed a trigonal bipyramidal geometry around Fe in the
solid state. The complex showed an effective magnetic moment of 3.87 μB at 25 °C. What is the spin
state of Fe? Draw a d-orbital splitting diagram of the complex.
Q6. Sketch the curve you would predict from crystal-field theory for the ionic radii of the first
transition series metal ions in cyanides, M(CN)2.
Q7. Predict whether (a) [Fe(OH2)]3+ or (b) [Co(CN)6]4- would Jahn Teller distorted.
Q8. An octahedral cobalt(II) complex ion was found to have a magnetic moment of 1.92 𝜇B. What is
the electronic configuration of the metal ion?
Q9. At room temperature, the observed value of 𝜇eff for [Cr(en)3]Br2 is 4.75 𝜇B. Is the complex high-
spin or low spin?
Q10. [Ru(ox)3]3— has the low-spin configuration t2g5 whereas [Fe(ox)3]3— has the high-spin
configuration t2g3 eg2. Why?
Q11. Given that [Co(OH2)6]3+ is low-spin, explain why it is possible to predict that [Co(bpy)3]3+ is
also low-spin.
Q12. An aqueous solution of Co(III) sulphate is diamagnetic but becomes paramagnetic when a large
excess of fluoride is added. Explain.
Q13. The structure of the two copper complexes is described below. It was determined that the Cu-
ligand bond distances are highly unsymmetrical in both complexes. Explain the observation.

Q14. An aqueous solution of [TiCl6]3− showed an absorbance maxima at 13000 cm−1 with a broad
hump at 12500 cm−1 in the UV-vis spectrum. Explain the origin of these transitions.