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Consider the Tanabe-Sugano diagram for a d4 electron arrangement and answer the questions that follow:
(i) What is the free-ion term for a d4 electronic arrangement?
(ii) What is the ground state term symbol for a d4 low-spin octahedral complex?
(iii) What is the ground state term symbol for a d4 high-spin octahedral complex?
(iv) List the spin-allowed transition(s) for a low-spin d4 octahedral complex?
(v) List the spin-allowed transition(s) for a high-spin d4 octahedral complex?
(vi) What are the values for L and S in the 3G term symbol?

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Greg Montoya
Greg MontoyaLv10
30 Apr 2021
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Show transcribed image text

1.(a) Calculate the gas phase or free ion term for Cr3+ and write down the term symbols expected when the symmetry is reduced to Oh or Td.

(b) By using a configuration diagram in the appropriate symmetry for each complex, determine the ground and excited state terms for [CrCl4]– and [CrCl6]3– and hence predict the UV/visible spectrum of each species. Draw an energy level diagram for each species, marking each level with the correct term symbol and show the transitions between the terms.

(c) Calculate the free ion terms for Fe2+ and Cr2+. When placed in a tetrahedral field, predict the symmetry of the terms for the ground and excited state or states. Which of these ions in tetrahedral symmetry will have an orbital contribution to observed magnetic moment in principle?

(d) The ligand field splitting in[FeCl4]2– is found to be4000 cm−1. From this value of ∆T, calculate the value of ∆O, the ligand field splitting in [FeCl6]4– and state the relationship that you have used. Is this relationship analytical or empirical? [4 marks]

(e) For the following geometries, sketch stereochemically accurate structures for the isomers (i)–(iii).

(i) fac−MX3Y3

(ii) mer−MX3Y3

(iii) MXY5

Which selection rules will apply for the d-d transitions of the electrons associated with the metal M? You can assume that ∆S = 0 applies to M in each case.

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