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Chapter 24: Problem 28

(a) Draw the two linkage isomers of \(\left[\mathrm{Co}\left(\mathrm{NH}_{3}\right)_{5} \mathrm{SCN}\right]^{2+}\). (b) Draw the two geometric isomers of \(\left[\mathrm{Co}\left(\mathrm{NH}_{3}\right)_{3} \mathrm{Cl}_{3}\right]^{2+}\). (c) Two compounds with the formula \(\mathrm{Co}\left(\mathrm{NH}_{3}\right)_{5} \mathrm{ClBr}\) can be prepared. Use structural formulas to show how they differ. What kind of isomerism does this illustrate?

Short Answer

Expert verified
The two linkage isomers of \(\left[\mathrm{Co}\left(\mathrm{NH}_{3}\right)_{5} \mathrm{SCN}\right]^{2+}\) are: 1. N-Bound Isomer: \(\left[\mathrm{Co}\left(\mathrm{NH}_{3}\right)_{5}\left( \mathrm{NCS}\right) \right]^{2+}\) 2. S-Bound Isomer: \(\left[\mathrm{Co}\left(\mathrm{NH}_{3}\right)_{5}\left( \mathrm{SCN}\right) \right]^{2+}\) The two geometric isomers of \(\left[\mathrm{Co}\left(\mathrm{NH}_{3}\right)_{3} \mathrm{Cl}_{3}\right]^{2+}\) are: 1. cis-Isomer: \(\left[\mathrm{Co}\left(\mathrm{NH}_{3}\right)_{3}\left(\mathrm{Cl}\right)_{3}\right]^{2+}_\text{cis}\) 2. trans-Isomer: \(\left[\mathrm{Co}\left(\mathrm{NH}_{3}\right)_{3}\left(\mathrm{Cl}\right)_{3}\right]^{2+}_\text{trans}\) The two compounds with the formula \(\mathrm{Co}\left(\mathrm{NH}_{3}\right)_{5} \mathrm{ClBr}\) exhibit ionization isomerism: 1. Isomer 1: \(\left[\mathrm{Co}\left(\mathrm{NH}_{3}\right)_{5}\left(\mathrm{Cl}\right)\right]^{+} \mathrm{Br}^{-}\) 2. Isomer 2: \(\left[\mathrm{Co}\left(\mathrm{NH}_{3}\right)_{5}\left(\mathrm{Br}\right)\right]^{+} \mathrm{Cl}^{-}\)

Step by step solution

01

Part (a) Step 1: Understanding Linkage Isomerism

Linkage isomers are coordination complexes that have the same composition but the connectivity of one ligand is different. In this case, we are looking at isomers of \(\left[\mathrm{Co}\left(\mathrm{NH}_{3}\right)_{5} \mathrm{SCN}\right]^{2+}\) where the thiocyanate ligand (SCN-) can bind through either the sulfur (S) or nitrogen (N) atom to the central cobalt (Co) atom.
02

Part (a) Step 2: Drawing the Isomers

There are two linkage isomers for this complex: 1. N-Bound Isomer: The nitrogen atom in SCN- is bound to the cobalt atom. \[ \left[\mathrm{Co}\left(\mathrm{NH}_{3}\right)_{5}\left( \mathrm{NCS}\right) \right]^{2+} \] 2. S-Bound Isomer: The sulfur atom in SCN- is bound to the cobalt atom. \[ \left[\mathrm{Co}\left(\mathrm{NH}_{3}\right)_{5}\left( \mathrm{SCN}\right) \right]^{2+} \]
03

Part (b) Step 1: Understanding Geometric Isomerism

Geometric isomerism occurs in coordination complexes when the arrangement of the ligands around the coordination center is different. In this case, we are looking at the isomers of \(\left[\mathrm{Co}\left(\mathrm{NH}_{3}\right)_{3} \mathrm{Cl}_{3}\right]^{2+}\). Geometric isomerism exists as cis- or trans-isomers based on the relative positions of the ligands.
04

Part (b) Step 2: Drawing the Isomers

There are two geometric isomers for this complex: 1. cis-Isomer: The three chlorine atoms are adjacent to each other. \[ \left[\mathrm{Co}\left(\mathrm{NH}_{3}\right)_{3}\left(\mathrm{Cl}\right)_{3}\right]^{2+}_\text{cis} \] 2. trans-Isomer: The three chlorine atoms are opposite to each other. \[ \left[\mathrm{Co}\left(\mathrm{NH}_{3}\right)_{3}\left(\mathrm{Cl}\right)_{3}\right]^{2+}_\text{trans} \]
05

Part (c) Step 1: Drawing the Structural Formulas

There are two compounds with the formula \(\mathrm{Co}\left(\mathrm{NH}_{3}\right)_{5} \mathrm{ClBr}\): 1. Isomer 1 \[ \left[\mathrm{Co}\left(\mathrm{NH}_{3}\right)_{5}\left(\mathrm{Cl}\right)\right]^{+} \mathrm{Br}^{-}\] 2. Isomer 2 \[ \left[\mathrm{Co}\left(\mathrm{NH}_{3}\right)_{5}\left(\mathrm{Br}\right)\right]^{+} \mathrm{Cl}^{-}\]
06

Part (c) Step 2: Identifying Type of Isomerism

In these two compounds, the ligands are in different locations around the cobalt atoms. Specifically, the chlorine is a ligand in one compound, while bromine is a ligand in the other. This type of isomerism is called ionization isomerism.

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Most popular questions from this chapter

The complexes \(\left[\mathrm{V}\left(\mathrm{H}_{2} \mathrm{O}\right)_{6}\right]^{3+}\) and \(\left[\mathrm{VF}_{6}\right]^{3-}\) are both known. (a) Draw the \(d\) -orbital energy-level diagram for \(\mathrm{V}(\mathrm{III})\) octahedral complexes. (b) What gives rise to the colors of these complexes? (c) Which of the two complexes would you expect to absorb light of higher energy? Explain.

Generally speaking, for a given metal and ligand, the stability of a coordination compound is greater for the metal in the \(3+\) rather than in the \(2+\) oxidation state. Furthermore, for a given ligand the complexes of the bivalent metal ions of the first transition series tend to increase in stability in the order \(\mathrm{Mn}(\mathrm{II})<\mathrm{Fe}(\mathrm{II})<\mathrm{Co}(\mathrm{II})<\) \(\mathrm{Ni}(\mathrm{II})<\mathrm{Cu}(\mathrm{II})\). Explain how these two observations are consistent with one another and also consistent with a crystal-field picture of coordination compounds.

(a) Sketch a diagram that shows the definition of the crystal-field splitting energy \((\Delta)\) for an octahedral crystal field. (b) What is the relationship between the magnitude of \(\Delta\) and the energy of the \(d-d\) transition for a \(d^{1}\) complex? (c) Calculate \(\Delta\) in \(\mathrm{kJ} / \mathrm{mol}\) if a \(d^{1}\) complex has an absorption maximum at \(590 \mathrm{~nm}\).

The value of \(\Delta\) for the \(\left[\mathrm{CrF}_{6}\right]^{3-}\) complex is \(182 \mathrm{~kJ} / \mathrm{mol}\). Calculate the expected wavelength of the absorption corresponding to promotion of an electron from the lower-energy to the higher-energy \(d\) -orbital set in this complex. Should the complex absorb in the visible range? (You may need to review Sample Exercise 6.3; remember to divide by Avogadro's number.)

The complex \(\left[\mathrm{Mn}\left(\mathrm{NH}_{3}\right)_{6}\right]^{2+}\) contains five unpaired electrons. Sketch the energy-level diagram for the \(d\) orbitals, and indicate the placement of electrons for this complex ion. Is the ion a high-spin or a low-spin complex?
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