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Chapter 24: Problem 50

(a) A compound with formula \(\mathrm{RuCl}_{3} \cdot 5 \mathrm{H}_{2} \mathrm{O}\) is dissolved in water, forming a solution that is approximately the same color as the solid. Immediately after forming the solution, the addition of excess \(\mathrm{AgNO}_{3}(a q)\) forms \(2 \mathrm{~mol}\) of solid \(\mathrm{AgCl}\) per mole of complex. Write the formula for the compound, showing which ligands are likely to be present in the coordination sphere. (b) After a solution of \(\mathrm{RuCl}_{3} \cdot 5 \mathrm{H}_{2} \mathrm{O}\) has stood for about a year, addition of \(\mathrm{AgNO}_{3}(a q)\) precipitates \(3 \mathrm{~mol}\) of \(\mathrm{AgCl}\) per mole of complex. What has happened in the ensuing time?

Short Answer

Expert verified
In the beginning, the complex compound is \(\mathrm{[Ru(H_{2}O)_{5}Cl]^{+2}Cl^{-}}\), with 2 chlorines in the coordination sphere. After a year, the complex compound changes to \(\mathrm{[Ru(H_{2}O)_{4}Cl_{2}]^{+}Cl^{-}}\), indicating that one of the water molecules has been replaced by a chlorine anion, making all 3 chlorines part of the coordination sphere.

Step by step solution

01

Analyzing the formation of original complex compound

We know that the formula of the compound is \(\mathrm{RuCl}_{3} \cdot 5 \mathrm{H}_{2} \mathrm{O}\). When it is dissolved in water, it forms a solution similar in color to the original complex. Upon reacting with silver nitrate, 2 moles of solid \(\mathrm{AgCl}\) form per mole of complex. This implies that 2 of the 3 chlorines are part of the coordination sphere in the original complex and the other one is a counter-ion.
02

Determine the ligands in the coordination sphere

Since there are 2 moles of \(\mathrm{AgCl}\) formed per mole of complex, it means that 2 chlorines are part of the coordination sphere. The remaining chlorine and some water molecules must be outside the coordination sphere acting as counter-ions. Therefore, the formula for the compound with the ligands in the coordination sphere would be: \[\mathrm{[Ru(H_{2}O)_{5}Cl]^{+2}Cl^{-}}\]
03

Analyzing the changes in the complex after a year

After a year, the chemical reaction with silver nitrate forms 3 moles of \(\mathrm{AgCl}\) per mole of complex. This suggests that the third chlorine has entered into the coordination sphere of the complex. One of the water ligands from the coordination sphere must have been replaced by the chlorine anion.
04

Determine the new formula of the complex after a year

After a year, the chemical reaction with silver nitrate forms 3 moles of \(\mathrm{AgCl}\) per mole of the complex, indicating that all 3 chlorines are now in the coordination sphere. Therefore, we will have to update the formula of the complex compound: \[\mathrm{[Ru(H_{2}O)_{4}Cl_{2}]^{+}Cl^{-}}\] In conclusion, the initial complex formula is \(\mathrm{[Ru(H_{2}O)_{5}Cl]^{+2}Cl^{-}}\). After a year, the complex formula has changed to \(\mathrm{[Ru(H_{2}O)_{4}Cl_{2}]^{+}Cl^{-}}\) due to the rearrangement of ligands, with one of the water molecules being replaced by a chlorine anion.

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Most popular questions from this chapter

(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?

The ion \(\left[\mathrm{Fe}(\mathrm{CN})_{6}\right]^{3-}\) has one unpaired electron, whereas \(\left[\mathrm{Fe}(\mathrm{NCS})_{6}\right]^{3-}\) has five unpaired electrons. From these results, what can you conclude about whether each complex is high spin or low spin? What can you say about the placement of \(\mathrm{NCS}^{-}\) in the spectrochemical series?

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) What is themeaning of the term coordination number as it applies to metal complexes? (b) Generally speaking, what structural feature characterizes substances that can serve as ligands in metal complexes? Give an example of a ligand that is neutral and one that is negatively charged. (c) Would you expect ligands that are positively charged to be common? Explain. (d) What type of chemical bonding is characteristic of coordination compounds? Illustrate with the compound \(\mathrm{Co}\left(\mathrm{NH}_{3}\right)_{6} \mathrm{Cl}_{3}\)

Metallic elements are essential components of many important enzymes operating within our bodies. Carbonic anhydrase, which contains \(\mathrm{Zn}^{2+}\), is responsible for rapidly interconverting dissolved \(\mathrm{CO}_{2}\) and bicarbonate ion, \(\mathrm{HCO}_{3}^{-} .\) The zinc in carbonic anhydrase is coordinated by three nitrogen-containing groups and a water molecule. The enzyme's action depends on the fact that the coordinated water molecule is more acidic than the bulk solvent molecules. Explain this fact in terms of Lewis acid-base theory (Section 16.11).
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