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Chapter 21: Problem 14

Predict the products of the following reactions: (a) \(\left[\mathrm{Pt}\left(\mathrm{PR}_{3}\right)_{4}\right]^{2+}+2 \mathrm{Cl}^{-}\) (b) \(\left[\mathrm{Pt} \mathrm{Cl}_{4}\right]^{2-}+2 \mathrm{PR}_{3}\) (c) \(c i s-\left[\mathrm{Pt}\left(\mathrm{NH}_{3}\right)_{2}(\mathrm{py})_{2}\right]^{2+}+2 \mathrm{Cl}^{-}\)

Short Answer

Expert verified
(a) \(\left[\mathrm{Pt}\left(\mathrm{PR}_{3}\right)_{2}\mathrm{Cl}_{2}\right]\); (b) \(\left[\mathrm{Pt} \mathrm{Cl}_{2}\left(\mathrm{PR}_{3}\right)_{2}\right]\); (c) \(cis-\left[\mathrm{Pt}\left(\mathrm{NH}_{3}\right)_{2}\mathrm{Cl}_{2}\right]\)."}

Step by step solution

01

Understanding the Type of Reaction

For each reaction, we need to predict the product based on the starting compounds and usual reactions of these types of complexes. In general, these reactions involve coordination sphere alterations where ligands are added or replaced in a metal complex.
02

Analyze Reaction (a)

Reaction (a): \(\left[\mathrm{Pt}\left(\mathrm{PR}_{3}\right)_{4}\right]^{2+}+2\mathrm{Cl}^{-}\)In this reaction, we expect chloride ions to displace two \(\mathrm{PR}_{3}\) groups in order to achieve a more stable complex. Therefore, the likely product is \(\left[\mathrm{Pt}\left(\mathrm{PR}_{3}\right)_{2}\mathrm{Cl}_{2}\right]\).This forms a neutral complex by balancing the 2+ charge of the platinum with the -1 charges from each of the chloride ions.
03

Analyze Reaction (b)

Reaction (b): \(\left[\mathrm{Pt} \mathrm{Cl}_{4}\right]^{2-}+2 \mathrm{PR}_{3}\) Here, the \(\mathrm{PR}_{3}\) groups can act as neutral ligands that replace some chloride ions around the platinum. This replacement usually happens in a square planar complex for Pt(II). Thus, the expected product is \(\left[\mathrm{Pt} \mathrm{Cl}_{2}\left(\mathrm{PR}_{3}\right)_{2}\right]\), where two chloride ions are replaced by two \(\mathrm{PR}_{3}\) groups, leading to a neutral complex.
04

Analyze Reaction (c)

Reaction (c): \(cis-\left[\mathrm{Pt}\left(\mathrm{NH}_{3}\right)_{2}(\mathrm{py})_{2}\right]^{2+}+2 \mathrm{Cl}^{-}\)In this case, chloride ions might replace other ligands or form additional interactions. Given that it is a cis complex, we can expect both chloride ions to replace the two pyridine (py) groups. The resulting complex would be \(cis-\left[\mathrm{Pt}\left(\mathrm{NH}_{3}\right)_{2}\mathrm{Cl}_{2}\right]\), which is a known stable compound.

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Key Concepts

These are the key concepts you need to understand to accurately answer the question.

Coordination Chemistry
Coordination chemistry is the study of compounds that feature a central metal atom or ion bonded to surrounding molecules called ligands. These metal-ligand combinations are known as coordination complexes. The central metal is typically a transition metal, which provides the complex with unique properties due to its ability to adopt various oxidation states and coordination numbers.
**Key features of coordination chemistry include:**
  • Coordination Sphere: Includes the central metal ion plus the ligands directly attached to it. These are often displayed in brackets, such as \([\text{Pt}(\text{PR}_3)_4]^{2+}\).
  • Coordination Number: Indicates the number of ligand atoms bonded directly to the metal center. In many cases, this is determined by the size and charge of the metal ion and the ligands.
  • Ligands: Molecules or ions that donate at least one pair of electrons to the metal, forming a coordinate covalent bond. They vary widely, including neutral molecules like water (\(H_2O\)) or ammonia (\(NH_3\)), and anions like chloride (\(Cl^-\)).
  • Complex Geometry: Depending on the coordination number and ligand types, complexes can adopt different shapes, such as tetrahedral, square planar, or octahedral.
Understanding these elements lays the foundation for grasping the transformation processes involved in reactions featuring coordination complexes.
Ligand Exchange Reactions
In ligand exchange reactions, ligands in a coordination complex are replaced by other ligands. These reactions are fundamental in coordination chemistry, frequently altering the physical and chemical properties of the complex. Ligand exchange can happen for various reasons:
  • **Stability:** Some ligand environments or arrangements around a metal ion are more stable than others.
  • **Reactant Availability:** Introduction of more robust ligands can lead to displacement of weaker ones.
  • **Geometric and Electronic Preferences:** The metal center prefers certain geometries and electronic configurations, which different ligands can influence.
The reactions given show how chloride ions participate in ligand exchange:
  • In reaction (a), chloride ions replace \(\text{PR}_3\) groups around platinum, which leads to new stability arrangements in the complex forming \(\left[\text{Pt}(\text{PR}_3)_2\text{Cl}_2\right]\).
  • In reaction (b), two chloride ions in \(\left[\text{Pt}\text{Cl}_4\right]^{2-}\) are exchanged with two \(\text{PR}_3\) ligands, forming a square-planar complex as \(\left[\text{Pt}\text{Cl}_2(\text{PR}_3)_2\right]\).
  • Reaction (c) illustrates the replacement of pyridine groups by chloride ions, forming \(cis-[\text{Pt}(\text{NH}_3)_2\text{Cl}_2]\), maintaining its cis configuration.
These examples illustrate the fluidity and dynamics inherent in coordination chemistry, where ligand identity and configurations profoundly impact the complex鈥檚 behavior.
Transition Metal Complexes
Transition metal complexes are a special subset of coordination compounds involving transition metals like platinum. These metals are known for their ability to form various compound types, thanks to their d-orbitals, enabling multiple geometric and electronic arrangements. Transition metals' characteristics:
  • **Variable Oxidation States:** Transition metals can show varied oxidation states, permitting complex formation with different charges.
  • **Variable Coordination Numbers:** Flexibility in the number of ligands bound, commonly ranging from 2 to 8, influencing complex shapes and stability.
  • **Diversity in Ligand Types:** Can interact with a broad array of ligands, altering the function and reactivity of the complexes.
  • **Catalytic Properties:** Many transition metal complexes act as catalysts, speeding up reactions without being consumed in the process, due to their redox abilities and coordination dynamics.
This field's dynamic nature allows transition metals like platinum to support diverse reactions, as seen in the original exercise. Each transformation discussed showcases different configurations and pathways possible within inorganic chemistry, highlighting the versatile chemistry of transition metal complexes.

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Most popular questions from this chapter

If a substitution process is associative, why may it be difficult to characterize an aqua ion as labile or inert?

State the effect on the rate of dissociatively activated reactions of Rh(III) complexes of (a) an increase in the overall charge on the complex, (b) changing the leaving group from \(\mathrm{NO}_{3}^{-}\)to \(\mathrm{Cl}^{-}\), (c) changing the entering group from \(\mathrm{Cl}\) - to \(\mathrm{I}^{-}\), (d) changing the cis ligands from \(\mathrm{NH}_{3}\) to \(\mathrm{H}_{2} \mathrm{O}\).

A Pt(II) complex of tetramethyldiethylenetriamine is attacked by Cl- \(10^{5}\) times less rapidly than the diethylenetriamine analogue. Explain this observation in terms of an associative rate-determining step.

Octahedral complexes of metal centres with high oxidation numbers or of \(\mathrm{d}\) metals of the second and third series are less labile than those of low oxidation number and \(\mathrm{d}\) metals of the first series of the block. Account for this observation on the basis of a dissociative rate- determining step.

The rate of reduction of \(\left[\mathrm{Co}\left(\mathrm{NH}_{3}\right)_{5}\left(\mathrm{OH}_{2}\right)\right]^{3+}\) by \(\mathrm{Cr}(\mathrm{II})\) is seven orders of magnitude slower than reduction of its conjugate base, \(\left[\mathrm{Co}\left(\mathrm{NH}_{3}\right)_{5}(\mathrm{OH})\right]^{2+}\), by \(\mathrm{Cr}(\mathrm{II})\). For the corresponding reductions with \(\left[\mathrm{Ru}\left(\mathrm{NH}_{3}\right)_{6}\right]^{2 *}\), the two differ by less than a factor of 10 . What do these observations suggest about mechanisms?
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