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The complexes \(\left[\mathrm{CrBr}_{6}\right]^{3-}\) and \(\left[\mathrm{Cr}\left(\mathrm{NH}_{3}\right)_{6}\right]^{3+}\) are both known. (a) Draw the \(d\) -orbital energy-level diagram for octahedral Cr(III) 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?

Short Answer

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(a) Draw d-orbital diagram for octahedral Cr(III) with t2g lower and eg higher. (b) Colors arise from light absorption corresponding to electron transitions between t2g and eg. (c) [Cr(NH3)6]^{3+} absorbs higher energy light.

Step by step solution

01

Understanding Octahedral Cr(III) Complexes

For Cr(III) complexes, the central chromium ion has a 3+ charge, meaning it loses three electrons. This results in a \(d^3\) electron configuration because chromium originally has the configuration \[3d^5 4s^1\]. By losing three electrons, it becomes \[3d^3\].
02

Drawing the d-Orbital Energy Level for Octahedral Complexes

In an octahedral field, the \(d\)-orbitals split into two sets: the lower-energy \(t_{2g}\) (d_{xy}, d_{xz}, d_{yz}) and the higher-energy \(e_g\) (d_{x^2-y^2}, d_{z^2}) orbitals. For a \(d^3\) configuration, the three electrons fill the \(t_{2g}\) orbitals, leaving the \(e_g\) orbitals unoccupied. The energy difference between these two sets is called the crystal field splitting energy, \Delta_o\.
03

Analyzing the Color of Complexes

The color of complexes arises from the absorption of light that corresponds to the energy difference \Delta_o\ between the \(t_{2g}\) and \(e_g\) orbitals. When light is absorbed, an electron can be excited from \(t_{2g}\) to \(e_g\). The complementary color of the absorbed light is what we observe.
04

Comparing the Ligand Field Strength

Ammonia \((NH_3)\) is a stronger field ligand than bromide \((Br^-)\). This means that \[\Delta_o(\text{NH}_3) > \Delta_o(Br^-)\]. Therefore, \left[\text{Cr}(NH_3)_6\right]^{3+}\ will absorb higher energy (shorter wavelength) light compared to \left[\text{CrBr}_6\right]^{3-}\ because it has a larger \Delta_o\.

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Key Concepts

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

Octahedral Complexes
Transition metal complexes can have different geometries depending on the ligands attached to the central metal ion. One common geometry is the octahedral complex, which involves six ligands symmetrically arranged around a central metal ion. This results in an octahedral shape, similar to two square pyramids joined at their bases.

In an octahedral complex, the coordination number is usually six, meaning there are six ligand atoms directly bonded to the metal center. These types of complexes are prevalent in chemistry because they can accommodate a wide range of ligands. The arrangement of ligands in an octahedral leads to significant interest in their electronic properties, particularly the distribution of the central metal's d-orbitals.
  • Common in transition metals, especially with electron-rich metals.
  • Helps stabilize the metal ion with its symmetrical arrangement.
  • Often lead to interesting magnetic and electronic properties.
Crystal Field Theory
This theory is essential for understanding how ligands affect the electronic structure of metal ions in complexes. According to crystal field theory, when ligands approach a metal ion, they exert an electrostatic force that splits the metal's degenerate d-orbitals into different energy levels. For octahedral complexes, this splitting results in a specific pattern due to the symmetrical arrangement of the ligands around the metal ion.

In the case of an octahedral field, the five d-orbitals split into two distinct groups:
  • The lower-energy set, known as the \(t_{2g}\) orbitals, includes \(d_{xy}, d_{xz}, \text{and} \,d_{yz}\) orbitals.
  • The higher-energy set, known as the \(e_g\) orbitals, is composed of \(d_{x^2-y^2}\) and \(d_{z^2}\) orbitals.
The difference in energy levels created by this splitting is referred to as the crystal field splitting energy, \(\Delta_o\). This energy gap determines many of the complex's optical and magnetic properties. A larger \(\Delta_o\) can lead to the absorption of light at higher energies, influencing the color we observe.
d-Orbital Splitting
At the heart of understanding the behavior of transition metal complexes in an octahedral field is d-orbital splitting. When metal ions engage with ligands, the symmetrical distribution in an octahedral arrangement leads to the d-orbitals splitting into different energy states due to repulsion and the electrostatic environment created by the ligands.

For a metal ion with a \(d^n\) electron configuration, electrons will fill the lower-energy \(t_{2g}\) orbitals first, followed by the \(e_g\) orbitals if there are remaining electrons. This distribution plays a crucial role in the properties and reactivity of the complex.
  • \(\Delta_o\), the energy difference between \(t_{2g}\) and \(e_g\) orbitals, influences electronic transitions.
  • The arrangement affects how electrons are distributed among the \(d\)-orbitals, impacting magnetic properties.
  • Ligands with stronger fields produce a larger \(\Delta_o\), leading to higher-energy absorption and often more intense colors.
Understanding the splitting of d-orbitals allows chemists to predict and explain the electronic behavior and physical properties of these complexes.

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Most popular questions from this chapter

Metallic elements are essential components of many important enzymes operating within our bodies. Carbonic anhydrase, which contains \(\mathrm{Zn}^{2+}\) in its active site, is responsible for rapidly interconverting dissolved \(\mathrm{CO}_{2}\) and bicarbonate ion, \(\mathrm{HCO}_{3}^{-}\). The zinc in carbonic anhydrase is tetrahedrally coordinated by three neutral nitrogencontaining groups and a water molecule. The coordinated water molecule has a p \(K_{a}\) of \(7.5,\) which is crucial for the enzyme's activity. (a) Draw the active site geometry for the \(\mathrm{Zn}(\mathrm{II})\) center in carbonic anhydrase, just writing "N" for the three neutral nitrogen ligands from the protein. (b) Compare the \(\mathrm{p} K_{a}\) of carbonic anhydrase's active site with that of pure water; which species is more acidic? (c) When the coordinated water to the \(\mathrm{Zn}(\mathrm{II})\) center in carbonic anhydrase is deprotonated, what ligands are bound to the \(\mathrm{Zn}(\mathrm{II})\) center? Assume the three nitrogen ligands are unaffected. (d) The \(\mathrm{pK}_{a}\) of \(\left[\mathrm{Zn}\left(\mathrm{H}_{2} \mathrm{O}\right)_{6}\right]^{2+}\) is \(10 .\) Suggest an explanation for the difference between this \(\mathrm{pK}_{a}\) and that of carbonic anhydrase. (e) Would you expect carbonic anhydrase to have a deep color, like hemoglobin and other metal-ion- containing proteins do? Explain.

(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 mol of AgCl per mole of complex. What has happened in the ensuing time?

The coordination complex \(\left[\mathrm{Cr}(\mathrm{CO})_{6}\right]\) forms colorless, diamagnetic crystals that melt at \(90^{\circ} \mathrm{C}\). (a) What is the oxidation number of chromium in this compound? (b) Given that \(\left[\mathrm{Cr}(\mathrm{CO})_{6}\right]\) is diamagnetic, what is the electron configuration of chromium in this compound? (c) Given that \(\left[\mathrm{Cr}(\mathrm{CO})_{6}\right]\) is colorless, would you expect CO to be a weak-field or strong-field ligand? (d) Write the name for \(\left[\mathrm{Cr}(\mathrm{CO})_{6}\right]\) using the nomenclature rules for coordination compounds.

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?

Which periodic trend is partially responsible for the observation that the maximum oxidation state of the transition-metal elements peaks near groups 7 and \(8 ?\) (a) The number of valence electrons reaches a maximum at group 8\. (b) The effective nuclear charge increases on moving left across each period. (c) The radii of the transition-metal elements reach a minimum for group \(8,\) and as the size of the atoms decreases it becomes easier to remove electrons.

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