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Chapter 23: Problem 45

Determine if each of the following metal complexes is chiral and therefore has an optical isomer: (a) tetrahedral \(\left[\mathrm{Zn}\left(\mathrm{H}_{2} \mathrm{O}\right)_{2} \mathrm{Cl}_{2}\right],(\mathbf{b})\) octahedral trans-[Ru(bipy) \()_{2} \mathrm{Cl}_{2} ],(\mathbf{c})\) octahedral cis-[Ru(bipy) \(_{2} \mathrm{Cl}_{2} ] .\)

Short Answer

Expert verified
In summary, the metal complexes have the following chirality: a) Tetrahedral \(\left[\mathrm{Zn}\left(\mathrm{H}_{2} \mathrm{O}\right)_{2} \mathrm{Cl}_{2}\right]\) is achiral (no optical isomer). b) Octahedral trans-\([\mathrm{Ru}(\mathrm{bipy})_{2} \mathrm{Cl}_{2}]\) is achiral (no optical isomer). c) Octahedral cis-\([\mathrm{Ru}(\mathrm{bipy})_{2} \mathrm{Cl}_{2}]\) is chiral (has an optical isomer).

Step by step solution

01

Understanding chirality

Chirality refers to the property of a molecule where it cannot be superimposed onto its mirror image. A chiral molecule has a non-superimposable mirror image, called an enantiomer. If a molecule has a center of symmetry or any point of symmetry, it is considered achiral.
02

Analyzing the first complex (a) Tetrahedral [Zn(H2O)2Cl2]

This complex has a tetrahedral geometry due to the coordination of 4 ligands to the central Zn atom. To determine its chirality, let's check for any symmetry elements. In this complex, there are 2 water ligands and 2 chloride ligands. The symmetry elements can be found by imagining a line (axis) connecting the Zn atom to the mid-point of the line connecting the two identical ligands. There are two symmetry elements in this complex, one passing through the two water ligands and the other passing through the two chloride ligands. Since the complex has symmetry elements, it is achiral and does not have an optical isomer.
03

Analyzing the second complex (b) Octahedral trans-[Ru(bipy)2Cl2]

In this complex, the Ru atom is coordinated to 2 bipy and 2 Cl ligands with an octahedral geometry. The trans-[Ru(bipy)2Cl2] complex has the two Cl ligands positioned opposite (trans) to each other. This conformation leads to the presence of a center of symmetry. Because of this symmetry, the complex is achiral and does not have an optical isomer.
04

Analyzing the third complex (c) Octahedral cis-[Ru(bipy)2Cl2]

Similar to the second complex, the Ru atom coordinates to 2 bipy and 2 Cl ligands with an octahedral geometry. The only difference is that the Cl ligands are now positioned adjacent (cis) to each other. In this conformation, there is no center of symmetry nor any other symmetry element in the cis-[Ru(bipy)2Cl2] complex. Therefore, this molecule is chiral and has an optical isomer. In summary: a) Tetrahedral [Zn(H2O)2Cl2] is achiral (no optical isomer) b) Octahedral trans-[Ru(bipy)2Cl2] is achiral (no optical isomer) c) Octahedral cis-[Ru(bipy)2Cl2] is chiral (has an optical isomer)

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Most popular questions from this chapter

If the lobes of a given \(d\)-orbital point directly at the ligands, will an electron in that orbital have a higher or lower energy than an electron in a \(d\)-orbital whose lobes do not point directly at the ligands?

Four-coordinate metals can have either a tetrahedral or a square-planar geometry; both possibilities are shown here for \(\left[\mathrm{PtCl}_{2}\left(\mathrm{NH}_{3}\right)_{2}\right] .\) (a) \(\mathrm{What}\) is the name of this molecule? (b) Would the tetrahedral molecule have a geometric isomer? (c) Would the tetrahedral molecule be diamagnetic or paramagnetic? (d) Would the square-planar molecule have a geometric isomer? (e) Would the square-planar molecule be diamagnetic or paramagnetic? (f) Would determining the number of geometric isomers help you distinguish between the tetrahedral and square-planar geometries? (g) Would measuring the molecule's response to a magnetic field help you distinguish between the two geometries? [Sections 23.4-23.6 ]

Consider the following three complexes: (Complex 1) \(\left[\mathrm{Co}\left(\mathrm{NH}_{3}\right)_{5} \mathrm{SCN}\right]^{2+}\) (Complex 2) \(\left[\mathrm{Co}\left(\mathrm{NH}_{3}\right)_{3} \mathrm{Cl}_{3}\right]^{2+}\) (Complex 3) \(\mathrm{CoClBr} \cdot 5 \mathrm{NH}_{3}\) Which of the three complexes can have (a) geometric isomers, (b) linkage isomers, (c) optical isomers, (d) coordination-sphere isomers?

Consider the tetrahedral anions \(\mathrm{VO}_{4}^{3-}\) (orthovanadate ion), \(\mathrm{CrO}_{4}^{2-}\) (chromate ion), and \(\mathrm{MnO}_{4}^{-}\) (permanganate ion). (a) These anions are isoelectronic. What does this statement mean? (b) Would you expect these anions to exhibit \(d-d\) transitions? Explain. (c) As mentioned in "A Closer Look" on charge-transfer color, the violet color of MnO \(_{4}^{-}\) is due to a ligand-to-metal charge transfer (LMCT) transition. What is meant by this term? (d) The LMCT transition in \(\mathrm{MnO}_{4}^{-}\) occurs at a wavelength of 565 \(\mathrm{nm} .\) The \(\mathrm{CrO}_{4}^{2-}\) ion is yellow. Is the wavelength of the LMCT transition for chromate larger or smaller than that for MnO \(_{4}^{-}?\) Explain. (e) The VO \(_{4}^{3-}\) ion is colorless. Do you expect the light absorbed by the LMCT to fall in the UV or the IR region of the electromagnetic spectrum? Explain your reasoning.

Given the colors observed for \(\mathrm{VO}_{4}^{3-}\) (orthovanadate ion), \(\mathrm{CrO}_{4}^{2-}\) (chromate ion), and \(\mathrm{MnO}_{4}^{-}\) (permanganate ion (see Exercise \(23.84 ),\) what can you say about how the energy separation between the ligand orbitals and the empty \(d\) orbitals changes as a function of the oxidation state of the transition metal at the center of the tetrahedral anion?
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