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Chapter 21: Problem 93

Which of the following crystal field diagram(s) is(are) correct for the complex given? a. \(\mathrm{Zn}\left(\mathrm{NH}_{3}\right)_{4}^{2+}\) (tetrahedral) b. \(\operatorname{Mn}(\mathrm{CN})_{6}^{3-}\) (strong field) c. \(\mathrm{Ni}(\mathrm{CN})_{4}^{2-}\) (square planar, diamagnetic)

Short Answer

Expert verified
All three options (a, b, and c) have the correct crystal field diagrams for their respective complexes. The Zn(NH3)4^2+ complex has a tetrahedral geometry, the Mn(CN)6^3- complex has an octahedral geometry with a strong field ligand, and the Ni(CN)4^2- complex has a square planar geometry and is diamagnetic.

Step by step solution

01

Determine the geometry of each complex

We first need to determine the geometry of each complex, which will help us understand the splitting diagram. a. \(\mathrm{Zn}\left(\mathrm{NH}_{3}\right)_{4}^{2+}\): The central atom Zn has a d10 configuration, and with Ammonia acting as a ligand, forms a tetrahedral complex. b. \(\operatorname{Mn}(\mathrm{CN})_{6}^{3-}\): Mn has a d4 configuration, and with Cyanide acting as a ligand, forms an octahedral complex. c. \(\mathrm{Ni}(\mathrm{CN})_{4}^{2-}\): Ni has a d8 configuration, and with Cyanide acting as a ligand, forms a square planar complex.
02

Determine the crystal field splitting diagram for each complex

Now, we can determine the crystal field splitting diagrams for each complex: a. Tetrahedral complex: The crystal field splitting diagram for a tetrahedral complex has the following energy levels, from lowest to highest: \(e^2t^2\). b. Octahedral complex with strong field ligand: The crystal field splitting diagram for an octahedral complex with a strong field ligand (such as Cyanide) has the following energy levels, from lowest to highest: \(t^2g^4e^2g^0\). c. Square planar complex: The crystal field splitting diagram for a square planar complex has the following energy levels, from lowest to highest: \(d_z^2xy^3z^2-x^2\).
03

Check if the complex is diamagnetic (for option c)

To determine if the Ni(CN)4^2- complex is diamagnetic, we need to review the electron configuration and the crystal field splitting diagram. As mentioned earlier, Ni has a d8 configuration, and the square-planar splitting for this complex would show that all d orbitals (d8) are completely filled, with no unpaired electrons. Thus, this complex is indeed diamagnetic.
04

Compare the properties of each complex to the options given

Here, we compare the properties (geometry and splitting) of each complex with the information given in each option: a. \(\mathrm{Zn}\left(\mathrm{NH}_{3}\right)_{4}^{2+}\) (tetrahedral): The geometry matches, so this option is correct. b. \(\operatorname{Mn}(\mathrm{CN})_{6}^{3-}\) (strong field): The complex has an octahedral geometry with a strong field ligand, causing large crystal field splitting. Therefore, this option is correct. c. \(\mathrm{Ni}(\mathrm{CN})_{4}^{2-}\) (square planar, diamagnetic): The complex has the correct geometry and is also diamagnetic. So this option is correct. All three options (a, b, and c) have the correct crystal field diagrams for their respective complexes.

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Most popular questions from this chapter

Write electron configurations for each of the following. a. \(\mathrm{Cr}, \mathrm{Cr}^{2+}, \mathrm{Crr}^{3+}\) b. \(\mathrm{Cu}, \mathrm{Cu}^{+}, \mathrm{Cu}^{2+}\) c. \(\mathrm{V}, \mathrm{V}^{2+}, \mathrm{V}^{3+}\)

The following statements discuss some coordination compounds. For each coordination compound, give the complex ion and the counterions, the electron configuration of the transition metal, and the geometry of the complex ion. a. \(\mathrm{CoCl}_{2} \cdot 6 \mathrm{H}_{2} \mathrm{O}\) is a compound used in novelty devices that predict rain. b. During the developing process of black-and-white film, silver bromide is removed from photographic film by the fixer. The major component of the fixer is sodium thiosul-fate. The equation for the reaction is: $$\operatorname{AgBr}(s)+2 \mathrm{Na}_{2} \mathrm{S}_{2} \mathrm{O}_{3}(a q) \longrightarrow \\ \quad\quad\quad\quad\quad\quad\quad\quad\quad\quad \mathrm{Na}_{3}\left[\mathrm{Ag}\left(\mathrm{S}_{2} \mathrm{O}_{3}\right)_{2}\right](a q)+\mathrm{NaBr}(a q)$$ c. In the production of printed circuit boards for the electronics industry, a thin layer of copper is laminated onto an insulating plastic board. Next, a circuit pattern made of a chemically resistant polymer is printed on the board. The unwanted copper is removed by chemical etching, and the protective polymer is finally removed by solvents. One etching reaction is: $$\mathrm{Cu}\left(\mathrm{NH}_{3}\right)_{4} \mathrm{Cl}_{2}(a q)+4 \mathrm{NH}_{3}(a q)+\mathrm{Cu}(s) \longrightarrow \\\ \quad\quad\quad\quad\quad\quad\quad\quad\quad\quad\quad\quad\quad\quad\quad\quad 2 \mathrm{Cu}\left(\mathrm{NH}_{3}\right)_{4} \mathrm{Cl}(a q)$$ Assume these copper complex ions have tetrahedral geometry.

a. In the absorption spectrum of the complex ion \(\mathrm{Cr}(\mathrm{NCS})_{6}^{3-}\) there is a band corresponding to the absorption of a photon of light with an energy of $1.75 \times 10^{4} \mathrm{cm}^{-1} .\( Given \)1 \mathrm{cm}^{-1}=1.986 \times 10^{-23} \mathrm{J},$ what is the wavelength of this photon? b. The \(\mathrm{Cr}-\mathrm{N}-\mathrm{C}\) bond angle in \(\mathrm{Cr}(\mathrm{NCS})_{6}^{3-}\) is predicted to be \(180^{\circ} .\) What is the hybridization of the N atom in the \(\mathrm{NCS}^{-}\) ligand when a Lewis acid-base reaction occurs between \(\mathrm{Cr}^{3+}\) and \(\mathrm{NCS}^{-}\) that would give a $180^{\circ} \mathrm{Cr}-\mathrm{N}-\mathrm{C}$ bond angle? \(\mathrm{Cr}(\mathrm{NCS})_{6}^{3-}\) undergoes substitution by ethylenediamine (en) according to the equation $$\mathrm{Cr}(\mathrm{NCS})_{6}^{3-}+2 \mathrm{en} \longrightarrow \mathrm{Cr}(\mathrm{NCS})_{2}(\mathrm{en})_{2}^{+}+4 \mathrm{NCS}^{-}$$ Does \(\mathrm{Cr}(\mathrm{NCS})_{2}(\mathrm{en})_{2}^{+}\) exhibit geometric isomerism? Does \(\mathrm{Cr}(\mathrm{NCS})_{2}(\mathrm{en})_{2}^{+}\) exhibit optical isomerism?

A coordination compound of cobalt (III) contains four ammonia molecules, one sulfate ion, and one chloride ion. Addition of aqueous \(\mathrm{BaCl}_{2}\) solution to an aqueous solution of the compound gives no precipitate. Addition of aqueous \(\mathrm{AgNO}_{3}\) to an aqueous solution of the compound produces a white precipitate. Propose a structure for this coordination compound.

Draw all geometrical and linkage isomers of square planar \(\operatorname{Pt}\left(\mathrm{NH}_{3}\right)_{2}(\mathrm{SCN})_{2}\) .
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