Ch.23 - Transition Metals and Coordination Chemistry
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- Complete the exercises below. Consider an octahedral complex MA₃B₃. How many geometric isomers are expected for this compound? Will any of the isomers be optically active? If so, which ones?
Problem 42
- Complete the exercises below. Determine if each of the following complexes exhibits geometric isomerism. If geometric isomers exist, determine how many there are. c. octahedral [Fe(o-phen)₂ Cl₂]⁺.
Problem 43
- Complete the exercises below. Determine if each of the following complexes exhibits geometric isomerism. If geometric isomers exist, determine how many there are. c. Square-planar [Pd(en)(CN)₂].
Problem 44
- Complete the exercises below. Determine if each of the following metal complexes is chiral and therefore has an optical isomer: b. octahedral trans-[Ru(bipy)₂Cl₂].
Problem 45
- Complete the exercises below. Determine if each of the following metal complexes is chiral and therefore has an optical isomer: a. square planar [Pd(en)(CN)₂].
Problem 46
- Complete the exercises below. Determine if each of the following metal complexes is chiral and therefore has an optical isomer: b. octahedral [Ni(en)(NH₃)₄]²⁺.
Problem 46
- Complete the exercises below. Determine if each of the following metal complexes is chiral and therefore has an optical isomer: c. octahedral cis-[V(en)₂ClBr].
Problem 46
- Complete the exercises below. a. If a complex absorbs light at 610 nm, what color would you expect the complex to be? b. What is the energy in joules of a photon with a wavelength of 610 nm? c. What is the energy of this absorption in kJ/mol?
Problem 47
- Complete the exercises below. a. A complex absorbs photons with an energy of 4.51 x 10⁻¹⁹ J. What is the wavelength of these photons? b. If this is the only place in the visible spectrum where the complex absorbs light, what color would you expect the complex to be?
Problem 48
- Complete the exercises below. Identify each of the following coordination complexes as either diamagnetic or paramagnetic: a. [ZnCl₄]²⁻ b. [Pd(NH₃)₂ Cl₂]
Problem 49
Problem 52a
The lobes of which d orbitals point directly between the ligands in a. octahedral geometry,
Problem 52b
The lobes of which d orbitals point directly between the ligands in b. tetrahedral geometry?
- Complete the exercises below. a. Sketch a diagram that shows the definition of the crystal-field splitting energy (∆) for an octahedral crystal-field. b. What is the relationship between the magnitude of ∆ and the energy of the d-d transition for a d¹ complex? c. Calculate ∆ in kJ/mol if a d¹ complex has an absorption maximum at 545 nm.
Problem 53
Problem 54
As shown in Figure 23.26, the d-d transition of [Ti(H2O)6]³⁺ produces an absorption maximum at a wavelength of about 500 nm .
a. What is the magnitude of ∆ for [Ti(H2O)6]³⁺ in kJ/mol?
b. How would the magnitude of ∆ change if the H2O ligands in [Ti(H2O)6]]³⁺ were placed with NH3 ligands?
- Complete the exercises below. Give the number of (valence) d electrons associated with the central metal ion in each of the following complexes: a. K₃ [TiCl₆], b. Na₃ [Co(NO₂)₆], c. [Ru(en)₃] Br₃, d. [Mo(EDTA)] ClO₄, e. K₃ [ReCl₆].
Problem 57
- Complete the exercises below. Give the number of (valence) d electrons associated with the central metal ion in each of the following complexes: a. K₃[Fe(CN)₆] b. [Mn(H₂O)₆](NO₃)₂ c. Na[Ag(CN)₂] d. [Cr(NH₃)₄Br₂]ClO₄ e. [Sr(EDTA)]²⁻
Problem 58
Problem 59
A classmate says, “A weak-field ligand usually means the complex is high spin.” Is your classmate correct? Explain.
Problem 60
For a given metal ion and set of ligands, is the crystal-field splitting energy larger for a tetrahedral or an octahedral geometry?
- Complete the exercises below. For each of the following metals, write the electronic configuration of the atom and its 2+ ion: a. Mn. Draw the crystal-field energy-level diagram for the d orbitals of an octahedral complex, and show the placement of the d electrons for each 2+ ion, assuming a strong-field complex. How many unpaired electrons are there in each case? b. Ru. Draw the crystal-field energy-level diagram for the d orbitals of an octahedral complex, and show the placement of the d electrons for each 2+ ion, assuming a strong-field complex. How many unpaired electrons are there in each case? c. Rh. Draw the crystal-field energy-level diagram for the d orbitals of an octahedral complex, and show the placement of the d electrons for each 2+ ion, assuming a strong-field complex. How many unpaired electrons are there in each case?
Problem 61
- Complete the exercises below. For each of the following metals, write the electronic configuration of the atom and its 3+ ion: a. Fe. Draw the crystal-field energy-level diagram for the d orbitals of an octahedral complex, and show the placement of the d electrons for each 3+ ion, assuming a weak-field complex. How many unpaired electrons are there in each case?
Problem 62
- Complete the exercises below. For each of the following metals, write the electronic configuration of the atom and its 3+ ion: b. Mo. Draw the crystal-field energy-level diagram for the d orbitals of an octahedral complex, and show the placement of the d electrons for each 3+ ion, assuming a weak-field complex. How many unpaired electrons are there in each case?
Problem 62
- Complete the exercises below. For each of the following metals, write the electronic configuration of the atom and its 3+ ion: c. Co. Draw the crystal-field energy-level diagram for the d orbitals of an octahedral complex, and show the placement of the d electrons for each 3+ ion, assuming a weak-field complex. How many unpaired electrons are there in each case?
Problem 62
- Complete the exercises below. Draw the crystal-field energy-level diagrams and show the placement of d electrons for each of the following: a. [Cr(H₂O)₆]²⁺ (four unpaired electrons).
Problem 63
- Complete the exercises below. Draw the crystal-field energy-level diagrams and show the placement of d electrons for each of the following: c. [Ru(NH₃)₅(H₂O)]²⁺ (a low-spin complex).
Problem 63
Problem 64a,b
Complete the exercises below. Draw the crystal-field energy-level diagrams and show the placement of electrons for each of the following complexes:
a. [VCl6]3–,
b. [FeF6]3– (a high-spin complex),
Problem 64d
Draw the crystal-field energy-level diagrams and show the placement of electrons for each of the following complexes:
d. [NiCl4]2+ (tetrahedral),
- Complete the exercises below. The complex [Mn(NH₃)₆]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?
Problem 65
- Complete the exercises below. The ion [Fe(CN)₆]³⁻ has one unpaired electron, whereas [Fe(NCS)₆]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 NCS⁻ in the spectrochemical series?
Problem 66
- Complete the exercises below. Explain why the transition metals in periods 5 and 6 have nearly identical radii within each group.
Problem 68
Problem 71a
Sketch the structure of the complex in each of the following compounds and give the full compound name:
a. cis-[Co(NH3)4(H2O)2] (NO3)2