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CHE322 PROBLEM SET 3 Solutions

The document contains the solutions to 9 problems related to coordination chemistry. Problem 1 summarizes why Cr(CO)6 is stable due to π-backbonding from CO ligands relieving electron density on Cr, while Cr(NH3)6 is not stable since NH3 is only a σ-donor ligand. Problem 2 explains that metal-to-ligand charge transfer bands occur when the metal is in a low oxidation state and the ligand has low-lying empty orbitals, such as CO or CN-, allowing an electron to transfer from the metal's t2g or eg orbitals to the ligand's orbitals. Problem 3 draws the structures of cis-[VO2Cl4

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AsHes Maswati Ash
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505 views

CHE322 PROBLEM SET 3 Solutions

The document contains the solutions to 9 problems related to coordination chemistry. Problem 1 summarizes why Cr(CO)6 is stable due to π-backbonding from CO ligands relieving electron density on Cr, while Cr(NH3)6 is not stable since NH3 is only a σ-donor ligand. Problem 2 explains that metal-to-ligand charge transfer bands occur when the metal is in a low oxidation state and the ligand has low-lying empty orbitals, such as CO or CN-, allowing an electron to transfer from the metal's t2g or eg orbitals to the ligand's orbitals. Problem 3 draws the structures of cis-[VO2Cl4

Uploaded by

AsHes Maswati Ash
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CHE322 PROBLEM SET 3 SOLUTIONS

1. Explain why Cr(CO)6 is stable, while Cr(NH3)6 is not.


Cr: 3d4
In Cr(CO)6: CO is a –acceptor ligand. There is –back bonding which relieves
electron density on the Cr.
In Cr(NH3)6: NH3 is a –donor ligand.

2. When do we expect MLCT bands in metal complexes?


If the metal is in a low oxidation state and the ligand possesses low‐lying empty
orbitals (for example CO or CN‐) then a MLCT transition may occur. This is the
transition of an electron from the t2g () and the eg (*) to the t1u (*/*). These
transitions arise from pi acceptor ligands and metals that are willing to donate
electrons into the orbitals of Ligand character. Examples of  accepting ligands are as
follows: CO, NO, CN‐, N2, bpy, o‐phen, RNC, C5H5‐, C=C multiple bonded groups.

Metal to Ligand Charge Transfer (MLCT) involving an octahedral d5 complex.

3. Carefully draw the structures of cis-[VO2Cl4]3- and cis-[VO2(ox)2]3-. The trans forms
of these complexes are not stable. Why not?
The bond distances trans to the oxo group are considerably longer than those cis to
the oxo group (trans influence). The trans ligands use d-orbitals to bond with the
central metal ion, strong electron donating from the oxo ligand (O2-) makes the
attachment of the ligand trans to the O2- unfavourable.

4. Describe the π-bond system in [Ru2OCl10]4-. (Draw a diagram.)


Yields a less polar M-L bond, resulting in diminished splitting.
Typical ligands that exhibit this type of bonding include hydroxide (OH-), oxide (O2-),
halides (I-, Br-, Cl-).
These ligands tend to be at the lower end of the spectrochemical series.

5. Is there a red spectral shift or is there a blue spectral shift when en is added to a
solution containing aqueous nickel(II) ion? Explain what is happening chemically and
why the spectrum shifts as it does.
Blue shift
Polarity causes the shifting

6. The following redox reaction between two coordination complexes occurs via an
outer sphere mechanism:
[Co(NH3)5Cl]2+ + [Ru(NH3)6]2+ [Co(NH3)5Cl]+ + [Ru(NH3)6]3+
a. What can be said about the mechanism, reactants and the rate of electron
transfer in this reaction?
Coordination numbers does not change
Fast electron transfer
Reactants do not bond
Rate = k[A][B]
Interchange
b. Give the name of either the reactants or products for the above redox reaction.
Reactants: pentaamminechlorocobalt(III)
Hexaammineruthenium(II)
Products: pentaamminechlorocobalt(II)
Hexaammineruthenium(III)
c. Give the mechanistic details if the redox reaction occurred instead via an inner
sphere mechanism.
Reactants bond.
Coordination number change.
Electron hops via M-L-M intermediate
Slower electron transfer

7. Sketch an approximate, but representative, reaction profile (free energy versus


reaction coordinate) if the rate determining step of the reaction involves:
(i) Association (ii) Dissociation (iii) Interchange
Refer to your notes

8. The high-spin d4 complex [Cr(H2O)6]2+ is labile, but the low-spin d4 complex ion
[Cr(CN)6]4- is inert . Explain.
[Cr(H2O)6]2+ is labile, and has 4 unpaired electrons, with 1 in the anti-bonding eg
orbital. Occupation of this orbital renders substitution easier by leading to relatively
weak chromium(II)–aqua ligand bonds. [Cr(CN)6]4– is inert. It has all 4 metal valence
electrons in the bonding t2g levels. These orbitals are rendered bonding in character
due to π-backbonding with the cyanide ligands.

9. Determine the ground terms for the following configurations:


a. d8 (Oh symmetry)
J values are included in these answers:

d8 Oh MS = 1 = S Spin multiplicity = 2 + 1 = 3
Max ML = 2+2+1+1+0+0–1–2 = 3 = L, so F term. J = 4, 3, 2
Ground term: 3F4
b. high-spin and low-spin d5 (Oh symmetry)
d5 Oh high spin MS = 5/2 = S Spin multiplicity = 5 + 1 = 6
Max ML = 2+1+0–1–2 = 0 = L, so S term. J = 5/2
Ground term: S5/26

d5 Oh low spin MS = 1/2 = S Spin multiplicity = 1 + 1 = 2


Max ML = 2+2+1+1+0 = 6 = L, so I term. J = |L ± S| = 11/2, 13/2
2 2
Ground terms: I11/2, I13/2
(J is uncertain in this case; the usual rule does not apply because the level is
exactly half full)
c. d4 (Td symmetry)
d4 Td MS = 2 = S Spin multiplicity = 4 + 1= 5
Max ML = 2+1+0–1 = 2 = L, so D term. J = 4, 3, 2, 1, 0
Ground term: D0 5
d. d9 (D4h symmetry, square-planar)
d9 D4h MS = 1/2 = S Spin multiplicity = 1+1= 2
Max ML = 2+2+1+1+0+0–1–1–2 = 2 = L, so D term. J = |L ± S| = 5/2, 3/2
Ground term: 2D5/2

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