Chemistry 312

Problem Set 5 (due Friday, August 5)

1. I stated in lecture that, for octahedral symmetry molecules, the ligand atom p orbitals
oriented perpendicular to the metal-ligand bond would belong to the symmetry species
T1g, T1u, T2g, and T2u. Using drawings or reducible representations, show that this is the
case. You will have to choose your phases wisely.
Using reducible representations:
Oh
E
reducible 12

8 C3
0

6 C2
0

6 C4
0

3 C2
4

i
0

6 S4
0

8 S6
0

3 h
0

3 d
0

which decomposes to T1g + T2g + T1u + T2u.

In order to get the reducible representation characters, I used drawings like the following
for determining the 3C2 character:

2. Diamagnetic complexes of cobalt (III) like [Co(NH3)6]3+ and [Co(en)3]3+ are orangeyellow, while paramagnetic cobalt (III) complexes like [CoF6]3 and [Co(H2O)3F3] are
blue. Explain, using abridged MO diagrams, this difference in color.
All these complexes are octahedral. The orange-yellow complexes appear that color
because they absorb (maximally) in the purple-violet region of the EM spectrum, whereas
the blue complexes absorb in the orange. This means that orange-yellow complexes have
a higher O than the blue complexes, which makes sense because the diamagnetic
complexes the energy separation between the t2g and eg* orbitals is great enough that the
electrons will overcome repulsion and pair in the t2g orbitals before they populate the eg*
level. See diagram below.

3. Predict which complex in each of the following pairs will have the lower energy dd
transition, and give a short reason for your choice:
a. [Co(NH3)5Cl]2+ or [Co(NH3)5NO2]2+
[Co(NH3)5Cl]2+ because Cl is a lower field strength ion than NO2, according to the
spectrochemical series. This means that the crystal (ligand) field splitting energy, O, is
lower for Cl than for NO2, making the d-d transition itself lower energy.
b. [Co(CN)6]3 or [Ir(CN)6]3
[Co(CN)6]3 for very much the similar reason as part a; according to the second list on
page 475 of the text, Co3+ is a lower field strength ion than Ir3+, so the cobalt ion has the
lower O.
4. a. The complex [Cu(H2O)6]2+ ought to be octahedral; however, measurements of the
bond lengths of the CuO bonds reveal that four of them, oriented along the x and y axes,
have a bond length of 280 pm, and the other two, oriented along the z-axis, have a bond
length of 318 pm. Use the octahedral MO diagram as a starting point, and show how that
MO diagram changes to accommodate the new point group of the distorted molecule.
Hint: there should be significant orbital changes.
The new point group is D4h, which is going to be similar to the square planar complexes.

b. Why is this distortion (the relative lengthening of the z-axis oriented bonds) is required
for this molecule? Hint: as always, it will be an energy-minimizing reason.
The t2g orbitals in the Oh symmetry split into the eg and b1g orbitals under D4h symmetry;
the eg* orbitals split into the a1g* and b1g* orbitals. When the orbitals split, they use the
original degenerate energy level (t2g or eg*) as the barycenter of the energies of the
separate orbitals. For instance, the energy that the a1g* orbital is lower than the original
eg* orbital energy level by the same amount that the b1g* orbital is higher. Thus, for filled
(octahedral) orbitals, there is no energy difference so there is no advantage for the
molecule to distort into D4h symmetry. However, for the octahedral eg* orbitals (which
were not completely filled), note that instead of having three electrons at the same energy
level, there are now two lower and one higher than originally even this small energy
difference will make a particular structure more energetically stable. This is called the
Jahn-Teller effect.
c. Explain, using part b, why [Cu(en)3]2+ cannot be made. (en) = NH3CH2CH2NH3 and is
a bidentate ligand.
Since (en) is a bidentate ligand, the complex is constrained; in other words, the z-axis
CuO bonds cannot lengthen without untethering one of the (en) lone pairs and thus
destroying the complex.
d. In some copper complexes, it is the x and y axis-oriented metal-ligand bonds that are
longer than the z axis-oriented metal-ligand bonds. Would the MO diagram for such a

distorted molecule be different than the one you created for part a? If so, show the new
energy order of orbitals.
See the abbreviated MO diagram below. The point is that the orbitals would still follow
the rules of crystal field theory in avoiding electron-electron repulsion; for instance,
because the z-axis bonds are shorter relative to the x and y-axis bonds, the dz2 orbital
would have more repulsion than the dx2y2 orbital and thus will have a higher energy. The
point of this is that whether the z-axis bonds lengthen or the x and y-axis bonds lengthen
will depend on the number of electrons populating these orbitals. The difference between
this picture and the one with the z-axis bonds longer is the reversal of the eg and b1g
orbitals. In the case below, the b1g orbital is twice as low (compared to the t2g energy
level from where it came) as the eg orbitals are high, which means that one electron
populating these orbitals will be lower energy than if it was populating these same levels
in part a.

5. Consider a metal-ligand complex in which ethylene (C2H4) is the ligand; recall that the
ethylene ligand is oriented such that the C=C bond is perpendicular to the line from the
metal center to the center of the C=C bond.
a. Draw the orbital(s) responsible for the ethylene ligands donation of electron density to
a 3d metal center.

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b. Draw the orbital(s) responsible for the metals donation of electron density to the
ethylene ligand.

d-orbital ielectron density from the metal is donated (bonding interaction)

into anti-bonding orbitals of the existing ethylene ligand

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c. Using the Dewar-Chatt-Duncanson Model, explain whether you would expect

(CO)5Cr(H2C=CH2) or (CO)3(PH3)2Cr(H2C=CH2) to have a longer C=C bond in the
ethylene ligand.
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The phosphine complex would be expected to most activate the ethylene bond. Carbonyl
ligands are pi-acceptors and therefore reduce the electron density at the metal center
available for back-donation to the side-on ethylene ligand. Phosphines, in contrast, are
not significant pi-acceptors, and thereby increase electron density at the metal center that
can be donated to the ethylene ligands anti-bonding orbital.