7/29/2018 EXAM #3

EXAM #3
Chem 50273, Fall 2010
100 points

Clearly mark your answers. Do the easiest questions first!

1. (15 pts) Using the attached angular overlap parameters, determine the energies of the d orbitals of the metal
for trigonal bipyramidal geometry first for ligands that act as s donors only, and then for ligands that act as both
s donors and p acceptors. Draw the resulting d orbital diagrams, labeling energies in terms of es and ep.

Answer: Trigonal bipyramidal, ligands are at positions 1, 6, 2, 11, and 12.

Sigma donors only:
dz2: 1es + ¼ es + 1 es + ½ es = 2 ¾ es
dx2-y2: ¾ es + 6/16 es = 1 1/8 es
dxy: 18/16 es = 1 1/8 es
dxz: 0

dyz: 0
Pi acceptors:
dz2: 0
dx2-y2: 6/4 ep = 1 ½ ep
dxy: 1ep + 2/4 ep = 1 ½ ep
dxz: 1 ep + 1 ep + 1 ep + ½ ep = 3 ½ ep
dyz: 1 ep + 1 ep + 6/4 ep = 3 ½ ep
The diagram shows the combination of s donor and p donor effects.

2. (8 points) Draw
a) the meridional isomer of CrCl3(NH3)3
b) the product obtained from the reaction of FeCl2 with N(CH2CH2NMe2)3.
c) the two chiral isomers of [Co(en)2(NO2)2], and label their handedness.

a.

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b.

c.

3. (12 points) a) Define DO in terms of ligand field theory.

b) Given a 4-coordinate d4 complex ML4, what is the LFSE (in terms of DO) for the high-spin cases of
tetrahedral and square planar structures?
[Tetrahedral levels are +0.178 and -0.267DO, and square planar are +1.228, +0.228, -0.428, and -0.514DO.]
c) What structure would you expect if the ligands are iodide? Why?
d) Choose either of the two systems you described in b) (and tell me which you’re choosing!). What would you
expect its magnetic moment to be? Would you expect it to be paramagnetic or diamagnetic?

a. DO is the energy difference between the eg and t2g levels of the frontier MO’s with most d orbital character.
b. For tetrahedral, LFSE = (2)(-0.267) + (2)(0.178) = -0.178DO
For square planar, LFSE = (2)(-0.514) + (1)(-0.428) + (1)(0.228) = -1.228DO
c. If the ligand is I, which favors high-spin, LFSE favors square planar. However, square planar is usually low
spin and tetrahedral high spin. Despite the LFSE results, I would expect tetrahedral, which is usually found for
high oxidation state metal halides due to the size of I and its pi donor capability.
d. For tetrahedral, m = 4.9 mB, paramagnetic.
For square planar, the same.

4. (12 points) Define the following 4 terms: chelate effect, linkage isomerism, circular dichroism, pi back-
bonding
chelate effect--a special stability of chelates over complexes with equivalent monodentate ligands--largely an
entropic effect, e.g.
Co(en)3 + 6 NH3 <==> Co(NH3)6 + 3 en
Linkage isomerism--isomers in which the same ligand is attached by different donor atoms, e.g. CN—, SCN—,
NO2—. The ligands will be called by different names depending on how they are connected to the metal.
(cyano, isonitrile, thiocyanato, isothiocyanato, nitrito, nitro...)
Circular Dichroism—A form of electronic spectroscopy used on chiral compounds, which determines the
specific rotation of circularly polarized light as a function of wavelength.
Pi back bonding—Donation of metal d orbital electrons to empty ligand orbitals that have a pi symmetry with
respect to the bonding axes.

5. (11 points) One pink solid has the empirical formula CoCl3·5 NH3·H2O. A solution of this salt is also pink
and rapidly gives 3 mol AgCl upon titration with silver nitrate solution. When the pink solid is heated, it loses 1
mol H2O to give a purple solid with the same ratio of NH3:Cl:Co. The purple solid releases two of its chlorides
rapidly; then, on dissolution and after titration with AgNO3, releases one of its chlorides slowly. Deduce the
structures of the two octahedral complexes and draw and name them. Explain the color change.

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Answer: The pink solid is , pentaamineaquacobalt(III) chloride.

The purple solid is , pentaaminechlorocobalt(III) chloride.

Chloride is a weaker field ligand than H2O, so the second complex is likely to have a smaller value of DO. This
means that it should absorb a lower energy color. According to the color wheel, the pink complex (red) should
absorb green, and the purple (violet) complex should absorb yellow. Yellow is lower energy than green, as
predicted.

6. (9 pts) Name the following compounds.

a.) [Ru(CN)6]3–
b.) [Ir(NCS)(NH3)5]2+
c.) K[PtCl3(bipy)]

Answer: a. hexacyanoruthenate(III) ion

b. pentaamineisothiocyanatoiridium(III) ion
c. potassium bipyridinetrichloroplatinate(II)
[note I count bipyridine as starting with b not p, since it is a single ligand, as opposed to trichloro where the
ligand starts with c and just the prefix starts with t]

7. (5 pts) Given that the maximum absorption in the d-d region for [Ti(H2O)6]3+ occurs at 20,300 cm–1, predict
where the d-d peaks will occur for [Ti(CN)6]3– and [TiCl6]3–. Explain.

Answer: H2O has a medium ligand field strength, so its DO will be an intermediate energy. Cyanide is a high
field ligand, causing a larger DO, so its absorption will be higher energy (perhaps ~22,000) and chloride is the
opposite, so the [TiCl6]3– absorption will be at a lower energy (perhaps ~19,000).

8. a) (8 points) Qualitatively describe the ligand field (or crystal field) effect on the d orbital energies in a
linear complex ML2. Label the 5 d orbitals and the energy ordering you would expect, and show or explain
why.
The dz2 orbital extends toward the two ligands and will have the most overlap, leading to the orbital with the
most antibonding character. The dxz and dyz can overlap only in a pi fashion with the ligand orbitals, which
tends to have less overlap, leading to again an antibonding character (and rise in energy), but less so. Finally, the

dxy and dx2-y2 orbitals have only delta symmetry with respect to the ligands and will not be affected.
b) (12 points) Draw the MO diagram for CuCl2, including only s bonding. Label the basis sets and MO’s, the
HOMO and LUMO, and the overall symmetry of the molecule, and draw pictures of the Cl basis set SALC’s.
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You do not need to label the symmetries of all the MO’s and basis set orbitals, but you do need to show which
basis set orbitals mix, as usual.

c) (6 points) If you incorporate p contributions of the chlorine p orbitals, explain (show) how will it change
your MO diagram.
d) (2 points) Compare the results of the MO diagram with the results of your ligand field diagram.
[Hint: Define your z axis as the L—M—L bonding axis.]

a. The strongest interaction would be between the ligands and the dz2 orbital, so it would be the highest energy.
The next strongest would be between the ligands and the dxy and dxz, because these orbitals have z components,
but there is a node on the axis where the ligand lies. Only pi intereactions will be possible, which tend to be
weaker than sigma. So they will lie below the dz2 in energy. Finally, the two orbitals with only x and y
components will not interact with the ligands (delta symmetry with respect to the ligands), so they will be the

lowest.
b. MO diagram. Overall symmetry D∞h. The SALC’s for the 2 Cl atoms will be the Cl + Cl and Cl – Cl
combinations.

c. If the Cl pi donor orbitals are considered, their SALC’s will be and , plus the
orthogonal pair. The first of these will mix with the metal p orbitals to make bonding and antibonding
combinations, but neither of these will affect the frontier orbital region. The second one has the proper

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symmetry to interact with dxz and dyz. The dxy and dx2-y2 will remain nonbonding. The new diagram will look

like this:
d. The sigma only version does not coincide with the ligand field diagram, but the sigma and pi version does.

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