Problem Set 6 Key

Chemistry 312
Problem Set 6 (due Monday, August 15) key

1. a. Give the ground-state ligand-field electronic configuration for the populated valence
molecular orbitals of the octahedral complex W(CO)6 (no Jahn-Teller distortion).
(a1g)2(eg)4(t1u)6(t2g)6
b. What is the term symbol (= term and multiplicity) for W in this state?
Look on the Tanabe-Sugano diagram; the lowest term for d6 is the ground state 5D.
c. Is the complex diamagnetic or paramagnetic?
All electons are paired, so this complex is diamagnetic.
d. The first electronic absorption band occurs at about 31,000 cm1. Assign this band to
an electronic transition in the complex.
The electronic transition is eg* t2g.
e. Calculate the wavelength (in nm) and the energy of this absorption (in kJ/mol).
31,000 cm1 is a wavenumber, so the inverse of the wavenumber is the wavelength:
(1/31,000 cm1)(109 nm/102 cm) = 323 nm. Then use E = hc/ = (6.626 1034 Js)(2.998
108 m/s)/(323 109 m) = 6.15 1019 J = 370 kJ/mol.
f. Is the photochemical dissociation of W(CO)6 to W(CO)5 + CO reasonable? Explain, in
terms of the population of bonding and antibonding orbitals.
The dissociation is reasonable because the photoexcitation of W(CO)6 takes an electron
from a bonding orbital (t2g) to an antibonding orbital (eg*) that is directed at the ligands.
What this does is weaken the M-L bond.
2. Ni(P(o-C6H4Me)3)2Cl2 is paramagnetic with a 3 BM, while Ni(PMe3)2Cl2 is
diamagnetic (see the structures note you are considering only the geometry of the metal
d orbitals, so the metal d orbitals will split into either a square planar or a tetrahedral
arrangement). Suggest a possible explanation, and show how it is compatible with their
different magnetic properties.
The nickel ion itself is 2+ in these complexes, so it is d8. The key to this problem is the
nature of these ligands. According to the spectrochemical series, the PR3 ligands are
strong field so d8 nickel with four ligands prefers a square planar orientation (page 481).
However, when some or all of the ligands are bulky and there are steric interactions
between them, as in the Ni(P(o-C6H4Me)3)2Cl2 complex, these will force the complex
into the less-hindered tetrahedral arrangement. Thus, the explanation for the difference in
magnetic properties: Ni(P(o-C6H4Me)3)2Cl2 has Td symmetry, so the nickel d-orbitals will
split into an e set and a higher t2 set, with the configuration (e)4(t2)4, where there will be
two unpaired electrons in the t MOs, which should have roughly a 2.83 B magnetic
moment (i.e., it is paramagnetic). By contrast, Ni(PMe3)2Cl2 has D4h symmetry so the
nickel d-orbitals will split into a b2g, an eg, a b1g and an a1g MOs, so there will be four
paired (filled) orbitals: (b2g)2(eg)4(b1g)2, which makes this complex diamagnetic.
3. The table below lists the carbonyl IR stretching frequencies for various molybdenum
carbonyl complexes with the formula [Mo(CO)3L3] (where L is the non-carbonyl ligand).
Every CO is opposite the molybdenum center from an L (see structure). Ph = phenyl
(C6H5) group.
L
PCl3
PPhCl2
PPh2Cl
PPh3
CO frequencies (cm1)
1989, 2041
1943, 2016
1885, 1977
1835, 1949
a. Draw the carbonylmolybdenumL pi system (use just the phosphorus atoms p or d

orbitals for L).
b. Write the trend in CO frequencies, in terms of the CO pi bond energy and the CMo
pi bond energy.
As more phenyl groups are substituted on the phosphorus ligand, the CO frequency
lowers, indicating that the CO pi bond is weakening as the antibonding orbitals on the
CO are filled with electron density from the metal. This also suggests that the CMo pi
bond is strengthening by the same mechanism.
c. Explain why adding phenyl groups to the phosphorus changes the strength of the CO
bond in the way that it does.
The phenyl groups have a well-developed pi system which tends to not draw electron
density away from the phosphorus as effectively as chloride does; the more phenyl
groups attached to the phosphorus, the more electron density that resides at the
phosphorus, which in turn means there is more electron density in the metal-ligand
bond. This leads to more density in the metal-CO bond, which strengthens that bond
and populates the antibond in the CO which weakens that bond and lowers its
vibrational frequency.
d. What would you expect for the CO stretching frequencies for the same structure above
with L = NH3? Why?
Note that all of the electrons in the ammonia are involved in bonding so there is no
system for ammonia; without that, the metal d-orbital involved in the M-CO bond can
have plenty of electron density, which will fully populate the antibond in the CO and
thus lower the vibrational frequency even lower than the other molecules mentioned.
4. a. Write the two isomers of a metal carbonyl complex with the formula [M(CO)4L2],
where both Ls are the same ligand. You may assume M is uncharged.
b. If you drew the isomers correctly, one should be in the point group D4h and the other
should be in C2v. Write the reducible representation for the carbonyls for each point
group, decompose them, and determine the number of IR absorptions each molecule
should exhibit. Can IR spectroscopy be used to distinguish the two isomers?
D4h
E
reducible 4
2C4
0
C2
0
2C2
2
2C2
0
i
0
2S4
0
h
4
2v
2
2d
0
Which decomposes to A1g + B1g + Eu, of which only Eu has linear basis functions (in this
case, (x,y)), so there will be only one IR vibrational mode from this molecule.
C2v
reducible
E
4
C2
0
v (xz)
2
v (yz)
2
Which decomposes to 2 A1 + B1 + B2, of which A1, B1 and B2 have the linear functions as
their basis there will be 3 IR vibrational modes from this molecule.
Since there are different numbers of IR vibrations from each molecule, IR spectroscopy
should be able to distinguish them.

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Chemistry 312

Problem Set 6 (due Monday, August 15) key

a. Draw the carbonylmolybdenumL pi system (use just the phosphorus atoms p or d

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