Chem.

312, Autumn '13 Problem Set #4, page 1

Problem Set 4 Due in class, Monday, October 21

1. (a) For what electron counts (dn) are both high-spin and low-spin forms possible in an
octahedral complex?
4 5 6 7
(a) Both high-spin and low-spin forms are possible in octahedral complexes with d , d , d , and d
configurations.

(b) For each of the following ions, give the electronic configuration [Ar]dn (n is the number of d
electrons). All of these transition metal ions have empty valence s orbitals (they are …s0).
This is true for all transition metal ions in chemical compounds, because the empty valence s
orbital is used for covalent bonding.
(i) Cu2+ (ii) Fe3+ (iii) Co2+ (iv) Ni2+
(c) Which of the ions in part (b) have both high-spin and low-spin configurations in octahedral
complexes? Give the d electronic configuration of these ions
as t2gx egy (where x, and y indicate numbers of electrons in the eg
respective orbitals). Show how many unpaired electrons are
present in each case, most easily by adding electrons to the
“two above three” orbital ladder shown at right. t2g
(b), (c) (i) Cu2+, [Ar]3d9, only one form,

d9, one unpaired electron

(ii) Fe3+, [Ar]3d5

high spin d5, five unpaired electrons low spin d5, one unpaired electron

(iii) Co2+, [Ar]3d7

high spin d7, three unpaired electrons low spin d7, one unpaired electron

(iv) Ni2+, [Ar]3d8, only one form

Chem. 312, Autumn '13 Problem Set #4, page 2

d8, two unpaired electrons

2. In tetrahedral complexes, the d orbitals split differently, in a “three above two” pattern.
Which of the ions in question 1(b) have both high-spin and low-spin configurations in
tetrahedral complexes? Again, show how many unpaired electrons are present in each case.
In tetrahedral complexes, where d orbitals split in a “three above two” pattern:

(i) Cu2+, [Ar]3d9, tetrahedral, only one form.

d9 , one unpaired electron

(ii) Fe3+, [Ar]3d5, tetrahedral

high spin d5, five unpaired electrons low spin d5, one unpaired electron

(iii) Co2+, [Ar]3d7, tetrahedral: only one form. (iv) Ni2+, [Ar]3d8, tetrahedral: only one form

d7, three unpaired electrons d8, two unpaired electrons

3. For each of the following complexes, give (i) the formal oxidation state of the central metal
and (ii) the number of d electrons on the metal in this oxidation state. For example:
Cu(H2O)62+ and CuCl42- both formally contain Cu2+, d9. Remember to divide the complex
up so that each ligand has a closed shell (octet) configuration. Also remember that all metal
complexes have empty valence s orbitals – configurations: [noble gas] ns0 (n-1)dx.
(a) Cr(NH3)3Cl3 (b) V(H2O)63+ (c) PtCl42–
Cr3+ (d3) + 3 NH3 + 3 Cl- V3+ (d2) + 6 H2O Pt2+ (d8) + 4 Cl
–
Chem. 312, Autumn '13 Problem Set #4, page 3

(d) (g) OH2 What is the common name (not the official IUPAC name)
H2 of the organic ligand bound to copper in the complex at
O O N left? (There are actually two copies of this ligand in the
Cu complex, and the ligand is the deprotonated form of the
N O O chemical I’m asking you to name.) Would you be more
H2 likely to find this ligand in the Aldrich Chemical Catalog
OH2 or the Sigma Catalog of biochemicals? (Actually, you
would find it in both.)
(g) OH2
H2
O O N
O:
Cu = Cu2+ (d9) + 2 H2O +

:
NH2
N O O 2 O
H2
Answer: OH2
The ligand is the deprotonated form of the amino acid alanine.

4. (a) [Cr(H2O)6]2+ is high spin. It is colored (blue) e

g h!
because a photon can be absorbed by promotion
of one electron from the t2g set of orbitals to the t2g
eg set. In a diagram like the one at right, add
ground state excited state
electrons to represent the ground state and the
lowest energy excited state.
When you put the electrons in, you should follow Hund’s rule, that a state is lower in energy
when the electrons are in different orbitals with their spins pointing in the same direction
(e.g., all spin up, ↑↑). It is higher energy if the electrons pair in one orbital or even if they
have opposite sign (↑↓) in two different orbitals (because when the electrons have opposite
spin they can get closer together and they therefore repel each other more). Note that the
absorption of a photon does not change the spin of the electron that is promoted. If it is spin
up in the ground state, it must be spin up in the excited (except in rare cases).
The ground state has four unpaired electrons
eg h! and therefore S = 2. When one electron is
promoted, its spin doesn’t change so the
t2g excited state has the same value, S = 2. It
doesn’t matter which electron is promoted.
The promoted electron has to go into the eg orbital that was empty in the ground state, because
two electrons of the same spin can’t occupy the same orbital (the Pauli exclusion principle).

(b) The spin state S of a complex is the sum of the spins of all of the electrons. If all the
electrons are paired (↑↓) then S = 0. But, for example, if there are two spin-up electrons
(↑↑), each with spin +½, then the complex will have S = 1. Give the spin states for the
ground and excited states in part (a). (answer in part (a))
(c) Now consider the same problem for the high spin [Mn(H2O)6]2+ ion. Draw in the electrons
for the high spin ground state. What is S for this state? Is there a problem promoting an
electron in this case?
The ground state has five unpaired electrons and therefore S = 5/2.
eg h! But in this case, an electron can’t be promoted from t2g to eg. All the
X
electrons are spin-up, and there is no place in the eg set to put a
t2g spin-up electron (without violated Pauli exclusion). So there is no
transition and no absorption, and the manganese ion is essentially
colorless.
(d) Use your answer to (b) to explain why the [Mn(H2O)6]2+ ion is essentially colorless, even
though it has a field splitting (∆o) close to that of [Cr(H2O)6]2+. (answer in part (c))
Chem. 312, Autumn '13 Problem Set #4, page 4

5. We have discussed the solvation of cations by water. Now consider the solvation of cations and
anions by methanol, CH3OH. Methanol is just like water except that one hydrogen has been
replaced by a methyl group. Methanol is a polar solvent, but less polar than water (due to the
non-polar methyl group ). Methanol has a lower dipole moment than water.
(a) Consider the primary hydration of cations, the formation of the first coordination sphere
(analogous to, for instance, Ca(H2O)x2+ in water). Which atom of methanol will bind to a
cation? Is this similar or different from water?
The oxygen of methanol binds to the cation, just as in water. The cation is the Lewis acid and the
oxygen is the Lewis basic part of the methanol, the only center with any lone pairs.

(b) Would you expect the heat of solvation of cations in methanol to be larger or smaller than in
water? Explain. [Hint: think about this in terms of a cation interacting with a dipole.]
The heat of solvation of cations in methanol is less favorable than in water (less negative). Since
methanol is less polar it has a smaller dipole and therefore smaller interactions with a cation.

(c) Would you expect secondary solvation to be stronger or weaker in methanol?

Secondary solvation should be much weaker in methanol since methanol is less polar than water
and has only one hydrogen so that the hydrogen-bonding network is much weaker. Methanol is
also larger in size than water, so the second solvation shell will be farther away from the cation.
(MeOH is an abbreviation for methanol.)

6. Look at: Insights into the Interplay of Lewis and Brønsted Acid Catalysts in Glucose and
Fructose Conversion to 5‑(Hydroxymethyl)furfural and Levulinic Acid in Aqueous Media
V. Choudhary, S. H. Mushrif, C. Ho, A. Anderko, V. Nikolakis, N. S. Marinkovic, A. I.
Frenkel, S. I. Sandler, and D. G. Vlachos J. Am. Chem. Soc. 2013, 135, 3997. This is a long
paper; you don’t need to read all of it (or even most of it) to answer the questions below.
(a) What kind of chemicals are glucose and fructose? The Introduction to the paper states that
the long-term ‘big picture’ goal is “cellulosic biomass conversion to platform chemicals.”
What does that mean?
Glucose and fructose are sugars, carbohydrates, monosaccharides. They are obtained from
plants, typically from sugars in plants. It would be best to make them from cellulose, which is a
carbohydrate polymer (a polysaccharide), since there isn’t much other use for the cellulose. For
instance, in corn the kernels have most of the sugars, but the majority of the corn is in the stalk
and the husks. It would be good to convert cellulose into chemicals that are solid in large
quantities, or that are “platform chemicals” that are materials that can converted to large volume
chemical products. HMF is thought to be a good precursor to a polymer that is like polyester
(recycle symbol 1).

(b) Give the d electron counts for the three chromium complexes in Scheme 2.
3+ 3
All three of the compounds are Cr , d .

(c) Does equation 1 look familiar? Is this reaction something that the authors think is important
enough to highlight in the Conclusions?
3+
Yes, equation 1 is just like the hydrolysis of Al that we’ve discussed in class. It’s basic inorganic
chemistry. Yet it’s highlighted as part of the key results of the paper, as indicated by the following
sentence.
“We also show for the first time that Brønsted acid catalysts inhibit the Lewis acid catalyzed
2+
isomerization by decreasing the concentration of the active Cr species CrOH due to a shift in the
chemical equilibrium of hydrolysis of the metal cation.
Chem. 312, Autumn '13 Problem Set #4, page 5

(d) There is a sentence at the end of p. 4002 “an increase in H+ concentration would shift the
thermodynamic equilibrium toward the left (Le Chatelier’s principle) in equation 1, and
suppress the formation of CrOH2+.” Do you agree with this statement?
Yes, I do, completely.

(e) Using the Table in our textbook, compare the pKa of the aqueous chromium ion that is the
focus of this paper with the pKas of the aquo ions of iron and aluminum with the same
charge. Which ion is the most acidic? Does the pattern of the three pKa values fit the Z2/r
periodic trend we have discussed in class? Or does it follow a different trend? I don’t expect
that you could have predicted this trend, but I think you can rationalize it with the data in the
book.
3+ 3+ 3+
In Table 2.2 (p. 25), the pKas are Cr - 4.0; Fe - 2.2; Al - 5.0. The primary trend that we’ve
2
talked about is the Z /r trend. Since all three are 3+ ions, this trend predicts that the pKa’s should
3+
be inversely related to the radii, but this isn’t the trend of those values. The radii are Cr - 75 pm;
3+ 3+ 3+
Fe - 78 pm; Al - 67. Al is the smallest, yet it is the least acidic (highest pKa), opposite to the
trend. The trend in pKa’s follows the trend in electronegativities, from inside the front cover:
Al, 1.61 < Cr, 1.66 < Fe, 1.83. As discussed in class and in the book, the lower the
electronegativity of the central ion the more covalent the complex ion, which favors loss of H+ and
formation of the hydroxide complex.

7. Look at: Synthesis, Electronic Structure, and Magnetism of [Ni(6-Mes)2]+: A Two-Coordinate

Nickel(I) Complex Stabilized by Bulky N‑Heterocyclic Carbenes by Rebecca C. Poulten, et
al., J. Am. Chem. Soc. 2013, 135, 13640.
This paper reports unusual two-coordinate nickel complexes. The nickel can only bind two
ligands because the ligands are so huge (also called bulky or sterically large or sterically
encumbered). Figures 1 and 3 show the large size of the ligands. They are the results of X-
ray diffraction experiments that give accurate atom positions in a crystal. The ligands are
neutral “N-heterocyclic carbenes”, which I will just abbreviate as NHC.
(a) Compound 2 is the neutral Ni(NHC)2 complex. Using the fact that the NHC ligands are
neutral, give the oxidation state and d-count of the nickel.
Since the complex is neutral and the ligands are neutral, the Ni must be neutral. A nickel atom is
2 8
[Ar]4s d in the gas phase, but in a complex the valence s orbital must be empty. So the central Ni
0 10
has the configuration [Ar]4s d .

(b) A calculation of the molecular orbitals of 2 gives a 2-above-1-above-2 splitting pattern for
the d orbitals, as shown in Figure 4. The top two orbitals are at essentially the same energy
(“near degenerate”) as are the bottom two. Using the electronic configuration in part (a) just
above, state how many electrons are in each of the orbitals for complex 2.
10
Since the configuration is …d , all five of the d orbitals must be filled with two electrons.

(c) I was surprised to see the 2-above-1-above 2 pattern. I would have expected a 1-above-2-
above-2 pattern. Based on the construction of the MO diagram we did in class, why did I
expect the single (non-degenerate) orbital to be at the top?
The d orbital(s) at the top are usually the one(s) that are most involved in bonding to the ligands,
because what we call “the d orbitals” are the antibonding component of the d-ligand interaction. It
looks to me that the dz2 orbital is the most involved in bonding, so I would have expected that its
antibonding component would be the highest.