Chemistry 507—F23

Problem Set #1 – Due Thursday, 9/14 at the start of class.

1. An elements’ reducing ability should correlate inversely with effective nuclear charge. Strong chemical
reductants, alkali metals for example, have valence electrons that experience low effective nuclear charge.
Oxidants, such as the halogens, have orbital vacancies that, if populated with an electron, would experience
a strong effective nuclear charge. This results in the qualitative periodic trends that oxidizing ability
increases across a row and decreases down a group.

A. The following chemical reaction is thermodynamically favorable:

Cl2 + 2 Br–  2 Cl– + Br2

Using Slater’s rules, determine the Zeff for a valence electron in both the Br– and Cl– ions. Do your results
agree with the physical data? Should an electron transfer from a Br– ion to a Cl atom (to form Cl–) be
favorable? Briefly justify your answer in the context of a columbic interaction (reliant on distance and
charge).

B. Use Slater’s rules to determine the effective nuclear charge felt for a valence electron each of the
following reductants:

I. Li0
II. Ca0
III. Zn0

The first ionization energies corresponding to these atoms (in no particular order) are: 906 kJ/mol, 590
kJ/mol, and 520 kJ/mol. Assign the correct first ionization energy to each species and rationalize your
selection.

C. Water oxidation is a critical half reaction in the context of clean energy, providing electrons and protons
for the reductive generation of “solar fuels” (Lewis, N.S.; Nocera, D.G. PNAS 2006, 103, 15729). A
highly active catalyst for alkaline water oxidation is a Nickel-Iron layered double hydroxide material.
Under anodic bias, the metal ions in this nanomaterial are proposed to oxidize from the Fe III/NiII state to
an FeVI/NiIII state (Gray, H.B. and coworkers Joule 2018, 2, 747).
 Chemistry 507 F23 PS #1

Iron(VI) is a very potent oxidant, and bridging hydroxide ligands generally provide strong electronic
coupling. With this in mind, an alternative oxidation state assignment of FeV/NiIV does not seem outside
of the realm of possibilities. While the coordination sphere of Fe and Ni will undoubtedly alter the metal
ion’s electronic structure, use Slater’s rules (Zeff) as a crude justification of the most stable redox pairing.
(Hint: Calculate Zeff for FeV/VI/VII and NiII/III/IV. Assuming facile electronic exchange, which redox pairing
do you expect to see? Note that the net oxidation state is conserved: FeV/NiIV, FeVI/NiIII, or FeVII/NiII).

Bonus: In one sentence, explain why cis-dioxo ligands stabilize a high oxidation state metal ion.

2. For each molecule or ion listed below:

A. Write acceptable Lewis structures and indicate non-zero formal charges. Limit your answer to no more
than the three most important contributing resonance structures. Indicate the major resonance
contributor. (Note: Connectivity should match the formula provided and is clarified when necessary…
CNMe is methyl isocyanide NOT acetonitrile, for instance).

B. For molecules with a unique central atom, illustrate and label the predicted shape for each molecule
(major resonance contributor). For molecules lacking a unique central atom, indicate predicted bond
angles for all atoms having more than one atom bonded to them (ignore the angles in methyl [Me]
substituents).

I. H2CN2
II. CNMe
III. MeCN
IV. [XeF3]+
V. ICl7
VI. S4N4 (alternating, cyclic)
VII. [(Me2N)2P]+
VIII. [(PPh3)2N]+
IX. OClF3

3. For IV, V, and IX above, illustrate one important “natural resonance theory” contributing structure.

4. The chemistry of “energy dense” materials is an explosive field of unique synthesis and structure. One
targeted structural motifs features nitrogen-nitrogen doubly and singly bonded chains and rings; these can
eliminate N2 in highly exergonic reactions.

A. For both [N7O]+ (C2v symmetry featuring an acyclic N7 chain) and (C2H2N3)NN(N3C2H2) (N8 chain with
two five-membered rings), draw two reasonable Lewis dot structures.

B. The [N5]+ cation (acyclic) can be prepared as follows:

[N2F][SbF6] + NH3  [N5][SbF6] + HF

Draw at least two Lewis dot structures for the cations [N 2F]+ and [N5]+.

Bonus: What is an abundant and stable molecule that is isoelectronic to [N2F] +?

C. [N5][Sb2F11] was structurally characterized by Christe and coworkers in 2001 (JACS 2001, 123, 6308).
The [N5]+ cation reacts as follows:

NO + [N5][SbF6]  [NO][SbF6] + 2.5 N2

Br2 + [N5][SbF6]  [Br2][SbF6] + 2.5 N2

For each reaction, assign the oxidation state of each atom and indicate which species is acting as an
oxidant and which is serving as a reductant.

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 Chemistry 507 F23 PS #1

D. A target molecule in this field is the complex salt [N5][N5], where [N5]+ is an acyclic cation and [N5]– is
a cyclic anion. N5– has thus far only been detected in the gas phase; however, P 2N3– is known (Velian,
A.; Cummins, C.C. Science 2015, 348, 1001) and the free anion and P5– has been assembled via transition
metal mediated P4 chemistry (Ellis, J.E. and coworkers Science, 2002, 295, 832). For each of these cyclic
compounds ([N5]–, [P5]–, and [P2N3]–), draw at least two Lewis dot resonance contributors, predict if the
molecule has Hückel aromaticity, and describe any structural deviation from an idealized pentagonal
geometry.