Chapter 8 Chemistry of the Main Group Elements

107

CHAPTER 8: CHEMISTRY OF THE MAIN GROUP ELEMENTS

8.1

a.

H2
H2+

74.2 pm
106 pm

436 kJ/mol
255 kJ/mol

These values are consistent with the molecular orbital descriptions. H2 has two
electrons in the bonding orbital, H2+ has only one. The net attraction between the
bonding electron and the nuclei are weaker in H2+ relative to that between the two
bonding electrons and the nuclei in [Link], the bond distance is longer in H2+.
b.
8.2

H3+ was described in Problems 5.21 and 5.43. It has a single pair of electrons in a
2-electron, 3-center bond, with bond orders of 1/3.

He2+ has 2 electrons in the bonding orbital and 1 in the antibonding * orbital, with a
bond order of . HeH+ has a bond order of one, but with a poorer match between the
energy levels of the two atoms (13.6 eV for H, 24.5 for He).
1s*

1s

1s*
1s

1s

1s
1s

1s
He

He2+

He+

HHe+

He

H+

8.3

If the isoelectronic series could be continued, the ion CsF4+ would be expected to have a similar

structure to XeF4 and IF4 , with two lone pairs in trans positions. However, a variety of factors

make such a species truly unlikely. For example, while the bonds in XeF4 and IF4 are best
described as polar covalent, the tremendous difference in electronegativity between Cs and F
suggest that ionic bonding would be necessary in CsF4+. However, complexes containing Cs(V)
are unknown.

8.4

The equilibrium constants for formation of alkali metal ion complexes with cryptands are listed in
Figure 8.7, with the formation constant for the sodium complex with cryptand [2.2.1] larger than
for either the lithium or potassium complexes. A similar trend is found for the alkaline earths,
with the maximum at strontium. Apparently the optimum size for an ion fitting in the cryptand is
larger than sodium (atomic radius: 107 pm), but smaller than barium (149 pm) or potassium (138
pm), leaving strontium (132 pm) as the closest fit.

8.5

The diagram at the right shows

the primary interactions forming
2p
molecular orbitals. The other
orbitals on the fluorine atoms
2s
form lone-pair orbitals and
orbitals. The interactions are similar to those in carbon
dioxide (Figure 5.25), but the poorer energy match
between the valence orbitals leads to significantly
less covalent character in the resulting bonds of BeF2.
Be

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2p

F Be F

108
8.6

Chapter 8 Chemistry of the Main Group Elements

A combination of the in-plane p orbitals of Cl and the s and in-plane p orbitals of Be form
orbitals that link the Be and Cl atoms in 3-atom, 2-electron bonds. The atomic orbital interactions
that result in bonding molecular orbitals involving these bridging chlorine atoms are shown
below. The antibonding orbitals also formed by these interactions, along with other orbitals with
significant contribution from the terminal chlorine atoms, are not shown.
pz

pz
px

Cl
Be

Be
Cl

pz
px

pz

px

px
s

The same orbitals, shown as calculated using extended Hckel theory software, are below.
Orbitals from the terminal chlorine atoms are included in these molecular orbitals.

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Chapter 8 Chemistry of the Main Group Elements

8.7

The much greater difference in

orbital energies of B (8.3 and 14.0
eV) and F (18.7 and 40.2 eV)
makes the BF bond weaker than that
of CO. The s orbital of B and the p
orbital of F can interact, but the p-p
combination cannot interact significantly
because of the large difference in p orbital
energies. This mismatch results
in weak single bonding, rather than
the triple bond of CO.

109

2p

2s

2p

2s

BF

F
R

8.8

a.

Evidence cited for a double bond

includes an X-ray crystal structure that shows
a very short boronboron distance (156 pm)
that is considerably shorter than compounds
having boronboron single bonds and
comparable to the bond distance in
compounds with double bonds between boron
atoms. Density functional theory
computations also showed a HOMO with
boronboron bonding.

R
H

B
R

N
B

R
N

R = isopropyl
R
R

b.

The product in this case was a silicon compound

having a structure similar to the boron compound
shown above, but lacking hydrogen atoms;
nevertheless, it has bent geometry at the silicon
atoms, leading to the zigzag structure shown at
right. An X-ray crystal structure similarly shows a
siliconsilicon distance consistent with a double
bond, and density functional theory yields a
HOMO with bonding between the silicon atoms.

N
N

R
Si
R

Si
R

R
N

8.9

The combination of orbitals forming the bridging orbitals in Al2(CH3)6 is similar to those of
diborane (Section 8.5.1). The difference is that the CH3 group has a p orbital (or sp3 hybrid
orbital) available for bonding to the aluminum atoms, with the same symmetry possibilities
as those of H atoms in B2H6.

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110
8.10

Chapter 8 Chemistry of the Main Group Elements

D2h
(pz)
(px)
(1s)
Ag
B2g
B1u
B3u

C2(z)
2
2
0
1
1
1
1

E
2
2
2
1
1
1
1

C2(y)
0
0
0
1
1
1
1

C2(x)
0
0
2
1
1
1
1

(xy)
0
0
2
1
1
1
1

i
0
0
0
1
1
1
1

(xz)
2
2
2
1
1
1
1

(yz)
2
2
0
1
1
1
1

z2
xz
xy
x

Reduction of the representations gives the following:

Boron orbitals:
a.

(pz) = Ag + B1u

b.

(px) = B2g + B3u

Hydrogen orbitals:
c.

(1s) = Ag + B3u

d.

Treating each group orbital as a single orbital, the orbitals below have the indicated
symmetries.

D2h

C2(z)

C2(z)

C2(z)

(xy)

(xz)

(yz)

Ag (pz)

B1u (pz)

B2g(px)
B3u (px)
Ag (s)
B3u
8.11

Carbon has two lone pairs in C(PPh3)2, with VSEPR predicting a tetrahedral electron group
geometry. The bulky phenyl groups limit the impact of the nonbonding pairs and force a larger
angle.

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Chapter 8 Chemistry of the Main Group Elements

8.12

111

The cations of CaC2, CeC2, and YC2 are not isoelectronic. While Ca 2+ has no valence electrons,
the unusual 2+ group 3 ion Y 2+ and the lanthanide Ce 2+ contain 1 and 2 valence electrons,
respectively. It has been suggested (Greenwood and Earnshaw, Chemistry of the Elements,
2nd ed., p. 299) that there is some transfer of this valence electron density to the * orbitals of the
dicarbide (or acetylide) ion, resulting in a longer bond.

8.13

Radioactive decay obeys a first order kinetic equation:

x
dx
kx; ln kt
dy
x 0

The relationship of the half-life (the time at which x = xo) and the rate constant is

x 1
ln ln kt1/ 2 0.693
x 0 2
k

0.693
t1/ 2

0.693

1.2110 4 y 1
t1/ 2
x
ln ln.56 1.21 10 4 t
x 0
k

8.14

t 4.8 10 3 y

Ih symmetry includes 12 C5 axes, 12 C52 axes, 20 C3 axes, 15 C2 axes, an inversion center, 12 S10
axes, 20 S6 axes, and 15 mirror planes. One of the C5 axes and an S10 axis can be seen in the
middle of the second fullerene figure (end view) in Figure 8.18. There are six of each of these,
each representing two rotation axes, C5 and C54, for a total of 12. The same axes fit the 12 S52
axes. If the structure is rotated to line up two hexagons surrounded by alternating pentagons and
hexagons, the 20 C3 and 20 S6 axes can be seen (one in the center, three in the first group around
that hexagon, and three adjacent pairs in the next group, doubled because of C3 and C32). The
C2 axes pass through bonds shared by two hexagons, with pentagons at each end. These original
hexagons each have two more, making five, the next ring out has eight, and the perimeter (seen
edge on) has two for a total of 20 C2. There are five mirror planes through the center of the
pentagons surrounded by five hexagons (see the end view of Figure 8.18 again), and there are
three sets of these for a total of 15. (All this is best seen using a model!)

8.15

a.

Td

b.

Ih

c.

D5h

d.

zigzag: C2h

armchair: D2h

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112

Chapter 8 Chemistry of the Main Group Elements

8.16

Graphane, obtained from the hydrogenation of graphene, was first reported in 2009 (see J.
Agbenyega, Mater. Today, 2009, 12, 13), and research interest has grown rapidly.

8.17

Printing on transparencies is suggested for this exercise. Rolling up of the diagram should
show that more than one chiral form is possible.

8.18

Readers are encouraged to search for the most recent references in this promising area. At this
writing (February 2013) the reference has been cited in 176 other articles in scientific journals.

8.19

The reference provides absorption spectra and colors of solutions containing mixtures
of armchair-enriched single-walled carbon nanotubes with different diameters, ranging from
0.83 nm to 1.5 nm. The strongest absorption band for the nanotubes shifted to longer wavelength
(lower energy) as the diameter increased, with the smallest absorbing at 407 nm and the largest at
785 nm, and the observed colors (complementary to the colors of the strongest absorption bands)
changed accordingly. The observations were consistent with the energy levels of the nanotubes
becoming closer as the diameters of the tubes increased. A similar size effect is observed for
quantum dots (Section 7.3.2).

8.20

The increased stability of 2+ oxidation states as compared to 4+ is an example of the inert

pair effect (see Greenwood and Earnshaw, Chemistry of the Elements, 2nd ed., pp. 226, 227,
374). In general, the ionization energy decreases going down a column of the periodic table,
because of greater shielding by the inner electrons. In this family, removal of the second
electron is fairly easy, as it is the first in the higher-energy p orbitals. However, the next two
electrons to be removed are the s electrons, and they are not as thoroughly shielded in the ions.
The effect is larger for the three lower members of the group because the d10 electrons are added
between the s and p electrons. The lower electronegativity of C and Si make them more likely to
form covalent bonds than ions.

8.21

a.

H2ISiSiH2I has a C2 axis perpendicular to the plane of the diagram as drawn, a

perpendicular mirror plane (the plane of the diagram), and an inversion center, C2h.

b.

The SiH stretches have the reducible representation shown below, which reduces to
= Ag +Bg +Au+Bu. Au and Bu are IR-active.
C2
C2h
E
i
h
4
0
0
0

1
1
1
1
Ag
Rz
1
1
1
1
R x, R y
Bg
1
1
1
1
Au
z
1
1
1
1
x, y
Bu

8.22

P4 (g)
2 P2 (g), H = 217 kJ mol1
P4 has six PP bonds, so six bonds are broken and two triple bonds are formed.
H = bond dissociation energy (reactant) bond dissociation energy (product)
217 = 6 200 2(bond dissociation energy of PP)
Bond dissociation energy of PP = 492 kJ mol1
The p orbitals in P2 do not overlap as effectively as those in N2 on the basis of the larger atomic
radius of P relative to N, resulting in weaker bonds in P2.

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Chapter 8 Chemistry of the Main Group Elements

8.23

a.

b.

c.

8.24

N3 has molecular orbitals similar to those of CO2 (Section

5.4.2), with two occupied orbitals and two
occupied orbitals for a total of four bonds. In contrast
to the situation in CO2 , the atomic orbitals involved in the

bonding in N3 have equal energies.

113

Because the HOMOs of N3 (at right) are primarily

composed of p orbitals of the terminal nitrogen atoms, H+
bonds at an angle to the N=N=N axis. The angle is 114,
larger than the 90 predicted by simple bonding to a p
orbital.
The HNN angle is 114. This observation suggests that
the first resonance structure (with an N(sp)H bond)
contributes less to the electronic ground state of HN3
relative to the second structure (with an N(sp3)H bond.
A decreased terminal NN distance relative to the central
NN distance is consistent with these contributions.

1+

1+

1+

N
N

The electronegativity of H (2.300) is less than that of N (3.066). Hydrazine has two hydrogen
atoms and an equally electronegative NH2 group bound to each nitrogen atom, while ammonia
has three hydrogens bound to N. In this way, ammonia features three polar covalent bonds
enriching the electron density at nitrogen, while hydrazine features two polar covalent NH
bonds and one nonpolar covalent bond (to the NH2 group). The N of ammonia is therefore more
electron-rich, and hydrazine is the weaker aqueous base.
Another factor is the potential for hydrogen bonding with water in the resulting conjugate acids.
An ammonium ion (NH4+) features four excellent hydrogen bond donors per N atom, while
hydrazinium ion features just three hydrogen atoms bound to a positively charged N atom. The
enhanced opportunities for NH4+ solvation relative to N2H5+ contribute to NH3 being a stronger
base.

8.25

The larger central atoms feature longer bond lengths, leading to lower concentrations of bonding
electron density close to the Group 15 atom, reducing bonding pair-bonding pair repulsion. The
lone pair subsequently exerts increasing influence down the column, forcing smaller angles as the
atomic radius of the central atom increases. This decrease in bonding pair-bonding pair repulsion
can also be explained using electronegativity arguments, with the most electronegative nitrogen
atom drawing a larger share of the bonding electron density towards it relative to the other group
15 elements that progressively become less electronegative down the column.

8.26

One p orbital of each oxygen is used for the bond to nitrogen, and the p orbital
perpendicular to the plane of the molecule is used for a orbital. The remaining p orbital
is in the plane of the molecule, so addition of a proton to this lone pair leaves the entire
molecule planar.

8.27

From Table 8.10

N2O
Cv
N2O4 D2h

NO2
C2v
HNO2 Cs

NO
N2O5

NO3
HNO3

Cv
D2h
D3h
Cs

NO2
C2v
NO+ Cv
N2O22 C2h

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N2O3 Cs
NO2+ Dh
NO43 Td

114
8.28

Chapter 8 Chemistry of the Main Group Elements

a.
b.

Computational work suggests that the electronic ground state of cis- N 2 F4 is 1.4 kcal/mol
lower than that of trans- N 2 F4 at 298 K.
Two trans-cis isomerization mechanisms are proposed. The simpler mechanistic
possibility involves rotation about the N=N bond. A lower limit of 59.6 kcal/mol was
calculated for this isomerization mechanism. The second possibility proceeds via a planar
transition state that resembles [N 2 F]F , with relatively short and long NF bonds, and a

nitrogennitrogen triple bond, respectively. The transformation of nitrogennitrogen

bonding electron density to nonbonding electron density at nitrogen completes the
isomerization. An activation barrier of 68.7 kcal/mol was determined for this mechanism.
The activation barrier for isomerization via N=N rotation is 9.1 kcal/mol less than the
proposed barrier for the [N 2 F]F mechanism.
c.

As a strong Lewis acid, SbF5 can engage in a donor-acceptor interaction with a

nonbonding pair on a fluorine atom (left). The structure on the right, where the F atom
has been completely transferred, resulting in [N 2 F][SbF6 ] , is the limiting result of this
interaction.
F
F
F
N
F

Sb

Sb

F
F

While fluoride transfer is not envisioned to occur when SbF5 assists in the isomerization,
this possibility is instructive since it suggests that the interaction on the left is expected to
lengthen one NF bond while shortening the other NF bond and the NN bond.
These changes are predicted to lower the activation barrier of the donor-acceptor complex
(left) towards formation of the planar isomerization transition state that resembles
[N 2 F]F , with a relatively short and long NF bonds, and a nitrogennitrogen triple
bond, respectively.
8.29

The balanced reduction half-reactions, for acidic and basic conditions, respectively, follow.
Acidic:

H 3PO4 (aq) + 2 H + (aq) + 2e

H 3PO3 (aq) + H 2O(l)
H 3PO3 (aq) + 2 H + (aq) + 2e
H 3PO2 (aq) + H 2O(l)

4 H 3PO 2 (aq) + 4 H + (aq) + 4e

P4 + 8 H 2O(l)
P4 + 8 H + (aq) + 8e
2 P2 H 4
P2 H 4 2 H +(aq) 2e
2 PH 3
Basic:

PO43 (aq) + 2 H 2O(l) + 2e

HPO32 (aq) + 3 OH (aq)

HPO32 (aq) + 2 H 2O(l) + 2e

H 2 PO2 (aq) + 3 OH (aq)

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Chapter 8 Chemistry of the Main Group Elements

115

4 H 2 PO 2 (aq) + 4e
P4 + 8 OH (aq)

P4 + 12 H 2O(l) + 12e
4 PH 3 + 12 OH (aq)
The Frost diagram for phosphorus in acidic solution features points at (5, 1.915; H 3PO4 ),
(3, 1.363; H 3PO3 ), (1, 0.365; H 3PO2 ), (0, 0; P4 ), (2, 0.200; P2 H 4 ), and (3, 0.206; PH 3).
The Frost diagram for phosphorus in basic solution features points at (5, 7.43; PO 43 ),
(3, 5.19; HPO32 ), (1, 2.05; H 2 PO 2 ), (0, 0; P4 ), (3, 2.67; PH 3).

8.30

The bonding between O2 units is proposed to

involve interactions between the singly occupied
* orbitals of neighboring molecules. Such
interactions would generate both bonding and
antibonding molecular orbitals, with the

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116

Chapter 8 Chemistry of the Main Group Elements

originally unpaired * electrons stabilized (i.e., lowered in energy) as they occupy the bonding
orbitals in O8. One such interaction is shown at right. Diagrams of the four highest occupied
molecular orbitals of O8 (which may be viewed as (O2) 4) are in the reference.

8.31

S2 is similar to O2, with a double bond. As a result, the bond is shorter than single bonds in S8.

8.32

MnF62 acts as a Lewis base, transferring two F ions to two SbF5 molecules:

MnF62 + 2 SbF5 2 SbF6 + MnF4

The MnF4 intermediate can then lose an F atom, with two of these radicals coupling to form F2:
2 MnF4 F2 + 2 MnF3
8.33

a.

Although the ClO3 groups in Cl2O7 are highly electronegative, their size is apparently
responsible for the larger angle in Cl2O7 (118.6) than in Cl2O (110.9).
O
Cl

O3Cl

Cl
110.9

b.

118.6

2-

O
ClO3

O3Cr

126

CrO3

In the dichromate ion the highly electropositive Cr atoms allow the central oxygen
to attract electrons more strongly than is possible in Cl2O7, resulting in stronger bonding
pair-bonding pair repulsions around the central oxygen in [Cr2O7]2 and a larger bond
angle (126).

8.34

I3 is linear because there are three lone pairs in a trigonal geometry on the central I. I3+ is
bent because there are only two lone pairs on the central I.

8.35

B has only three valence electrons. Adding six from the hydrogen atoms gives B2H6 a total of 12
electrons. The 3-center 2-electron bonds result in four pairs around each boron atom and
nearly tetrahedral symmetry at each boron atom. Iodine has
seven valence electrons initially. In I2Cl6, five more are added
Cl
Cl
Cl
to each iodine, resulting in 12 electrons and octahedral
I
I
Cl
Cl
Cl
geometry around each iodine.

8.36

F + BrF3 BrF4

KF acts as a base; BrF4 is the solvent anion.

SbF5 + BrF3 BrF2+ + SbF6

8.37

a.

BrF2+ is the cation of the solvent; SbF5 acts as the acid.

Br2+ and I2+ have one less antibonding electron than Br2 and I2, so the cations have bond
orders of 1.5 and shorter bonds than the neutral molecules:
Br2
Br2+

b.

Bond Order
1.0
1.5

Bond Distance (pm)

228
213

I2
I2+

Bond Order
1.0
1.5

Bond distance (pm)

267
256

The most likely transition is from the g* (HOMO) to u* (LUMO) (see Figure 5.7 for
comparable energy levels of F2). Because the observed colors are complementary to the
colors absorbed, Br2+ is expected to absorb primarily green light, and I2+ is expected to
absorb primarily orange light. Because orange light is less energetic than green, I2+ has

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Chapter 8 Chemistry of the Main Group Elements

117

the more closely spaced HOMO and LUMO.

8.38

c.

In both I2 and I2+ the HOMO and LUMO are the g* and u*, respectively. I2 absorbs
primarily yellow light (to give the observed violet color) and I2+ absorbs primarily orange
(to give blue). Because yellow light is more energetic than orange, I2 has the more
widely spaced HOMO and LUMO.

a.

In I2+ there are three

electrons in the * orbitals that
result from interactions between 5p

orbitals (these are the orbitals

I
I
labeled 4g* in Figure 6.10).
I
I
Interaction between the singly
I2+
I42+
occupied * orbitals of two
I2+ ions can lead to stabilization of electrons by formation of a bonding
molecular orbital that can connect the I2+ units when I42+ is formed.

b.

I2+

Higher temperature would provide the energy to break the bonds between
the I2+ units and favor the monomer. In addition, formation of two I2+ ions from I42+
would be accompanied by an increase in entropy, also favoring the monomer at higher
temperatures.
F

8.39

There are three possibilities:

O
F
F
F
The third structure, with the lone
pair and double bonds in a facial
F
O
arrangement, is least likely because it
C2v
Cs
would have the greatest degree of
electron-electron repulsions involving these regions of high electron concentrations.

O
O

F
Cs

Infrared data can help distinguish between the other two structures. In the first structure, only the
antisymmetric stretch would be IR-active, giving a single absorption band. In the second
structure, both the symmetric and antisymmetric stretches would be IR-active, giving two bands.
Observation of two IO bands is therefore consistent with the second structure. This structure,
which has fewer 90 lone pairdouble bond repulsions than the first structure, is also most likely
by VSEPR considerations. Other experimental data are also consistent with the second structure.
8.40

Superhalogens are species which, like the halogens, have very high electron affinities. Classic
superhalogens contain a central atom surrounded by highly electronegative atoms or groups of

atoms. Examples include MnO4, AlCl4 , and BO2 . See K. Pradhan, G. L. Gutsev, P, Jena, J.
Chem. Phys., 2010, 133, 144301; C. Sikorska, P. Skurski, Inorg. Chem., 2011, 50, 6384; and
references cited therein.

8.41

These reactions take place in the gas phase. The initial product of Xe with PtF6 is believed

to be Xe+ PtF6 ; however, when these two ions are in close proximity, they may react further

to give [XeF]+, [Pt2F11] , and other products. SF6, if present in large excess, prevents the
formation of these secondary products, apparently by acting as an inert diluent and preventing
effective collisions between the desired products.

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118

Chapter 8 Chemistry of the Main Group Elements

8.42

F
Xe

F
F

Xe

Xe

O
C4v

F
C2v

8.43

F
F

Xe

F
C2v

F
D3h

Two electrons are in the bonding orbital and two are in the nonbonding orbital:

5p
2p

Xe

8.44

F Xe F

Xe(OTeF5)4: The OTeF5 group has one electron available for bonding on the O, so the four
groups form a square planar structure around Xe, with lone pairs in the axial positions.
O=Xe(OTeF5)4: A square pyramidal structure, with O in one of the axial positions and a
lone pair on the other, and OTeF5 groups in the square base.

8.45

Half reactions:

Mn2+ + 4 H2O MnO4 + 8 H+ + 5e

XeO64 + 12 H+ + 8e Xe + 6 H2O
Overall reaction:

8 Mn2+ + 5 XeO64 + 2 H2O 8 MnO4 + 4 H+ + 5 Xe

8.46

XeF5 has D5h symmetry. The reducible representation for XeF stretching is
D5h

E
5

2C5
0

2C52
0

5C2
1

h
5

2S5
0

2S53
0

which reduces to A1+ E1+ E2, with only E1 IR-active.

O
F

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5v
1

Xe

F
F

Chapter 8 Chemistry of the Main Group Elements

8.47

a.

Point group: C4v

C4v

A1
A2
B1
B2
E

8.48

119

E
18
1
1
1
1
2

2C4
2
1
1
1
1
0

C2
2
1
1
1
1
2

2v
4
1
1
1
1
0

b.

= 4 A1 + A2 + 2B1 + B2 + 5E

c.

Translation: A1 + E (match x, y, and z)

Rotation: A2 + E (match Rx, Ry, and Rz)
Vibration: all that remain: 3 A1 + 2B1 + B2 + 3E

2d
2
1
1
1
1
0

z
Rz
(x, y), (Rx, Ry)

By the VSEPR approach, XeF22 would be

F
expected to have a steric number of 6, with
four lone pairs on xenon. Two structures,
F
Xe
Xe
cis and trans, need to be considered. In
F
the cis structure there would be five lone
pairlone pair interactions at 90, and in the
F
trans structure there would be only four such
cis
trans
interactions. The trans structure, therefore,
would be expected to be more likely. However,
the number of lone pairlone pair repulsions would still be high, likely making this a difficult ion
to prepare.

8.49

The energy necessary for vibrational excitation decreases with reduced mass; consequently, the
lowest energy band, at 1003.3 cm-1, is assigned to the XeD stretch of DXeOXeD, the deuterium
analogue of HXeOXeH. The remaining unassigned bands, at 1432.7 and 1034.7 cm-1, are
therefore due to the XeH and XeD stretches, respectively, of HXeOXeD, which is also formed.

8.50

a.

HXeO63 2 H 2O(l) 2e
HXeO4 4 OH o 0.94 V
HXeO 4 3 H 2O(l) 6e
Xe + 7 OH o 1.24 V

b.

The disproportionation reaction of interest is:

4 HXeO4 5 OH
Xe + 3 HXeO63 3 H 2O(l) o 0.30 V
G o nFE o (6 mol)(96485
8.51

a.

C
J
)(0.30 ) 1.7 *105 J (170 kJ ) .
C
mol

The synthesis of XeO 2 is very challenging to carry out. A special reactor composed of
a perfluoro-ethylene/propylene copolymer must be rendered completely moisture free by
extended treatment under vacuum. The reactivity of the container surface is then further
reduced by treatment with F2 gas. Once the container is prepared, a small volume of
water is added in an Ar gas atmosphere, and cooled to 0 C. The reaction is initiated by

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Chapter 8 Chemistry of the Main Group Elements

slowly adding XeF4 crystals. The authors emphasize the importance of both the order of
the addition (water first, then XeF4 ) and the speed of addition. The large and negative
reaction H , coupled with the relatively small volume of solvent to dissipate the
heat, can result in complications, including decomposition of the product; the mixture
must be kept at 0 C. Within 30 seconds after mixing, yellow XeO 2 precipitates from the
solution. The XeO 2 solid is then separated from the reaction mixture via centrifugation
of the mini-reactor itself at 0 C. The resulting solid is thermally unstable at ambient
temperature and must be kept cold (-78 C) for long-term storage.
b.

VSEPR theory predicts monomeric XeO 2 to be a bent molecule with a persistent dipole
moment that should permit solubility in water. The insolubility of obtained XeO 2
samples suggests an extended XeO 2 structure; individual monomeric units apparently do
not persist in water.

c.

Application of isotopically labeled water in the synthesis facilitated XeO 2

characterization. The presence of exclusively Xe O bonding was inferred by preparing

XeO 2 as described in (a) using H 216O and H 218O , respectively. The Raman spectrum of
the H 216O -derived XeO 2 was identical to that of the H 218O -derived XeO 2 sample,
except that all of the bands of the H 216O -derived XeO 2 sample were shifted to slightly
higher energies. The identical spectral patterns, coupled with an isotopic shift in each
band, suggested that only Xe O bonding was present. Identical Raman spectra were
obtained for XeO 2 samples prepared with either H 216O or D 216O , suggesting no
hydrogen in the samples; no isotopic shifts of any Raman bands were observed. These
chemists were particularly interested in the possibility of Xe OH units, which was
ruled out by the previous observations.
8.52

a.

The [XeF]+ ion, with a total of 14 valence s and p electrons, would be expected to have a
bond order of 1 (see Section 5.2.1).

b.

Using the VSEPR approach, the following structures can be drawn for the cations of
compounds 1-4:
F

F
S

Xe

F
F

F
F

Xe

F
F

F F

S
F

H
Xe

The [F3NXeF]+ ion, 1, with a triple bond between sulfur and nitrogen, has the shortest
NS distance (139.7 pm), and [F5SN(H)Xe]+, with a single bond, has the longest distance
(176.1 pm). The other ions have bond distances between these extremes that are
consistent with double bonds between sulfur and nitrogen.
c.

Compound 1 is expected to have a cation with linear bonding around nitrogen, as shown.
However, its crystal structure shows significant bending, with an SNXe angle of
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Chapter 8 Chemistry of the Main Group Elements

121

142.6. This bending is attributed to close NF contacts within the crystalline lattice.

8.53

8.54

d.

VSEPR would predict linear bonding with three lone pairs on xenon as, for example, in
XeF2. The angle measured by X-ray crystallography is 179.6.

e.

With significant SN double bonding, these groups are equatorial.

f.

The SFaxial bonds are longer, as in many other VSEPR examples (see Figures 3.17
through 3.19). Average distances for these ions are: (2: SF (axial), 158.2 pm; SF
(equatorial), 152.4 pm) and (3: SF (axial), 156.1 pm; SF (equatorial), 151.8 pm).

a.
b.

D2h
D4d

c.
d.

C1
C2v

e.
f.

Cs
C2

[FBeNe]+ The relative order of molecular orbitals may vary depending on the software used. A
simple approach, using an extended Hckel calculation, gave the following results:
FBe bonding

Several orbitals involved:

HOMO: degenerate pair

bonding between Be and F

Next orbital below HOMO

bonding by the F pz and the Be s

BeNe bonding

One molecular orbital contributing significantly:

Four orbitals below HOMO

bonding by the Ne pz and the Be s and pz

Overall, the interactions between Be and F are stronger than between Be and Ne.
8.55

In Xe2+, there are a total of 54 orbitals. We will classify only the higher-energy orbitals
here, starting with the highest energy (as calculated using the relatively simple extended Hckel
approach). The orbitals used are the 5s, 5p, and 4d.

Molecular
Orbital
HOMO

Type of
Interaction

HOMO 1

HOMO 2
HOMO 3

HOMO 4

Atomic
Orbitals
pz

px

py
pz
px

py

Molecular
Orbital
HOMO 8
HOMO 9
HOMO 10
HOMO 11

Type of
Interaction

Atomic
Orbitals
d 2 2 , d xy

d x 2 y 2 , d xy

HOMO 12
HOMO 13
HOMO 14
HOMO 15

d xz , d yz

d xz , d yz

dz2

HOMO 5
HOMO 6

HOMO 16

HOMO 7

HOMO 17

x y

dz2

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Chapter 8 Chemistry of the Main Group Elements

If this were neutral Xe2, there would be no bond, because every occupied bonding orbital
would be offset by an occupied antibonding orbital. In Xe2+, one electron has been removed, so
the bond order is

1
2

, making for a long bond. The large atomic radius of Xe further predisposes

Xe2+ to having a long bond. It is noteworthy that bonding is exceedingly weak in this species
since the overlap leading to formation of the and * orbitals is very small.
8.56

The reference by Steudel and Wong provides illustrations for the four highest occupied molecular
orbitals. In addition to the interesting symmetry of these orbitals, the way in which the * orbitals
of O2 are imbedded in the molecular orbitals of O8 should be noted.

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