Chemistry 3830 Lecture Notes Dr. M.

Gerken Page

94
6. Group 18 elements


6.1 Elements

The elements all exist as monatomic gases. The only interactions possible between He, Ne, Ar, Kr, Xe and Rn atoms are weak
London dispersion forces. Thus their volatility is directly related to the size of the atoms, since larger atoms with the same
electron configuration are more polarizable, and increased polarizability is the main factor in stronger London dispersion
forces. Noble gases have a stable electron configuration, positive
EA
H, and very large I
1
. As a consequence, noble gases
cannot be oxidized or reduced easily to form compounds.

Element Electronic structure mp, C
EA
H, kJ mol
-1
I
1
, kJ mol
-1
Electronegativity van der Waals radius,
pm
He 1s
2
-272 48 2373 5.5 179
Ne [He] 2s
2
2p
6
-249 116 2080 5.1 159
Ar [Ne] 3s
2
3p
6
-189 96 1520 3.3 191
Kr [Ar] 3d
10
4s
2
4p
6
-157 96 1351 3.1 201
Xe [Kr] 4d
10
5s
2
5p
6
-112 77 1170 2.4 220
Rn [Xe] 4f
14
5d
10
6s
2
6p
6
-71 ? 1036 ? 230

Neon, argon, krypton, and xenon are obtained directly from air via fractional distillation of liquefied air (see Table for
composition of air). Helium is present in natural gas (0.2 to 7 Vol %) In the past, most of the helium was obtained from
American natural gas well, which contain a high percentage of helium. Helium is heavily used in its liquid form as a cryogen
for superconducting magnets (in NMR spectroscopy and MRI instruments). Recently, helium is becoming more and more
expensive, since natural gas production in the US is declining and new sources of He-rich natural gas have not be found to a
sufficient extent.

Selected components of air in order of increasing b.p.
boiling point, C percent abundance
He -269 5.2410
-4
Ne -246 1.81810
-3

N
2
-196 78.085
Ar -186 0.934
O
2
-183 20.948
Kr -153 1.1410
-4

Xe -108 8.710
-6




The heavier noble gases are used as fill gases in incandescent lamps, permitted higher temperatures of the filament. Discharge
tubes (neon tubes) contain noble gases with the emitted coloured light being a result of excited noble gas and Hg atoms.
Fluorescent tubes are also filled with noble gases; in these tubes the light is emitted from compounds (called phosphors)
covering the walls of the tubes. Rn in medicine as source in treatment of cancer.








He
Ne
Ar
Kr
Xe
Rn




Chemistry 3830 Lecture Notes Dr. M. Gerken Page

95


6.2 Compounds

6.2.1 Reactivity of Noble Gases
Before 1962, the noble gases were also called inert gases, since it was thought that they were unable to form covalent
bonds with other elements. Several attempts to make noble gas compounds failed prior to 1962; sometimes because of minor
details in the experiment. A historic account can be found in article: Lazlo, P.; Schrobilgen, G. J. Angew. Chem., Int. Ed. Engl.
1988, 27, 479-489.
In 1962, Neil Bartlett, a professor at UBC, reacted oxygen with PtF
6
, which is a strong oxidizer, producing a salt containing the
dioxygenyl, O
2
+
, cation. (Calculate the bond order for this real diatomic species using MO theory!).

O
2
+ PtF
6
O
2
+
PtF
6
-

The ionization potential for molecular oxygen is 12.2 eV and Neil Bartlett was looking for elements with a similar ionization
potential. He noticed that xenon has a ionization potential of 12.13 eV and designed an experiment with PtF
6
, which is a red
gas. Immediately after combining Xe gas with PtF
6
gas a solid formed: the first noble gas compound, which he postulated as
Xe
+
PtF
6
-
. The composition of this solid is still not fully characterized but contains XeF
+
. Although the product was not Xe
+
,
as postulated, this historic experiment proved the reactivity of noble gases. Shortly after this experiment a few labs in the world
worked on xenon chemistry producing a large number of new compounds.


6.2.2 Fluorides

One of the first compounds made after Bartletts experiment was XeF
2
. It turns out that three xenon fluorides can be made,
XeF
2
, XeF
4
, and XeF
6
; all of them being thermodynamically stable compounds.
XeF
2
,
f
H = -164 kJ/mol XeF
4
,
f
H = -284 kJ/mol XeF
6
,
f
H = -361 kJ/mol
The strongly oxidizing power of fluorine is needed to oxidize xenon to oxidation states +2, +4, and +6. However, the reaction
of xenon and fluorine has to be performed at elevated temperatures or under photochemical conditions, first producing a certain
concentration of atomic fluorine, F. Xenon difluoride has been produced by exposing a bulb filled with Xe and F
2
to sunlight.

Xe
(g)
+ F
2(g)
XeF
2
(400C, 1 atm, xenon in excess)

Xe
(g)
+ 2F
2(g)
XeF
4
(600C, 6 atm, Xe : F
2
= 1 : 5)

Xe
(g)
+ 3F
2(g)
XeF
6
(300C, 60 atm, Xe : F
2
= 1 : 20)

The reaction conditions have to be controlled due to equilibria between these xenon fluorides in order to avoid a mixture of
products.
Chemistry 3830 Lecture Notes Dr. M. Gerken Page

96


Xenon difluoride is a solid containing linear molecule with an AX
2
E
3

VSEPR geometry. Bonding in XeF
2
has been described with the two
resonance structures:
F-Xe
+
F
-
F
-

+
Xe-F

indicating a bond order of 0.5 for each Xe-F bond. In terms of MO
theory, the bonding can be described as a three-centre two-electron
interaction, giving also a bond order of 0.5 per bond. Hence, the
bonding in xenon fluorides can be described as having a large ionic
component.
Xenon tetrafluoride is a colourless solid containing square planar
molecules in accordance with the VSEPR model. The structure of XeF
6

is more complicated with an AX
6
E VSEPR geometry. Because of the
lone pair it is not an octahedral molecule. In the gas phase it is believed
to have a C
3v
-distorted octahedral geometry with the lone pair in a
trigonal face. This distorted molecule is fluxional with the lone pair
changing from one face to another. In the solid state XeF
6
forms at least
six different modifications with tetrameric and hexameric units. In the
crystal structures, bridging fluorides are present resulting in XeF
5
+

moieties.

modification structural units method of crystallization
XeF
6
(mP32) tetramers, (XeF
5
+
F
-
)
3
XeF
6
sublimation at 30C
XeF
6
(mC32) tetramers, (XeF
5
+
F
-
)
3
XeF
6
rapid sublimation above room temperature
XeF
6
(mP8) tetramers???? crystallization from melt
XeF
6
(cF144) tetramers, (XeF
5
+
F
-
)
4

and hexamers (XeF
5
+
F
-
)
6

maintaining sample at 4-18 C
XeF
6
(mP16) hexamers (XeF
5
+
F
-
)
6
crystallization form solution at -40 to -18C
XeF
6
(oP16) hexamers (XeF
5
+
F
-
)
6
low-temperature sublimation

The nature of XeF
6
in solution has been an important question. For a monomeric fluxional XeF
6
, a septet in the
129
Xe NMR
spectrum is expected arising from the coupling of xenon to the six averaged fluorine environments. However, a multiplet of
higher order is observed (see below). Detailed analysis of relative intensities indicate the presence of tetrameric (XeF
6
)
4

molecules in solution. Even at low temperature (-145 C) (XeF
6
)
4
is completely fluxional with one xenon and one fluorine
environment. Of the expected 25 lines, only 11 are observed in the
129
Xe NMR spectrum.




2p
Xe
2F
bonding
non-bonding
antibonding

Chemistry 3830 Lecture Notes Dr. M. Gerken Page

97






6.2.2 Reactivity of Fluorides
6.2.2.1 Hydrolysis.
All three xenon fluorides are oxidizing agents that can readily react with oxidizable substances. Although thermodynamically
stable, they have to be kept in an inert atmosphere without any traces of moisture. Xenon tetrafluoride and xenon hexafluoride
readily react with water, producing oxide fluorides as the first hydrolysis product using stoichiometric amounts of water.
XeF
4
+ H
2
O XeOF
2
+ 2HF
XeF
6
+ H
2
O XeOF
4
+ 2HF
XeF
6
+ 2H
2
O XeO
2
F
2
+ 4HF
Among the xenon oxide fluoride, XeOF
4(l)
is a noteworthy compound. It is a thermodynamically stable liquid at room
temperature, which is used as a reference for
129
Xe NMR spectroscopy.

If excess water is used, both fluorides produce XeO
3
, which is highly explosive in the solid state.
3XeF
4
+ 6H
2
O XeO
3
+ 2 Xe + 3/2 O
2
+ 12 HF
XeF
6
+ 3H
2
O XeO
3
+ 6HF

The hydrolysis reaction of XeF
4
results in dispoportionation; no evidence for a XeO
2
has been found. Aqueous solutions of
XeO
3
are strong oxidizing agents with E(XeO
3
,Xe) = 2.12 eV.


In basic aqueous solutions, XeO
3
disporportionates providing a preparative path to xenon(VIII) compound: perxenate, XeO
6
4-
.

2 HXeO
4
-
+ 2 OH
-
XeO
6
4-
+ Xe + O
2
+ 2 H
2
O

Several salts have been isolated, e.g., Na
4
XeO
6
, K
4
XeO
6
, Ba
2
XeO
6
. The reaction of perxenate salts with concentration sulfuric
acid yield the second xenon oxide, XeO
4
. Xenon tetroxide is tetrahedral, has a high vapour pressure, and is highly explosive in
the solid state. However, XeO
4
can be kept safely in solutions at low temperature.

In contrast to XeF
4
and XeF
6
, xenon difluoride decomposes more slowly in water producing xenon gas. It is also a
strong oxidizing agent used in inorganic and organic chemistry as a fluorinating agent.





6.2.2.2 Reaction with strong Lewis acids.

129
Xe NMR spectrum at 145C of the (XeF
6
)
4
tetramer
(1.44 M XeF
6
in 50 mol% SO
2
ClF/50 mol% CF
2
Cl
2
)
Chemistry 3830 Lecture Notes Dr. M. Gerken Page

98
Xenon fluorides react with strong Lewis acids, such as AsF
5
and SbF
5
, upon fluoride-ion donation.

XeF
2
+ AsF
5
XeF
+
AsF
6
-
XeF
4
+ SbF
5
XeF
3
+
SbF
6
-
XeF
6
+ SbF
5
XeF
5
+
SbF
6
-
These cations are strongly fluorine bridged in the solid state.


6.2.2.3 Reaction with fluoride.
Xenon tetrafluoride and XeF
6
react with F
-
to form xenon fluoride anions, while XeF
2
does not accept a fluoride ion.
XeF
4
+ F
-
XeF
5
-
XeF
6
+ F
-
XeF
7
-
XeF
6
+ 2F
-
XeF
8
2-
Xenon hexafluoride can accept two F
-
anions forming the XeF
8
2-
anion, which is a regular archimedian antiprism (square
antiprism). The presence of the lone pair in XeF
8
2-
does not have any effect on the geometry. The lone pair is stereochemically
inactive. The eight fluorine ligands about xenon take up a lot of space, forcing the lone pair into the centre of the molecule. We
will encounter other examples for stereochemical inactivity during our discussion of halogen compounds.

6.2.3 Oxides and Oxide Fluorides

We have discussed already the synthetic route to oxides and oxide fluorides. Most of these xenon oxygen compounds are
endothermic compounds, the pure oxides are even explosive. It is interesting to note that xenon in the +8 oxidation state can be
stabilized using oxide ligands instead of fluoride. While XeF
8
is not known, XeO
4
has been prepared. This can be attributed
to the high electronegativity of fluorine, leaving a xenon(VIII) centre more electron-deficient and a more strong oxidizing
centre that can oxidize F
-
to F
2
. In addition, it is unlikely to put 8 fluorine atoms around a small xenon(VIII) centre, while only
four oxide ligands are necessary to stabilize the formal +8 oxidation state of xenon.

6.2.4 Other Xenon Compounds and Organo-xenon compounds.

Besides fluoride and oxide, xenon compounds with other ligands have been prepared. These compounds include (a) oxygen
bonded ligands, such as OTeF
5
, nitrogen-bonded ligands, such as N(SO
2
F)
2
, chloride, and carbon-bonded ligands, such as
C
6
F
5
. The requirement is that the ligands are oxidatively resistant. The more resistant the ligands are, the more likely it is to
form compound with xenon in higher oxidation states.

Frequently, such compounds are prepared via a condensation reaction starting from the fluorides upon HF elimination.
XeF
2
+ HN(SO
2
F)
2
FXeN(SO
2
F)
2
+ HF

The OTeF
5
group is very stable towards oxidation and xenon(IV) and xenon(VI) compounds have been prepared. The
19
F
NMR spectrum shown below of XeF
2
(OTeF
5
)
2
is an excellent example how NMR spectroscopy can be used in the
characterization of inorganic compounds.



Organo xenon compounds have been prepared by xenodeborylation, i.e., the substitution of boron by xenon, using Lewis
acidic boron compounds.
Chemistry 3830 Lecture Notes Dr. M. Gerken Page

99
XeF
2
+ B(C
6
F
5
)
3
[(C
6
F
5
)Xe]
+
[B(C
6
F
5
)
n
F
4-n
]
-
n =1,2
The use of the F
2
B(C
6
F
5
) Lewis acid, produced stable BF
4
-
salts of Xe(II) and even Xe(IV).
XeF
2
+ F
2
B(C
6
F
5
) [(C
6
F
5
)Xe]
+
[BF
4
]
-

XeF
4
+ F
2
B(C
6
F
5
) [(C
6
F
5
)XeF
2
]
+
[BF
4
]
-

The number of organoxenon compounds has grown in the recent past and includes now the neutral Xe(C
6
F
5
)
2
using a trimethyl
silyl reagent. The driving force of these types of reactions is the strong Si-F bond formation. The B-F and Si-F bonds are the
strongest single bonds.
2XeF
2
+ 3Me
3
Si(C
6
F
5
) Xe(C
6
F
5
)
2
+ (C
6
F
5
)XeF + 3Me
3
SiF


6.2.5 Krypton Chemistry

Krypton chemistry is much more limited than xenon chemistry, since Kr cannot be oxidized that easily. Only Kr(II)
compounds have been prepared, with KrF
2
being the starting point of all krypton chemistry. For the synthesis of KrF
2
atomic
fluorine has to be generated at low temperature, since KrF
2
decomposes at room temperature to Kr and F
2
. The generation of
atomic F can be achieved using hot-wire reactors or photochemically, while the reaction mixture is immersed in liquid
nitrogen.

As XeF
2
. KrF
2
can react with strong Lewis acids yielding KrF
+
salts.

6.2.6 Xenon as a Ligand to Gold an Mercury.

The synthesis of compounds with xenon-gold bonds is a story about a surprising outcome of a reaction that was designed to
prepare something completely different.
Since AgF is a stable compound, K. Seppelt in Berlin started out to synthesize the unknown AuF (AuF
3
and AuF
5
are known).
He attempted to reduce AuF
3
with a variety of reducing agents, producing compounds that are interesting in their own right.
Xenon can be considered a very (!) mild reducing agent that may react with the oxidizing agent AuF
3
. Under normal
conditions, no reaction was found. Conducting the reaction in superacidic media (HF/SbF
5
), however, produced the
[AuXe
4
]
2+
[Sb
2
F
11
-
]
2
salt, which was characterized by X-ray crystallography. Superacids are defined as Brnsted acids that are
stronger than sulfuric acid. Superacidic media are very electron poor and in HF/SbF
5
, no better ligand is available than xenon.
The AuXe
4
2+
cation is a square planar cation with gold in the +2 oxidation state and xenon as a ligand (peripheral atom).
The parameters on which the [AuXe
4
]
2+
formation is dependent are xenon pressure and acid strength of the solution. By
varying the reaction conditions several other xenon-gold compounds could be synthesized: trans-AuXe
2
2+
[SbF
6
-
], [Xe-Au-F-
AuXe
3+
][SbF
6
-
]
3
, trans-[AuXe
2
F
2+
][SbF
6
-
][Sb
2
F
11
-
]. The question arises if other metals could act as central metals for xenon
ligands and, so far, only mercury is the only other metal that forms such compounds: [HgXe
2+
][SbF
6
-
][Sb
2
F
11
-
]. Relativistic
effects, which peak for Au and Hg in the periodic table, are likely important for such compounds.