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The noble gases
462
Coordination Chemistry Reviews, 34 (1981)462-466 Elsevier8cientificPublishingCompany, Amsterdam-PrintedinThe Netherlands
Chapter THE
NOBLE
8 CASES
M.F.A.Dove
8.1
THE
ELEMENTS
8.2
XENON(I1)
............................................
463
8.3
XENON(V1)
............................................
464
REFERENCES
The
investigated
are
in
atoms of
are
lowest found
formed
when noble
cavities
gas
are
of
Hawkins, noble
published the
deals passage the or
and
in years
chemistry
with of
noble Xe,
Falconer gases
of
the an
the
of
a.c. and
et
the
64 bar by
complexes
conditions
host
(rotational
xenon
electric
have
compounds
5
compounds.
cf
the
were
be
the
grown
half
of
in the
to
helium
the
plane
novel are the
presence
4.721 diameter
concentration related
of
radon
reservoir
3 compiled
has A
a bibliography
all
review XeF
throilgh
have
some by
aspects
mixtures MF,
commenced
6
Fudrews
in matrixes.
binary
of
papers
paper
monofluorides
Howorka8
the
reviewed
transient
discharge
SF produces 76 Kuen and yield.
cooling
CdPt(CN)6.1.128Xe
covering
Seppelt
1962-1976.
from the
The
conditions.
Bartlett4
their
away
been
molecules
the
that
: only
can
the
axis
and
atoms.
sources
have
shown
compound
pressure
operating and
C 6 symmetry 2 al. have 1.046Kr
guest
spectroscopy
gases
in high
in
geothermal and
Waals
in which over 95% of 1 In both complexes level.
CdPt(CN)6.
at
der
under
Weiss
occupied
characteristics
of
lie
crystals
a variety
the
to ring.
van
expansion)
rovibronic
compounds
of
the
He2 -benzene
supersonic
benzene
inclusion
in
and
spectroscopically
by the
the
466
ELEMENTS
He-benzene
achieved
462
.................................................
THE
8.1
.........................................
M = Ar, an
The of Kr
463
investigation studied ratios and
of
were varying
ArI+
of
of
rare
Kr(Ar)+CF4, 19:l
observed from
mechanisms
properties
between
were
conditions,
8.2
the
Kr(Ar)+C12,
which
and
1:lO.
but
under
the
authors
gas
halide
Kr+SF S, The
widely
and
ions. AH12
ions
KrCl+,
differing
have
The
with
systems'
mixture ArCl+
KrF+,
reaction
inferred
the
likely
formation.
XENON(I1)
A
large
number
spectroscopy Of
all
of
of
'*'X8 .
xenon(I1)
together,
but
strength
of
F-Xe-O-
and
Xenon(IV) Xe(I1)
xenon
compounds
The
compounds
a small
the
group groups
compounds
compounds
quadrupole with
the
was
Q.S.
from
lie
the
For
of Q.S.
acceptor
compounds was
of
(Q-S.)
close
with
established.
in magnitude that
Mijssbauer
strengths
with
similar
distinct
by
groups
observed_
a Q.S.
quite
studied'
F-Xe-F
a reduction
exhibit
but
of
been
interaction
linear
increase
adduct
-0-Xe-O-
have
to
that
of
xenon(V1)
derivatives. The with The
collision XeF2
ion
than
of
currents
that
electron
molecules
for
due
F-.
to
standard
heat
of
the
reaction
with
solid
well
with
with
PF3.
that,
Bancroft Ge(s)
of
et
+
gas
shake-up
M,O.
diagram
* In the
spectrum, for
using
molecule
XeF2.
this
has in
-163.2
the
Xe
ground
they
from
have
The
F2-
and
lo*
times
were
been
3d
peaks
the
"shared"
is promoted
to
energy with
an
of
the
valence
excited
from
for
4d
the
by
reaction
shake-up*
spectra
. ..(l)
Xe
and
spectra, a Xe
have
XeF2, and
3d hole
been
photoelectron
electrons
state.
- 10 _
smaller
*Xc(g)
U-V.
constructed
shake-up
XeF
detected.
determined"
and
M.O.‘s
the
also
20eV
and
a calorimetric bomb, -1 , agrees 5 1.3kJ mol
+
state
XeF2
0 to
F-,
obtained
GeFq(g)
and
range of
the
and
Xe
state
satisfactorily
diagram.
process is
XeF2
mol-',
-
lo3
XeF3-
metal
reported
energy
are
and
obtained,
have
Xe
XeF-
of
it 0.9kJ
Using for
a shake-up
electron
12
XeF2.
levels
assigned
value
the
production
XeF2-
germanium
-162.8
al.
and
of
in
the
formation
2XeF2(s)
gaseous
Rydberg
The
(1).
in
F2-
Traces
The
equation
beams
results
leaving a valence
464 A volatile, container
waxy,
white
solid with
of approximately
3Omin.
a half-life
in a Kel-F
has been obtained by the reaction of XeF2 with gaseous CF3 radicals. 13 The product is believed to be Xe(CF3)2 and has been characterised by F analysis and by i-r. and 19 F n.m.r. spectra of partially decomposed
samples.
first
reported
Kel-F
at 20°C
Xe (CF3)
basis
according
+
reduction
involved
They
dichloromethane
reactions
investigated Cr3+
.
to the
of aryl bromides XeF2
in the presence
yields
of these
-7oOc.
Chemical reactions
8.3
as
and
intermediate solutions 15
is
reactions.
of norbornene
2-endo-5-exoknown
by XeF2
in
and 2-exo-5-exo-
anti-
and syn-
and colleagues l7 have an
oxidant for the determination of 18 have reported the fluorination
BrF2-derivatives
of BF3.Et20
with
on the
The use of ether as solvent yields the are then isomerised to the other pair
et al.
for their
arenes
by the action
or HF in CH2C12
intermediates
evidence
data
in aqueous
of the well
related
reactive
coupling
of XeF2
Lempert
Nesmeyanov
in
one-
solution
the active
of competitive
the use of XeF2 2+
andMn
literature
that
the novel
instead 16 2,7-difluoronorbornanes. 2,7-difluoro isomers, which by BF3.Et20.
place
the successive
in aqueous
fluorination
difluoronorbornanes
of isomers
calculated
of XeF2
of a study
produces
the
takes
(2).
thermodynamic
The BF3. Et20-initiated
compound,
to xenon,
. ..(2)
have proposed
in oxidation
on the basis
of the novel
CnFm
potentials
of the available
temperature
d bonded
and coworkers 14 have
correlations. XeO,
carbon
to equation
XeF2
Goncharov electron
Decomposition
to contain
___t
2
at room
was
formation
to give
The
or SO2.
claimed
to be
was provided
diarylbromonium
of at
by the
salts.
XENON(V1)
Mijssbauer studies in this oxidation
of
129
Xe in xenon(V1)
state-the
quadrupole
compounds
interaction
have
shown
strengths
that
(Q.S.)
are appreciably different from those of the two lower oxidation states. 9 In XeF6 the Q.S. is. indicative of appreciable distortion from octahedral the adducts fluoride according
: even
coordination
and for compounds
reacts
very
to equation
slowly (3).lg
with
with
larger mixed
values
were
found
0 and F lignads.
B(OTeF5)3
(molar ratio
The new xenon(V1)
1:2)
derivative,
for
Xenon(V1)
465
-4o*c XeF6
+
2B(OTeF5)3
-b
2BF3
+
Xe(OTeF516
. ..(3)
"'=sF12
Xe (OTeF5) thermal even
at -23O*C,
reaction was
precipitates
6I
decomposition
shown
reaction
produces
of the compound between
OXeF4
and N2H4,
has been
presented
kinetic
which
(daylight)
and F5TeOOTeF5. reported; was
solid: decomposition,
A slow hydrolysis
the hydrolysis
also prepared
from
product the
and B(OTeF5j3.
investigated
or radical,
is apparently perchloric
also
as an oxidant data
photosensitive
or photolytic
Xe(OTeF5)4
was
to be 0Xe(OTeF5)4,
The use of Xe03
molecule
as a red-violet,
at -1OOC
in inorganic by Lempert
for the decomposition
which
responsible acid. 20
is a product
analysis, et al.: 17 of Xe03.
for Fe they
2+
also
A short-lived
of the H 0 -Xe03 reaction, . for the oxidation of Np252 to Np6+ in
466
REFERENCES
4
10 11 12 13 14 15 16 17 18 19 20
S-M-Beck, M.G.Liverman, D.L.Monts, and R.E.Smalley. J_ Chem. PhYS., 70(1979)232. M.KPmper, M-Wagner, and A-Weiss, Angew. Chem. Int. Ed. Engl., 18(1979)486. P-Kruger, G-Warren, and B.D.Honeyman, Proc. Int. Conf. Nucl. Metho-ds Environ. Energy Res., 3rd.(1977)225 (Chem. Abs., 92(1979)8810). D.J.Hawkins, W.E.Falconer, and N-Bartlett, "Noble Gas Compounds", Bibliography 1962-1976, (1978) I.F.I. Plenum Data Corp., New York. K.Seppelt, Act. Chem. Res., 12(1979)211. L.Andrews, Ber. Bunsenges. Phys. Chem., 82(1978)65. A.K.Shuaibov and V.S.Shevera, Zh. Tekh. Fiz., 49(1979)1747. I.Kuen and F.Howorka, J. Chem. Phys., 70(1979)595. H. de Waard, S.Bukshpan, G.J.Schrobilgen, J.E.EIolloway, and D-Martin, J. Chem. Phys., 70(1979)3247. G.M.Begun and R.N.Compton, Int. J. Mass Spectrom. Ion Phys., 30(1979)379. V. Ya. Leonidov, I.V.Timofeev, and Yu. M.Kiselev, Dokl. Akad. Nauk. SSSR, 248(1979)1375. J.S.Tse, D.J.Bristow, G.M.Bancroft, and G.Schrobilgen, Inorg. Chem., 18(1979)1766. L.J.Turbini, R.E.Aikman, and R.J.Lagow. J. Am. Chem. Sot., 131(1979)5833. A.A.Goacharov, Yu. N. Kozlov, and A.P.Purmal', Russ. J. Phys. Chem., 53(1979)1541. A.A.Goncharov, Yu. N.Kozlov, and A.P.Purmal', Russ. J. Phys. Chem., 53(1979)1648. S.A.Shackleford, Report 1978, FJSRL-TR-78-0008, (Chem. Abs., 91(1979)9965). .S.A.Lempert, D.B.Lempert, N.N.Aleinikov, and P.K.Agasyan, Zh. Obshch. Khim., 49(1979)2172. A.N.Nesmeyanov, I.N.Lisichkina, A.S.Kulikov, A.N.Vanchikov. T.P.Tolstaya, and V.A.Chertkov, Doklady Chem., 243(1979)618. D.Lentz and K.Seppelt, _Angew. Chem. Int. Ed. Engl., 18(1979)66. V.P.Shilov, Radiokhim., 21(1979)449.
Coordination Chemistry Reviews, 34 (1981)462-466 Elsevier8cientificPublishingCompany, Amsterdam-PrintedinThe Netherlands
Chapter THE
NOBLE
8 CASES
M.F.A.Dove
8.1
THE
ELEMENTS
8.2
XENON(I1)
............................................
463
8.3
XENON(V1)
............................................
464
REFERENCES
The
investigated
are
in
atoms of
are
lowest found
formed
when noble
cavities
gas
are
of
Hawkins, noble
published the
deals passage the or
and
in years
chemistry
with of
noble Xe,
Falconer gases
of
the an
the
of
a.c. and
et
the
64 bar by
complexes
conditions
host
(rotational
xenon
electric
have
compounds
5
compounds.
cf
the
were
be
the
grown
half
of
in the
to
helium
the
plane
novel are the
presence
4.721 diameter
concentration related
of
radon
reservoir
3 compiled
has A
a bibliography
all
review XeF
throilgh
have
some by
aspects
mixtures MF,
commenced
6
Fudrews
in matrixes.
binary
of
papers
paper
monofluorides
Howorka8
the
reviewed
transient
discharge
SF produces 76 Kuen and yield.
cooling
CdPt(CN)6.1.128Xe
covering
Seppelt
1962-1976.
from the
The
conditions.
Bartlett4
their
away
been
molecules
the
that
: only
can
the
axis
and
atoms.
sources
have
shown
compound
pressure
operating and
C 6 symmetry 2 al. have 1.046Kr
guest
spectroscopy
gases
in high
in
geothermal and
Waals
in which over 95% of 1 In both complexes level.
CdPt(CN)6.
at
der
under
Weiss
occupied
characteristics
of
lie
crystals
a variety
the
to ring.
van
expansion)
rovibronic
compounds
of
the
He2 -benzene
supersonic
benzene
inclusion
in
and
spectroscopically
by the
the
466
ELEMENTS
He-benzene
achieved
462
.................................................
THE
8.1
.........................................
M = Ar, an
The of Kr
463
investigation studied ratios and
of
were varying
ArI+
of
of
rare
Kr(Ar)+CF4, 19:l
observed from
mechanisms
properties
between
were
conditions,
8.2
the
Kr(Ar)+C12,
which
and
1:lO.
but
under
the
authors
gas
halide
Kr+SF S, The
widely
and
ions. AH12
ions
KrCl+,
differing
have
The
with
systems'
mixture ArCl+
KrF+,
reaction
inferred
the
likely
formation.
XENON(I1)
A
large
number
spectroscopy Of
all
of
of
'*'X8 .
xenon(I1)
together,
but
strength
of
F-Xe-O-
and
Xenon(IV) Xe(I1)
xenon
compounds
The
compounds
a small
the
group groups
compounds
compounds
quadrupole with
the
was
Q.S.
from
lie
the
For
of Q.S.
acceptor
compounds was
of
(Q-S.)
close
with
established.
in magnitude that
Mijssbauer
strengths
with
similar
distinct
by
groups
observed_
a Q.S.
quite
studied'
F-Xe-F
a reduction
exhibit
but
of
been
interaction
linear
increase
adduct
-0-Xe-O-
have
to
that
of
xenon(V1)
derivatives. The with The
collision XeF2
ion
than
of
currents
that
electron
molecules
for
due
F-.
to
standard
heat
of
the
reaction
with
solid
well
with
with
PF3.
that,
Bancroft Ge(s)
of
et
+
gas
shake-up
M,O.
diagram
* In the
spectrum, for
using
molecule
XeF2.
this
has in
-163.2
the
Xe
ground
they
from
have
The
F2-
and
lo*
times
were
been
3d
peaks
the
"shared"
is promoted
to
energy with
an
of
the
valence
excited
from
for
4d
the
by
reaction
shake-up*
spectra
. ..(l)
Xe
and
spectra, a Xe
have
XeF2, and
3d hole
been
photoelectron
electrons
state.
- 10 _
smaller
*Xc(g)
U-V.
constructed
shake-up
XeF
detected.
determined"
and
M.O.‘s
the
also
20eV
and
a calorimetric bomb, -1 , agrees 5 1.3kJ mol
+
state
XeF2
0 to
F-,
obtained
GeFq(g)
and
range of
the
and
Xe
state
satisfactorily
diagram.
process is
XeF2
mol-',
-
lo3
XeF3-
metal
reported
energy
are
and
obtained,
have
Xe
XeF-
of
it 0.9kJ
Using for
a shake-up
electron
12
XeF2.
levels
assigned
value
the
production
XeF2-
germanium
-162.8
al.
and
of
in
the
formation
2XeF2(s)
gaseous
Rydberg
The
(1).
in
F2-
Traces
The
equation
beams
results
leaving a valence
464 A volatile, container
waxy,
white
solid with
of approximately
3Omin.
a half-life
in a Kel-F
has been obtained by the reaction of XeF2 with gaseous CF3 radicals. 13 The product is believed to be Xe(CF3)2 and has been characterised by F analysis and by i-r. and 19 F n.m.r. spectra of partially decomposed
samples.
first
reported
Kel-F
at 20°C
Xe (CF3)
basis
according
+
reduction
involved
They
dichloromethane
reactions
investigated Cr3+
.
to the
of aryl bromides XeF2
in the presence
yields
of these
-7oOc.
Chemical reactions
8.3
as
and
intermediate solutions 15
is
reactions.
of norbornene
2-endo-5-exoknown
by XeF2
in
and 2-exo-5-exo-
anti-
and syn-
and colleagues l7 have an
oxidant for the determination of 18 have reported the fluorination
BrF2-derivatives
of BF3.Et20
with
on the
The use of ether as solvent yields the are then isomerised to the other pair
et al.
for their
arenes
by the action
or HF in CH2C12
intermediates
evidence
data
in aqueous
of the well
related
reactive
coupling
of XeF2
Lempert
Nesmeyanov
in
one-
solution
the active
of competitive
the use of XeF2 2+
andMn
literature
that
the novel
instead 16 2,7-difluoronorbornanes. 2,7-difluoro isomers, which by BF3.Et20.
place
the successive
in aqueous
fluorination
difluoronorbornanes
of isomers
calculated
of XeF2
of a study
produces
the
takes
(2).
thermodynamic
The BF3. Et20-initiated
compound,
to xenon,
. ..(2)
have proposed
in oxidation
on the basis
of the novel
CnFm
potentials
of the available
temperature
d bonded
and coworkers 14 have
correlations. XeO,
carbon
to equation
XeF2
Goncharov electron
Decomposition
to contain
___t
2
at room
was
formation
to give
The
or SO2.
claimed
to be
was provided
diarylbromonium
of at
by the
salts.
XENON(V1)
Mijssbauer studies in this oxidation
of
129
Xe in xenon(V1)
state-the
quadrupole
compounds
interaction
have
shown
strengths
that
(Q.S.)
are appreciably different from those of the two lower oxidation states. 9 In XeF6 the Q.S. is. indicative of appreciable distortion from octahedral the adducts fluoride according
: even
coordination
and for compounds
reacts
very
to equation
slowly (3).lg
with
with
larger mixed
values
were
found
0 and F lignads.
B(OTeF5)3
(molar ratio
The new xenon(V1)
1:2)
derivative,
for
Xenon(V1)
465
-4o*c XeF6
+
2B(OTeF5)3
-b
2BF3
+
Xe(OTeF516
. ..(3)
"'=sF12
Xe (OTeF5) thermal even
at -23O*C,
reaction was
precipitates
6I
decomposition
shown
reaction
produces
of the compound between
OXeF4
and N2H4,
has been
presented
kinetic
which
(daylight)
and F5TeOOTeF5. reported; was
solid: decomposition,
A slow hydrolysis
the hydrolysis
also prepared
from
product the
and B(OTeF5j3.
investigated
or radical,
is apparently perchloric
also
as an oxidant data
photosensitive
or photolytic
Xe(OTeF5)4
was
to be 0Xe(OTeF5)4,
The use of Xe03
molecule
as a red-violet,
at -1OOC
in inorganic by Lempert
for the decomposition
which
responsible acid. 20
is a product
analysis, et al.: 17 of Xe03.
for Fe they
2+
also
A short-lived
of the H 0 -Xe03 reaction, . for the oxidation of Np252 to Np6+ in
466
REFERENCES
4
10 11 12 13 14 15 16 17 18 19 20
S-M-Beck, M.G.Liverman, D.L.Monts, and R.E.Smalley. J_ Chem. PhYS., 70(1979)232. M.KPmper, M-Wagner, and A-Weiss, Angew. Chem. Int. Ed. Engl., 18(1979)486. P-Kruger, G-Warren, and B.D.Honeyman, Proc. Int. Conf. Nucl. Metho-ds Environ. Energy Res., 3rd.(1977)225 (Chem. Abs., 92(1979)8810). D.J.Hawkins, W.E.Falconer, and N-Bartlett, "Noble Gas Compounds", Bibliography 1962-1976, (1978) I.F.I. Plenum Data Corp., New York. K.Seppelt, Act. Chem. Res., 12(1979)211. L.Andrews, Ber. Bunsenges. Phys. Chem., 82(1978)65. A.K.Shuaibov and V.S.Shevera, Zh. Tekh. Fiz., 49(1979)1747. I.Kuen and F.Howorka, J. Chem. Phys., 70(1979)595. H. de Waard, S.Bukshpan, G.J.Schrobilgen, J.E.EIolloway, and D-Martin, J. Chem. Phys., 70(1979)3247. G.M.Begun and R.N.Compton, Int. J. Mass Spectrom. Ion Phys., 30(1979)379. V. Ya. Leonidov, I.V.Timofeev, and Yu. M.Kiselev, Dokl. Akad. Nauk. SSSR, 248(1979)1375. J.S.Tse, D.J.Bristow, G.M.Bancroft, and G.Schrobilgen, Inorg. Chem., 18(1979)1766. L.J.Turbini, R.E.Aikman, and R.J.Lagow. J. Am. Chem. Sot., 131(1979)5833. A.A.Goacharov, Yu. N. Kozlov, and A.P.Purmal', Russ. J. Phys. Chem., 53(1979)1541. A.A.Goncharov, Yu. N.Kozlov, and A.P.Purmal', Russ. J. Phys. Chem., 53(1979)1648. S.A.Shackleford, Report 1978, FJSRL-TR-78-0008, (Chem. Abs., 91(1979)9965). .S.A.Lempert, D.B.Lempert, N.N.Aleinikov, and P.K.Agasyan, Zh. Obshch. Khim., 49(1979)2172. A.N.Nesmeyanov, I.N.Lisichkina, A.S.Kulikov, A.N.Vanchikov. T.P.Tolstaya, and V.A.Chertkov, Doklady Chem., 243(1979)618. D.Lentz and K.Seppelt, _Angew. Chem. Int. Ed. Engl., 18(1979)66. V.P.Shilov, Radiokhim., 21(1979)449.