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, 2013, 49, 4588--4590 This journal is c The Royal Society of Chemistry 2013
Cite this: Chem. Commun., 2013,
49, 4588
Bartletts discovery of noble gas fluorides, a milestone
in chemical history
Karl O. Christe*
In 1962, Neil Bartlett published a terse note in Proc. Chem. Soc. eradicating the long held dogma that
noble gases are inert and cannot form stable compounds. This historical discovery has revolutionized
our views on chemistry and has given rise to thousands of papers on noble gas chemistry. The fact that
his proposed reaction product Xe
+
[PtF
6
]
experimentally is presented.
Attempts to prepare compounds of the noble gases date back
all the way to the 19th century.
1
Although Walther Kossel
2
in
1916 and Linus Pauling
3
in 1932 had correctly predicted that
krypton and xenon fluorides could exist, very notable experi-
mentalists including William Ramsay, Henri Moissan,
1
Andreas von Antropo,
4
Otto Ru and Walter Menzel,
5
Don
Yost and Albert Kaye
6
had failed to isolate noble gas com-
pounds. This led to the conclusion that noble gases were
indeed inert, and this statement could be found in essentially
all the chemistry textbooks prior to 1962.
Neil Bartlett did not set out to prepare noble gas com-
pounds. In 1962, while pursuing the synthesis of PtF
2
by
reduction of PtF
4
, Bartlett carried out experiments to purify
his PtF
4
starting material which was contaminated by BrF
3
. He
heated it in a stream of diluted fluorine in a Pyrex apparatus to
convert the BrF
3
to the more volatile BrF
5
. In these experiments,
he consistently obtained a red sublimate which he originally
thought
7
to be OPtF
4
but subsequently identified as O
2
+
[PtF
6
]
.
8
While this was an accidental discovery,
9
the recognition of the
significance of this result and its broader implications was a
stroke of genius, worthy of a Nobel Prize but which was never
awarded.
10,11
Bartlett reasoned that PtF
6
had to be an extraordi-
narily strong oxidizer because of its ability to oxidize O
2
to
O
2
+
[PtF
6
]
.
9
Does this
flaw in the interpretation of the original product diminish the
significance of Bartletts breakthrough discovery? The answer is
a clear-cut NO. Bartlett combined logical reasoning and
creative thinking while seeing problems in a broad context.
This enabled him to overcome existing dogmas and to shatter
them. It opened a whole new field of exciting chemistry.
Fig. 1 The historical Bartlett experiment, the oxidation of Xe by PtF
6
(reproduced
with permission from ref. 9).
Loker Research Institute and Department of Chemistry, University of
Southern California, Los Angeles, CA 90089, USA. E-mail: kchriste@usc.edu;
Tel: +1 213 740 3552
Received 22nd February 2013,
Accepted 25th March 2013
DOI: 10.1039/c3cc41387j
www.rsc.org/chemcomm
ChemComm
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This journal is c The Royal Society of Chemistry 2013 Chem. Commun., 2013, 49, 4588--4590 4589
The elusiveness of Xe
+
[PtF
6
]
anion of C
s
symmetry (Fig. 2). This anion can spontaneously lose an F atom
under formation of PtF
6
.
In classical transition metal heptafluoro anions, the nega-
tive charge is distributed relatively evenly over all the F atoms in
the cluster, resulting in structures of D
5h
, C
2v
, C
3v
symmetry
having similar energies. By contrast, in non-classical PtF
7
the
unpaired electron is localized on the external F atom which also
carries much less negative charge than the remaining fluoride
ligands. The non-classical structure is best described as an F
atom weakly complexed to PtF
6
catalyzed
system (F
forming Pt
2
F
11
. In this
manner, the only observed product is XeF
+
Pt
2
F
11
, while
Xe
+
PtF
6
anion serves
as a catalyst to lower the activation energy barrier for the
formation of a fluorine radical and its transfer to xenon. The
proposed mechanism can be summarized by the following
equations.
PtF
6
F
! PtF
7
PtF
7
Xe ! XeF
PtF
6
XeF
PtF
6
! XeF
PtF
6
PtF
6
! PtF
5
F
XeF
PtF
6
PtF
5
! XeF
Pt
2
F
11
Xe 2PtF
6
! XeF
Pt
2
F
11
(reproduced
with permission from ref. 14).
Fig. 3 Coordination of the metal center (M = Zn and Cu) in [M(XeF
2
)
6
](SbF
6
)
2
(reproduced with permission from ref. 24).
Fig. 4 Structure of the square planar [AuXe
4
]
2+
cation in tetragonal AuXe
4
-
(Sb
2
F
11
)
2
(reproduced with permission from ref. 29c).
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4590 Chem. Commun., 2013, 49, 4588--4590 This journal is c The Royal Society of Chemistry 2013
The first metalXeF2 adduct, Ag(XeF
2
)
2
(AsF
6
),
23
was discovered
in 1991 by Bartletts group. In this compound, Ag has a
coordination number of 8 with 4 fluorine atoms originating
from XeF
2
and four from AsF
6