The sal
t [F
5SN(H)Xe][AsF
6] has been syn
thesized by
the reac
tion of [F
5SNH
3][AsF
6] wi
th XeF
2 in anhydrous HF (aHF) and BrF
5 solven
ts and by solvolysis of [F
3S
![](h<font color=)
ttp://
pubs.acs.org/images/en
ti
ties/
tbd1.gif">NXeF][AsF
6] in aHF. Bo
th F
5SN(H)Xe
+ and F
5SNH
3+ have been charac
terized by
129Xe,
19F, and
1H NMR s
pec
trosco
py in aHF (−20 °C) and BrF
5 (su
percooled
to −70 °C). The yellow [F
5SN(H)Xe][AsF
6] sal
t was crys
tallized from aHF a
t −20 °C and charac
terized by Raman s
pec
trosco
py a
t −45 °C and by single-crys
tal X-ray diffrac
tion a
t −173 °C. The Xe−N bond leng
th (2.069(4)
xc5;) of
the F
5SN(H)Xe
+ ca
tion is among
the shor
tes
t Xe−N bonds
presen
tly known. The ca
tion in
terac
ts wi
th
the AsF
6− anion by means of a Xe---F−As bridge in which
the Xe---F dis
tance (2.634(3)
xc5;) is significan
tly less
than
the sum of
the Xe and F van der Waals radii (3.63
xc5;) and
the AsF
6− anion is significan
tly dis
tor
ted from
Oh symme
try. The
19F and
129Xe NMR s
pec
tra es
tablished
tha
t the [F
5SN(H)Xe][AsF
6] ion
pair is dissocia
ted in aHF and BrF
5 solven
ts. The F
5SN(H)Xe
+ ca
tion decom
poses by HF solvolysis
to F
5SNH
3+ and XeF
2, followed by solvolysis of F
5SNH
3+ to SF
6 and NH
4+. A minor decom
posi
tion channel leads
to small quan
ti
ties of F
5SNF
2. The colorless sal
t, [F
5SNH
3][AsF
6], was syn
thesized by
the HF solvolysis of F
3S
![](h<font color=)
ttp://
pubs.acs.org/images/en
ti
ties/
tbd1.gif">NAsF
5 and was crys
tallized from aHF a
t −35 °C. The sal
t was charac
terized by Raman s
pec
trosco
py a
t −160 °C, and i
ts uni
t cell
parame
ters were de
termined by low-
tem
pera
ture X-ray diffrac
tion. Elec
tronic s
truc
ture calcula
tions using MP2 and DFT me
thods were used
to calcula
te
the gas-
phase geome
tries, charges, bond orders, and valencies as well as
the vibra
tional frequencies of F
5SNH
3+ and F
5SN(H)Xe
+ and
to aid in
the assignmen
t of
their ex
perimen
tal vibra
tional frequencies. In addi
tion
to F
5TeN(H)Xe
+,
the F
5SN(H)Xe
+ ca
tion
provides
the only o
ther exam
ple of xenon bonded
to an s
p3-hybridized ni
trogen cen
ter
tha
t has been syn
thesized and s
truc
turally charac
terized. These ca
tions re
presen
t the s
tronges
t Xe−N bonds
tha
t are
presen
tly known.