Page 346 - Academic Press Encyclopedia of Physical Science and Technology 3rd InOrganic Chemistry

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Encyclopedia of Physical Science and Technology EN010K-480 July 16, 2001 17:22

456 Noble-Gas Chemistry

−
◦
AsF , which is stable at room temperature (dec 89 C). The pseudo-octahedral and highly electronegative
6
−
The crystal structure of orange HOTeF 4 OXe AsF , OIOF 4 group exists as a mixture of cis and trans iso-
+
6
obtained from HF solvent, has been shown to be mers and forms derivatives with xenon in its +2 and
˚
−
HF·HO TeF 4 OXe AsF [Xe O, 1.962(9) A]. +4 oxidation states. The interaction of IO 2 F 3 dimer
+
6
◦
◦
The OTeF 5 derivatives of xenon in its +4 and +6 and XeF 2 in SO 2 ClF (−5 C) and CFCl 3 (24 C) sol-
oxidation states are well characterized. The derivative vents produces the xenon(II) compounds Xe(OIOF 4 ) 2 and
Xe(OTeF 5 ) 4 is the only example known where xenon in FXeOIOF 4 . The compound FXeOIOF 4 is also prepared
the +4 oxidation state is coordinated exclusively to oxy- by the stoichiometric reaction of XeF 2 with Xe(OIOF 4 ) 2 .
Both compounds are isomeric mixtures in which the
gens. The compound is prepared by reaction of XeF 4
with B(OTeF 5 ) 3 . It is a dark yellow solid which decom- oxygen bonds in the pseudo-octahedrally coordinated
poses at 72 C to give Xe(OTeF 5 ) 2 and F 5 TeO OTeF 5 . OIOF 4 ligands are cis or trans to one another, i.e.,
◦
The X-ray crystal structure of Xe(OTeF 5 ) 4 reveals square cis,cis-Xe(OIOF 4 ) 2 , cis,trans-Xe(OIOF 4 ) 2 , trans,trans-
planar coordination at xenon and an average Xe O Xe(OIOF 4 ) 2 , cis-FXeOIOF 4 , and trans-FXeOIOF 4 . The
˚
bond length of 2.032(5) A. The mixed ligand deriva- mixture of cis- and trans-FXeOIOF 4 is a pale yellow liq-
tives FXe(OTeF 5 ) 3 , cis- and trans-F 2 Xe(OTeF 5 ) 2 , and uid which is stable for periods exceeding1hat room
F 3 XeOTeF 5 have been observed in CFCl 3 solution and temperature (mp −5to0 C). Pure cis,cis-Xe(OIOF 4 ) 2 ,
◦
prepared by the reaction of Xe(OTeF 5 ) 2 and HOIOF 4 at
result from the ligand redistribution upon mixing XeF 4
◦
and Xe(OTeF 5 ) 4 . The mixed ligand cations FXe(OTeF 5 ) , 0 C in CFCl 3 solvent or neat, is a yellow solid which de-
+
2
+
F 2 XeOTeF , and Xe(OTeF 5 ) + are formed by the re- composes rapidly at room temperature. Combination of
5 3
◦
action of Xe(OTeF 5 ) 4 with SbF 5 solvent at 5 C. The Xe(OTeF 5 ) 2 and cis,cis-Xe(OIOF 4 ) 2 results in the forma-
reddish-violet solid Xe(OTeF 5 ) 6 is prepared by reac- tion of the mixed ligand species cis-F 4 OIOXeOTeF 5 and
◦
◦
tion of XeF 6 and B(OTeF 5 ) 3 at −40 C in perfluoro- trans-F 4 OIOXeOTeF 5 in CFCl 3 solvent at 5 and 24 C.
◦
n-pentane solvent. An incomplete X-ray analysis of Solvolysis of FXeOIOF 4 in SO 2 ClF solvent at −5 C re-
sults in the formation of cis-FO 2 SOXeOIOF 4 and trans-
Xe(OTeF 5 ) 6 suggests that, unlike XeF 6 , solid Xe(OTeF 5 ) 6
is monomeric and isostructural with Te(OTeF 5 ) 6 , with FO 2 SOXeOIOF 4 . The xenon(IV) derivative, F 3 XeOIOF 4 ,
possible C 3v or D 3d local point group symmetry around has been prepared by reaction of XeF 4 and IO 2 F 3 in CFCl 3
◦
xenon. The colorless compound O Xe(OTeF 5 ) 4 (mp solution at 24 C.
◦
◦
56 C) is prepared by hydrolysis of Xe(OTeF 5 ) 6 or by The fluorosulfate derivatives FXeOSO 2 F (mp 36.6 C)
◦
reaction of O XeF 4 with B(OTeF 5 ) 3 . Slow decom- and Xe(OSO 2 F) 2 (mp 43–45 C) are colorless and light
position (over several months) at room temperature yellow solids, respectively, at room temperature. The ther-
produces F 5 TeOTeF 5 and O 2 Xe(OTeF 5 ) 2 . The mixed mal decomposition of Xe(OSO 2 F) 2 provides a method for
ligand derivatives O XeF(OTeF 5 ) 3 ,O XeF 2 (OTeF 5 ) 2 , the preparation of very pure S 2 O 6 F 2 , which is formed
and O XeF 3 (OTeF 5 ) are formed by reaction of in quantitative yield with the liberation of xenon gas.
O Xe(OTeF 5 ) 4 and O XeF 4 in CFCl 3 or XeOF 4 sol- The crystal structure of FXeOSO 2 F has been determined
˚
˚
+
+
vents. The cations O Xe(OTeF 5 ) ,O XeF(OTeF 5 ) , [Xe O, 2.155(8) A; Xe F, 1.940(8) A]. The solids
3 2
and O XeF 2 (OTeF 5 ) + are formed upon dissolution FXeOSO 2 CF 3 and FXeOSO 2 CH 3 are yellow and sta-
◦
of O Xe(OTeF 5 ) 4 in SbF 5 solution at 5 C. Color- ble at 0 C, but decompose explosively when warmed
◦
+
less O 2 Xe(OTeF 5 ) 2 may be prepared by reaction of to room temperature. The complex salt Xe 2 F AsF −
3 6
O 2 XeF 2 with B(OTeF 5 ) 3 or from slow decomposition of reacts with HSO 3 FinHForinHSO 3 F solvent to
O Xe(OTeF 5 ) 4 at room temperature. The X-ray crys- form the (FXeO) 2 SOF + cation as the pale yellow salt
−
+
+
tal structure of O 2 Xe(OTeF 5 ) 2 reveals a local geom- (FXeO) 2 SOF AsF . Alternatively, (FXeO) 2 SOF AsF −
6
6
etry at xenon which may be described as a pseudo- has been prepared by the reaction of XeF 2 with HSO 3 F
trigonal bipyramid or a distorted tetrahedron. The av- and AsF 5 in HF solvent. The (FXeO) 2 SOF + cation is
˚
+
erage Xe O double bond lengths are 1.729(5) A, and V-shaped, similar to Xe 2 F , with the fluorosulfate group
3
˚
the Xe O single bond lengths are 2.022(4) A. The in the bridging position. The XeOSO 2 F cation has been
+
mixed ligand compound O 2 XeF(OTeF 5 ) is formed in observed as the product resulting from the solvolysis
+
−
SO 2 ClF solution by reaction of excess O 2 XeF 2 and of XeOTeF AsF in HSO 3 F solution. The compounds
5
6
+
B(OTeF 5 ) 3 . The O 2 XeOTeF cation is formed by decom- FXeOPOF 2 and Xe(OPOF 2 ) 2 are both orange solids and
5
+
position of the O XeF(OTeF 5 ) cation in SbF 5 solvent are formed in the reaction of XeF 2 with one and two equiv-
2
◦
◦
at 5 C. Decomposition of the O 2 XeOTeF + cation also alents of P 2 O 3 F 4 , respectively, at −22 C in CFCl 3 solvent.
5
◦
◦
occurs in SbF 5 solution at 5 C, forming oxygen and the Both compounds rapidly decompose at 22 C. The per-
XeOTeF cation. chlorate derivatives FXeOClO 3 [colorless solid, mp (dec),
+
5