COMMUNICATIONS
constant, can be shown by changing to acidic solvents.
Compounds 3, 6, and 4, also differ significantly in terms of
the 13C NMR shift values of C(1) as well as in terms of the
2
1JC,Xe and JC(1),F coupling. The 129Xe shift values reveal a
systematic change in the shielding from 4 to 6 to 3 in accord
with the increasing interaction with the nucleophile.
Experimental Section
Pentafluorophenylxenon(ii) chloride 3: Compound 4 (223 mg, 0.46 mmol)
was suspended at 788C in CH2Cl2 (1 mL) and treated under vigorous
stirring with 5 (69 mg, 0.46 mmol). After 3 h the suspension was centrifuged
at 788C, the mother liquor was decanted and the colorless residue was
washed with CH2Cl2 (1 mL). Both CH2Cl2 phases were combined, CCl3F
(3 mL) was added, and the mixture was stored for 12 h at 788C. This led
to the precipitation of a small amount of the originally dissolved coproduct
[4-C5H4NH][AsF6]. The mother liquor was decanted and evaporated to
dryness at 60 to 508C and 0.1 hPa. Compound 3 (130 mg, 0.39 mmol)
was isolated in 85% yield. M.p. 368C (decomp). NMR: see Table 1.
Figure 1. Structure of 6 ´ CH2Cl2 in the crystal. Selected distances [] and
angles [8]: Xe(1) Cl(1) 2.847(2), Xe(1) C(1) 2.111(9), Xe(2) Cl(1)
2.784(2), Xe(2) C(7) 2.116(9); C(1)-Xe(1)-Cl(1) 176.0(3), C(7)-Xe(2)-
Cl(1) 178.8(2), Xe(1)-Cl(1)-Xe(2) 116.96(8); selected intermolecular dis-
tances []: Xe(1) F(13) 3.372(7), Xe(2) F(15) 3.158(7).
occurs with a longer Xe Cl distance and vice versa. The two
Xe Cl distances are 2.847(2) and 2.784(2) , respectively, and
are significantly shorter than the values reported for isoelec-
tronic iodine ± chlorine distances, for example, the 1:1 donor±
acceptor complex from p-C6F4I2 and [NMe4]Cl (3.153 and
3.134 )[10] and the intermolecular I Cl distances in a-ICl
(3.00 )[11] and b-ICl (2.939 ).[12] The Xe-Cl-Xe angle in 6 ´
CH2Cl2 of 116.96(8)8 is larger than that of the corresponding
I-Cl-I angle in the above-mentioned complex (77.28).[10] Weak
Xe F contacts occur between the [AsF6] ion and Xe(1) and
Xe(2) in 6, with the most significant (3.158(7) ) being 9%
shorter than the sum of the van der Waals radii (Xe F)
according to Bondi[13] (3.47 ).
m-Chlorobis[pentafluorophenylxenon(ii)]hexafluoroarsenate 6: Compound
4 (216 mg, 0.44 mmol) was suspended at 408C in CH2Cl2 (5 mL) and
treated with Me3SiCl (144 mg, 1.33 mmol). The suspension was stirred for
4.5 h at 40 to 308C. The mother liquor turned yellow and the originally
pale yellow solid became colorless. The suspension was centrifuged at
788C, the mother liquor was decanted, and the colorless solid was washed
with cold CH2Cl2 ( 788C, 3 Â 2 mL) and then dried at 408C and 0.1 hPa.
Yield of 6: 166 mg (0.20 mmol, 91%). M.p. 1008C (decomp). NMR: see
Table 1; Raman (glass capillary): nÄ 1418 (22.6), 1286 (11.1), 1085 (20.6),
784 (63.5), 490 (58.4), 278 (12.8), 197 (100) (nas(Xe C)), 181 (82.4)
(ns(Xe C)), 128 cm 1 (13.5).
Received: March 26, 1999 [Z13217IE]
German version: Angew. Chem. 1999, 111, 2751 ± 2753
The multinuclear NMR data of 3 and 6 are given in Table 1.
The comparison of the 19F NMR spectroscopic data of the F
atoms bonded to the arene in 3, 6, and 4 shows the effect of
nucleophiles of varying strength (Cl , ClXeC6F5, and MeCN)
on the C6F5Xe fragment. The stronger the nucleophile
interacts with XeII, the weaker is the polarizing effect that is
exerted from the Xe center onto the fluoroaromatic moiety.
As the nucleophile ± electrophile interaction becomes stron-
ger, the 3JF,Xe coupling constant increases. The influence of the
solvent, both on the chemical shifts and on the 3JF,Xe coupling
Keywords: hypervalent compounds ´ xenon
[1] B. Zemva in Encyclopedia of Inorganic Chemistry, Vol. 5 (Ed.: R. B.
King), Wiley, New York, 1994, p. 2660.
[2] a) L. Y. Nelson, G. C. Pimentel, Inorg. Chem. 1967, 6, 1758; b) I. R.
Beattie, A. German, H. E. Blayden, S. B. Brumbach, J. Chem. Soc.
Dalton Trans. 1975, 1659.
[3] a) D. Boal, G. A. S. Ozin, Spectrosc. Lett. 1971, 4, 43; b) K. A. R.
Mitchell, J. Chem. Soc. A 1969, 1637.
[4] G. J. Perlow, M. R. Perlow, J. Chem. Phys. 1968, 48, 955.
Table 1. 129Xe, 19F, and 13C NMR data of 3, 6, and 4.[a]
3
129Xe
3
6
4
CD2Cl2/ 608C
CD3CN/ 408C
CD3CN/ 408C*
4116.5 (t, JXe,F 95, t1/2 58 Hz)
3937.6 (s, t1/2 196 Hz)
3807.8 (t, 3JXe,F 69 Hz)
[b] 3
19F
3
3
3
6
CD2Cl2/ 608C
EtCN/MeCN(3/1)/ 608C*
SO2/ 708C*
130.84 (m,
131.03 (m,
129.84 (m,
128.57 (m,
J
J
J
J
94.2 Hz, o-F), 146.21 (tt, JF,F 21.0, JF,F 3.1 Hz, p-F), 155.49 (m, m-F)
3
4
F,Xe
F,Xe
F,Xe
F,Xe
[b] 3
[b] 3
[b] 3
3
4
94.1 Hz, o-F), 147.51 (tt, JF,F 20.3, JF,F 3.5 Hz, p-F), 156.97 (m, m-F)
3 4
86.4 Hz, o-F), 146.21 (t, JF,F 18.5, JF,F 3.1 Hz, p-F), 155.70 (m, m-F)
3
4
CD3CN/ 408C
81.4 Hz, o-F), 144.28 (tt, JF,F 20.2, JF,F 3.8 Hz, p-F), 155.50 (m, m-F),
1
64.27 (1:1:1:1-q, JF,As 927.0 Hz, [AsF6] )
[b] 3
3
4
4
CD3CN/ 408C*
125.45 (m,
J
67.8 Hz, o-F), 141.83 (tt, JF,Xe 20.2, JF,F 5.4 Hz, p-F), 154.69 (m, m-F),
F,Xe
1
64.29 (1:1:1:1-q, JF,As 929.7 Hz, [AsF6] )
[b] 1
2
1
13C
3
6
4
CD2Cl2/ 608C
CD3CN/ 408C
CD3CN/ 408C*
101.57 (t,
J
208.1, JC,F 29.1 Hz, C(1)), 137.62 (dm, JC,F 260.7 Hz, C(3,5)),
C,Xe
1
1
2
3
142.62 (dm, JC,F 250.3 Hz, C(2,6)), 143.26 (dtt, JC,F 259.6, JC,F 13.4, JC,F 4.6 Hz, C(4))
[b] 1
2
1
92.91 (t,
J
194.6, JC,F 27.2 Hz, C(1)), 138.49 (dm, JC,F 256.4 Hz, C(3,5)),
C,Xe
1
1 2 3
143.68 (dm, JC,F 253.0 Hz, C(2,6)), 144.84 (dtt, JC,F 254.2, JC,F 13.5, JC,F 3.1 Hz, C(4))
[b] 1
2
1
82.16 (t,
J
117.4, JC,F 25.6 Hz, C(1)), 137.79 (dm, JC,F 258.3 Hz, C(3,5)),
C,Xe
1
1 2 3
143.37 (dm, JC,F 257.2 Hz, C(2,6)), 144.82 (dtt, JC,F 260.7, JC,F 13.2, JC,F 4.1 Hz, C(4))
[a] Measured with a Bruker-AVANCE-DRX-500 instrument, the measurements marked with an asterisk were recorded with a Bruker-WP-80-SY
instrument; d(Xe) relative to XeOF4, 248C, d(F) relative to CCl3F with C6F6 as internal standard and d(C) relative to TMS with the respective solvent as
internal standard. In parentheses after the d values, information on the signal multiplicity, the coupling constant J [Hz], and the signal assignment. [b] With
129Xe satellites.
Angew. Chem. Int. Ed. 1999, 38, No. 17
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