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Bis( pentafI uoro-h6-sulfanyl)amines* *
By Alfred Waterfeld, Heinz Oberhammer*, and
Rudiger Mews*
F,C(SF,),"] and F5SOSF512,31
are the only compounds
with two geminal pentafluoro-h6-sulfanyl groups to have
been reported in the literature so far. The N-(pentafluoroh6-sulfanyl)iminosulfur tetrafluoride 1 prepared by
now opens u p access to bis(pentafluor0-h6-sulfanyl)amines. Thus, addition of hydrogen fluoride to 1 affords
(SF,)*NH 2 in quantitative yields:
F,SNSF,+ HF + (SF2),NH
The colorless liquid 2, b.p. 60.4"C, is stable at room temperature in glass; at elevated temperature in presence of
alkali-metal fluorides, it loses H F with re-formation of 1 .
2 is a weak acid; with large cations, salts such as
Ph4P'N(SF5)20 3 can be precipitated.
The N-halobis(pentafluoro-h6-sulfanyl)amines5 and 6
are accessible in 91 and 87% yield, respectively, via the cesium salt 4i4]:
Cs@N(SFc)ZO F2
5 and 6,b.p. 51.6 and 78"C, respectively, are stable, colorless liquids at room temperature. Owing to the polarity
of the CI-N bond, 6 is considerably more reactive than
5 ; 6 is rapidly decomposed by halide ions (Cl-, Br-).
Since the two SF5 groups couple with each other, the N M R
spectra of the bis(pentafluor0-h6-suIfanyl)amines are quite
complicated (AA'B4B4 or AA'B4BkX spectra).
The structures of 2 and 5 were determined by electron
[ I ] A. F. Clifford, H. K. El-Shamy, H. J. Emeleus, R. N. Haszeldine, J. Chem.
SOC.1953, 2372; E. A. Tyczkowski, L. A. Bigelow, J. Am. Chem. SOC.75
(1953) 3523; R. D. Dresdner, J. A. Young, ibid. 81 (1959) 574.
[2] H. L. Roberts, J . Chem. SOC.1960, 2774.
[3] H. Oberhammer, K. Seppelt, Angew. Chem. 90 (1978) 66; Angew. Chem.
Int. Ed. Engl. 17(1978) 69; Inorg. Chem. 17(1978) 1435.
141 A. Waterfeld, R. Mews, Angew. Chem. 94 (1982) 389; Angew. Chem. Int.
Ed. Engl. 21 (1982) 354.
[ 5 ] J . Haase, H. Oberhammer, W. Zeil, 0. Glemser, R. Mews, Z . Narur/orsch.
A 26 (1971) 1333.
(Ch1oroacyl)diphenylphosphanes as Sources of
Halogenated Ketenes**
By Ekkehard Lindner*, Michael Steinwand. and
Sigurd Hoehne
Because o f their polar cumulative double-bond system,
chloroketenes are highly reactive compounds, which add to
olefins, and thus are of special preparative interest141.We
have now s~cceeded''~in isolating and characterizing the
pure chloroketones 3a and 3b, hitherto unknown in substance. Thermolysis of the (chloroacy1)diphenylphosphanes 2a and 2b, which were synthesized for the first
time by reaction of (CH3)3SiPPh2with the acyl halides 1 ,
afforded 3a and 3b, which were isolated and characterized
by freezing out at -8O"C, and by I3C-NMR spectroscopic
measurements at - 60 "C.
+ (CH,),SiPPh,
Et,O/- 80°C
The crystalline acylphosphanes 2a-2c, which are readily soluble even in slightly polar solvents, were identified
by elemental analyses and by their I3C-, "P('H]-NMR, IR,
and mass spectra; in the case of 2a, also by an X-ray structure analysis (Fig. 1). 2a-2c are thermally labile and decompose even under mild conditions into CIPPh, and ketene derivative.
2,X=H; 5 , X = F
2 and 5 have planar SzNX frameworks with large SNS angles (134.8f I " and 138.3k 1.0", resp.). The S N distances
increase with increasing electronegativity of the substituents, e. g . 2 < 5 < F,SNF,['l, but in all cases are shorter
than the Schomaker-Stevenson value (1.74 A). The average
SF distances show an opposite trend.
The two latter mentioned findings can be qualitatively
explained by a simple electrostatic model.
Received: December 7, 1981 [Z 78b IE]
German version: Angew. Chem. 94 (1982) 390
The complete manuscript of this communication appears in:
Angew. Chem. Suppl. 1982. 834-845
['I Prof. Dr. R. Mews, Dr. A. Waterfeld
Anorganisches-chemisches lnstitut der Universitat
Tammannstrasse 4, D-3400 Gattingen (Germany)
Prof. Dr. H. Oberhammer
lnstitut fur Physikalische und Theoretische Chemie der Universitat
Auf der Morgenstelle 8, D-7400 Tubingen (Germany)
This work was supported by the Deutsche Forschungsgemeinschaft. We
thank Prof. Dr. G. V. Roschenthaler and Dr. M. Feigl, Universitat Bremen, for the NMR spectra.
Angew. Chem. Inr. Ed. Engl. 21 11982) No. 5
3a could be trapped with cyclohexene as 8-chlorobicyclo[4.2.0]octan-7-one. Various products are formed on decomposition of 2c, depending on the temperature: Between 0 and 40°C, CI3PPh2 is formed; on briefly heating
to 80°C, ClPPh2 can be observed 3'P/'H)-NMR spectroscopically and is found to be further chlorinated to
C13PPh2 after a short while. This would suggest that dichloroketene occurs as intermediate. The signals of the C 1
atoms in the I3C-NMR spectra o f 3a and 3b are shifted
upfield compared to the corresponding signals of ketene
and methylketene["] ["C('HJ-NMR (CDCI3) 3a: 6 = 166.2;
3b : 6 = 168.9); consistent with this finding the C2 atoms in
3a and 3b are less shielded [l3C-NMR (CDC13) 3a:
6 ~ 7 0 . 1(d, ' J o = 1 8 4 . 4 Hz); 3b: 6=85.0 (q, 'JCH=4.5
[*] Prof. Dr. E. Lindner, M. Steinwand, Dr. S. Hoehne
lnstitut fur Anorganische Chemie der Universitat
Auf der Morgenstelle 18, D-7400 Tubingen I (Germany)
This work was supported by the Deutsche Forschungsgemeinschaft and
BASF Aktiengesellschaft.
0 Verlag Chemie GmbH. 6940 Weinheim, 1982
0570-0833/82/0505-0355 $02.50/0
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bis, amines, pentafluoro, sulfanyl
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