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New Method of Preparing Iminosulfur Oxydifluorides.

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tron-attracting action still more powerful than that of the
already powerful acceptor PF,.
This remarkable property can be ascribed at least in part
to the weaker donor character of AsF, than of PF, ligands.
The ionization potentials measured by us amount to
11.7 eV for PF, and 12.8 eV for AsF, ;the lone pair involved
in the ionization thus lies at a lower energy level in the case
of AsF,.
The fluorine atoms in ( I ) can be very readily exchanged
in nucleophilic reactions, even at room temperature,
without simultaneous attack on the Mn-As bond. If a
benzene solution of ( I ) is treated with ethanol at 20°C, a
very rapid reaction affords
C,H,Mn(CO),AsF,OC,H,
together with a small amount of
This is due, not only to the relatively great stability of
OSF,, but also to the facts that the relevant amines in part
do not react and in part do not exist, the latter particularly
in those cases where two or more NH, groups should be
attached to one atom. As a result, compounds containing
more than one NS(O)F, group attached to one atom are
accessible only by special reactions and indeed are known
only in three cases, namely, F,C(NSOF,),, OC(NSOF,)212J,
and mercury bis(iminosu1fur oxydifluoride), Hg(NSOF,),
(1)[31.
Synthesis of the last-mentioned compound and its reactions
with polar halides have now provided a method of introducing the NSOF, group, by means of which a large number
of new iminosulfur oxydifluorides can be prepared. For
instance, phosphorus trichloride reacts with ( I ) in methylene chloride to give phosphorus tris(iminosu1fur oxydifluoride) (2).
C,H,Mn(CO),AsF(OC,H,),
3 Hg(NSOF2)Z
The PF, complex is inert under these conditions.
+
2 PC1,
-+
2 P(NSOF2)s
[l] T h . Kruck, Angew. Chem. 79, 27 (1967); Angew. Chem. internat.
Edit. 6, 53 (1967).
[2] E. W Abel, M . A . Bennet, and G . W k i n s o n , J. Chern. SOC.1959,
2323.
[3] R . Bouquet and M. Bigorgne, Bull. SOC.Chim. Fr. 1962,433.
[4] R. J . Angelici and W Loewen, Inorg. Chem. 6 , 682 (1962).
[ 5 ] J . M u l k r , K . Fender!, and B. Mertschenk, Chem. Ber. 104, 700
(1971).
[6] F . A . Cotton and C. S. Kraihnnzel, J. Amer. Chem. SOC.84, 4432
(1962).
New Method of Preparing Iminosulfur
Oxydifluorides
By WoEfgang Sundermeyer, Achim Roiand, and
Konrad Seppelt "1
It is not always possible to prepare a desired iminosulfur
oxydifluoride by the method most used hitherto''], namely,
reaction of an NH, group with sulfur oxide tetrafluoride.
3 HgClz
(2)
(
Received. March 26,1971 [ Z 405 IE]
German version: Angew. Chern. 83,445 (1971)
+
Similarly, arsenic
tris(iminosu1fur
oxydifluoride),
As(NSOF,), (3), is obtained from arsenic trichloride, and
silicon tetrachloride can be converted into silicon tetrakis(iminosulfur oxydifluoride) ( 4 ) , which is to date the most
highly substituted compound of this type.
It is evident that alkyl- and aryl-substituted inorganic
halides can be subjected to this reaction. For example, all
the members of the series (CH,),Si(NSOF,),_, have been
prepared [ ( 4 a ) to ( 4 c ) ] , and it could thus be shown that
compounds with more than two NSOF, groups are also
stable, although the Si-N bond itself usually reacts with
S-F compounds.
The most interesting example so far of an iminosulfur
oxydifluoride of a Group 6 B element is thionyl bis(iminosulfur oxydifluoride) ( 5 ) which is formed by the reaction
of ( I ) with thionyl chloride. Analysis and the mass spec-
Table 1. Properties of some iminosulfur oxydifluorides.
__
,
I Yield
Compound
M. p.
("C)
B. p.
I9F-NMK
("C/torr) ( P P ~[a1
)
IR spectra (cm- ') [c]
vS0
I vSN I v,,SF
/v,SF
Other bands
~
-21.5
48.5112
-51.7 D
PI
1415 s, br
1238 s
509,453,360
- 3
38/0.4
- 54.9
s
15-14OO s
1215 s
- 39
61/13
-48.4
s
1481-66 s
1308 s
- 65
47/12
-49.6 S
1460 s. br
1295 s
505,430, 320
550,485,460
R,Si(NSOF,)
(4c)
OS(NSOF,),
(5)
85
50
- 86
24/10
- 92
85.5/160 -55.9s
56/30
-51.7 D
__
-50.6s
1455s, br
1495s,br
1415 s
791 YCH,. 772.
705, 550, >20,
461
1289s 880s 832s 2915 v,,CH,
2940 v,CH,
801 yCH, 710,
552,520,455
1275s 852s 819s (cf.[31)
1166s 865s 845 m 690, 650, 560,
515,450
[a] 2 4 ° C CFCI, as external standard. S=singlet, D=doublet.
[b] 5,_,=4.5 Hz; 31P-NMR: 6 = -84.5 ppm, H,PO, as external standard.
[c] ( 2 ) and (3) as film, all others as gases. Provisional assignments.
Angew. Chem. internat. Edit. J Vol. 10 (1971) / No. 6
419
trum lead to the conclusion that this is a homogeneous
substance, but spectroscopic findings, in particular the
19F-NMR spectrum, indicate the presence of isomers.
resembling pseudohalides although the corresponding
anions have not yet been isolated-but we have obtained
all the N-haloiminosulfur oxydifluorides XNSOF, (X = F,
Clt6I,Br, and I"'). If this view is accepted, compound ( 5)
is the first stable thionyl pseudohalide (cf. ['I).
Received : March 25, 1971 [Z 404 IE]
German version: Angew. Chem. 83,443 (1971)
Experimental:
The imide (I) (15g) is suspended in methylene chloride
(ca. 50 ml ; partially dissolved ; 5 g/lOO ml), treated with
the appropriate inorganic halide [slight excess of (I); if
necessary, diluted with CH,CI,), and heated under reflux
for 5-10h. The products are obtained analytically pure
by fractional distillation in a vacuum.
All the products are water-clear liquids of unexpectedly
high stability and low sensitivity to hydrolysis. Boiling
points are similar to those of the corresponding bromides
(differences ca. 7 "C per NSOF, group). Physical data of
the products, whose structures are proved by elemental
analysis and by mass spectra, are shown in Table
+
As we have also shown in previous experiments[3.' I , the
OSN, F,SN, and F,S(O)N groups can be regarded as
p] Prof. Dr. W. Sundermeyer, Dip1.-Chem. A. Roland, and
Dr. K. Seppelt
Anorganisch-chemisches Institut der Universitat
69 Heidelberg, Im Neuenheimer Feld 7 (Germany)
[l] R . Cramer and D.D. Cofman, J. Org. Chem. 26,4010 (1961).
[2j 0. Glemser and S. P . u. Halasz, 2. Naturiorsch. 236, 743 (1968);
Inorg. Nucl. Chem. Lett. 5, 321 (1969).
[3j K . Seppelt and W Sundermeyer, Angew. Chem. 82, 931 (1970);
Angew. Chem. internat. Edit. 9,905 (1970).
141 We thank Prof. E. Fluck and Dr. G. Heckmann of the Technische
Universitat Stutlgart for measurement and discussion of the NMR
spectra, and Dr. R. Geist for measurement of the mass spectra.
[S] W Verbeek and W Sundermeyer, Angew. Chem. 81, 331 (1969);
Angew. Chem. internat. Edit. 8,376 (1969).
[6] J . K . Ruff;Inorg. Chem. 5,1787 (1966).
[7] K . Seppelt and W Sundermeyer, 2. Naturforsch. 266, 65 (1971).
[S] P. W Schenk and H.Eloching, Chem. Ber. 92,2333 (1959).
CONFERENCE REPORTS
Porous Plastic Foils as Functional Models of
Excitable Nerve Membranes
By U.F. Franck and S. Searty"]
Membranes are among the most important functional
building units of living organisms, where they undertake
physicochemical processes that are essential for life. Such
processes are, above all:
polystyrene, etc.). The kinetic behavior of such membranes,
which contain traces of fixed ions in their pores, is analogous to that of excitable nerve membranes, and all the
fundamental electrophysiological properties such as excitability, accommodation, action potential, and rhythmic
behavior can be demonstrated with these materials.
Lecture at Aachen (Germany) on January 22,1971 [VB 280 IE]
German version: Angew. Chem. 83,410 (1971)
a) separation of materials;
b) energy transfer ;
c) transfer and processing of information.
In spite of the variety of these processes they can be referred
in principle to two elementary properties of membranes,
namely :
Mechanism of the Radiolysis of Cyclohexane
By Horst Herler[']
Coupling mechanisms of this kind are observed also with
non-living membranes, e. g., with porous plastic foils (PVC,
Cyclohexane is very useful in studying reactions that are
initiated by ionizing radiation since it contains only one
kind each of C--C and C-H bonds. The three main products-hydrogen, cyclohexene (C,H, ),, and bicyclohexane
(C,,H,,)-are
formed by rupture of C-H bonds. Absorption of ionizing radiation leads to excited and ionized
cyclohexane molecules and to electrons. Experimental
results and theoretical considerations both indicate that
most of these electrons are thermalized whilst still in the
Coulomb field of their parent ion. A few electrons, however,
have sufficient energy to escape from the parent ion, the
number of these amounting to ca. 0.10 electron per 100 eV.
The lifetime of ions and electrons up to their recombina-
[*I
[*] DipLChem. H. Herber
a) selectivity with respect to permeability ;
b) capability to couple in all the processes that can occur
in the neighborhood of the membrane.
Selectivity leads to effects such as electric potentials, mechanical pressure etc. On the other hand, coupling mechanisms enable membranes to exhibit excitability, rhythmic behavior, and propagation phenomena.
Such phenomena play an important part in rapid transfer
of information in nerves, muscles, and sensorial organs.
Prof. Dr. U. F. Franck and Dr. S. Searty
Institut fur Physikalische Chemie der Technischen Hochschule
51 Aachen, Templergraben 59 (Germany)
420
Institut fur Radiochemie der Technischen Universitat Miinchen
8046 Garching (Germany)
Angew. Chem. internat. Edit. Val. 10 (1971) / No. 6
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