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Isomeric Chlorides and Fluorides of Sulfenic Acids.

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rgi
I
IR-absorption bands (cm-1) [bl
~
F-CO-SCI
-33.24
461740
-97
F-CO-NCS
-16.05
(-70OC)
-43.45
-23.46
63.5
-73
-
-27
-86
F-CO-S-SCN
F-CO-S-NCO
74
~~
~
1857 (s) vC=O; 1055 (s)
751 (m)
; 570 (m)
1844 (s) vC=O; 1050 (s) vCF; 747 (m) vC-C f 6C-F; 564 (m) vS-CI
740 (m)
558 (m)
1044 (s)
1966 (VS) vasNCS; 1848 (VS)vC=O; 1237 (s) VSNCS;1028 (VS)vC-F;
762 (m) vC-S
6C-F
1018 (vs)
2160 (m) vaSSCN; 1820 (vs) vC=O; 1035 (vs) vC-F; 739 (s) vC-S
6C-F
2245 (s) vasNCO; 1840 (s) vC=O; 1365 (w)VSNCO;1080 (s) vC-F;
1820 (s)
1058 (s)
753 (m)
vC-S
SC-F
740 (m)
3250 (ms) vNH; 1805 (s) v C ~ - 0 1505
;
(ms) SN-H; 1059 (s) vC-F;
1665 (s)
741 (m) vC-S
FC-F; 650 (vbr) yNH (not flat)
2250 (s) vNCO; 1800 (vs) v C 0 ; 830 (vs) vC-CI
1490 (s) 6NH; 831 (s) vC-CI; 655 (mbr)
3230 (s) vNH; 1780 (s)
yNH (not flat)
1770 (s) vC0;
1665 (s)
3225 (s) vNH; 1730 (s)
1491 (s) S N H ; 1450(m) SCH30;
1647 (s)
1429 (ms) 6asCH3
1203 (s)
674 (m) yNH (not flat)
1191 (s) v C - 0 ;
+
+
+
-
-
125 (decamp.)
-
CI-CO-S-NCO
(CI-CO-S-NH)>CO
-
110/748
-
135 (decamp.)
-
-
[a] Referred t o CC!.TFas internal standard. [bl br
194
=
+
broad, m = medium, s = strong, vs = very strong, w = weak.
COS and (SCN),, together with small amounts of phosgene
and S2Clz are found after reaction of (I) with AgSCN. We
assume that both chlorine atoms in (I) react with AgSCN.
Reaction of( Ijwithsilvercyaoide is exp1osive;CI-CO-S-CN
could not be isolated. Reaction of (2) with AgCN is also very
violent but, when less than 5 g of (2) is used, S(CN)2, COS,
COF2, and F-CO-NCS
are o b t a i n d . We postulate the
following reactions:
(2)
+ AgCN
--D
F-CO-S-CN
80-90%
S(CN)2 t
cos
i
110-20x
CaFZ
F-CO-NCS
The Table lists the physical properties of the new compounds.
is reproduced by the
The vapor pressure of F-CO-SCl
following equation:
log p
=
7.316-1426JT
Thence b.p. 48.5 "C/760 mm can be calculated, in agreement
with the experimental value. The heat of vaporization of this
compound is calculated to be 6521 kcal mole-1. The Trouton
constant is 20.3 cal degree-1 mole-1.
Received May 12th and June Sth, 1967
[Z 540a IE]
German version: Angew. Chem. 79, 687 (1967)
During hydrothermal synthesis of tellurium crystals in concentrated hydriodic acid (21, we observed the occurrence of
needle-shaped crystals with a metallic sheen. Their structure
did not agree with that of any of the compounds described for
the tellurium-iodine system 131. Analysis showed a tellurium:
iodine ratio greater than one.
Larger amounts of the crystals are formed regularly when
tellurium-iodine mixtures containing less than 40 wt- % of
iodine are heated with concentrated hydriodic acid in a
temperature gradient. Reaction occurs in sealed quartz ampoules; the temperature must be below 210 OC. Crystals obtained under various conditions contain between 35 and 48 %
of iodine, which indicates a considerable phase width. The
crystals are insoluble in non-oxidizing acids, in alkali hydroxide solutions, and in organic solvents, but dissolve in hot
concentrated sulfuric or nitric acid.
Single-crystal studies show a monoclinic structure with a =
,l5.44 A, b = 4.17 A, and c = 12.05 A, f3 = 128.1 '. Dcalc =
$.55'g/cm3; Dabs. = 5.57 g/cm3.
It has so far not been possible to obtain this phase by solidStafe reactions of tellurium with iodine, which indicates
stro:tlg kinetic hindrance. However, crystals of this phase have
also been observed on forced sublimation with very pure
argon as carrier gas[Jl.
[Z 541 IEI
Received: May 16th and June 9th, 1967
German version: Angew. Chem. 79. 688 (1967)
[*] Priv.-Doz. Dr. A. Rabenau, Dr. H. Rau, and
['I Doz. Dr. A. Haas and Dip1.-Chem. H. Reinke
Anorganisch-Chemisches Institut der Universitat
Hospitalstr. 8-9
34 Gottingen (Germany)
[I] French Pat. 1372911, California Research Corp.; Chem.
Abstr. 62, 1363 (1965); German Pat. 1224720, Farbenfabriken
Bayer.
A Halogen-deficient Phase in the System
Tellurium-Iodine
By A . Rabenau, H. Rau, and P. Eckerlin[*l
Dr. p. Eckerlin
philips Zentrallaboratorium GmbH
Weisshausstr.
51 Aach en (Germany)
[I] A . F. w e l l s : Structural Inorganic Chemistry. Clarendon
Press, Oxford 1962, P. 426ff.
[2] H . Rau a n d A. Rabenau, Solid State Commun. 5, 331 (1967).
[3] w. R . Bldckmore, S . C. Abrahams, and J. Kalnajs, Acta
crystallogr. 9, 9 2 5 (1956).
[4] H . Rau and A . Rabenau, Material Res. Bull. 2, 609 (1967).
Isomeric Cbloridm and Fluorides of Sulfenic Acids
Dedicated to Professor F. Asinger on his 60th Birthday
The halides of sulfur, selenium, and tellurium constitute an
interesting group of compounds because of their structural
and bonding relations [I]. Their systematics are, however,
not yet fixmly founded. Only monohalides and compounds
of high halogen content have been described.
706
B y F. Seel, W. Gombler, and R. Budenz[*]
We have proved t h a t substitution of chlorine bonded to
carbon in perchlor0 methane sulfenyl chloride, CC13ScI ( I ) ,
and in the chloroflu~romethane sulfenyl chlorides, CFC12SCI
(2), and CF2C]SC1 (3) by fluorine proceeds via previously
Angew.
c&m. internat. Edit. 1 Vol. 6 (1967)
No. 8
unknown sulfenyl fluorides. The intermediate products are
sufficiently stable to permit a study of their N M R and IR
spectra at -5OOC (as liquids) and at room temperature (as
0
The fluorination of ( I ) ,
gases at low pressure ( ~ 1 mm)).
(2), and ( 3 ) has been effected in the gas phase at 15OoC with
active potassium fluoriderll. The 19F-NMR spectra of the
condensed products thus obtained exhibit the unusually high
positive shifts characteristic of sulfenyl fluorides 121, as well
as the multiplet structure expected for the CF-SF and
F2-SF groupings (Table 1). It is evident from the IR
spectra that the carbon atoms of the C-SF, CF-SF, and
CF2-SF groupings are converted by chlorine into perhalomethyl groups. IR spectra of the sulfenyl fluorides show a
band of type C in a constant position at 790 cm-1 which is
assigned to S-F stretching.
At room temperature, rapid rearrangement of the liquid
sulfenyl fluorides, CF,CI,-,SF
to the isomeric sulfenyl
chlorides, CF,+ 1C12_,SCl ( n = 0,1,2) takes place.
Finally, our experiments demonstrate a decrease in the rate
of substitution of chlorine by fluorine at the sulfur atom
as the number of fluorine atoms on the carbon atom increases.
We were also able to prepare the concluding member of the
series, trifluoromethanesulfenyl fluoride.
Table 1. Chemical shifts (6 ppm.) and coupling constants ( J Hz) for the
IQF-NMR spectra of perhalomethane sulfenyl halides (based on CFCl3
as external reference).
6 0%)
8 (Fc)
C13C-SF
FC12C-SCl
FC12C- SF
F2CIC-SCI
F*CIC--SF
F3C-SCI
F,C-SF
(F3C)zCF-SF I21
-
249
-
265
(doublet)
4.85
-
27.9
31
(doublet)
37.5
45
(doublet)
51
58
(doublet)
73.9
158.9
(multiplets)
-
297
(triplet)
-
351
(quartet)
361
(multiplet)
-
6.85
-
27
22
10
IZ 542a IEI
German version: Angew. Chem. 79, 686 (1967)
[*I Prof.
F. Seel, W. Gombler, and R. Budenz
Insitut fur Anorganische Chemie der Universitat
66 Saarbrucken 1 5 (Germany)
[l] Obtained by the decomposition of potassium fluorosulfite.
F. Seel and D. Golitz, 2. anorg. allg. Chem. 327, 28 (1964).
[2] Cf. R . M. Rosenberg and E. L . Muetterties, Inorg. Chem. I ,
756 (1962).
Anomalous Course of the Neutralization of
Periodic Acid by Sodium Hydroxide
H:IOs+ O H Q =
H4106@+
HzO
Angew. Chent. internat. Edit.
Vol. 6 (1967) / No. 8
20
10
rnl NaOH
Fig. I . Dilatometric titration of 100 ml of 0.1
1 N NaOH.
30
M
H ~ 1 0 6with
Ordinate: Position of meniscus (cm)
is superposed by a change in coordination and thus by a dehydration that also occurs with dilatation:
The considerable volume contraction between the first and
the second equivalence points can then be explained by resolvation, which occurs with a further change in coordination:
H20
+ 1040+ OH@= H3IO:O
[**I
The slow further rise in the titration curve after the second
equivalence point indicates further, incomplete neutralization of a weak acid. There are no other inflections.
That iodine can occur with various coordination numbers
(4, 5, and 6) in periodates is proved by preparation of neutral
anhydrous salts and by evaluation of their I R spectrarzl.
Further, the central iodine atom does not retain its original
coordination number during dissociation of periodic acid
H5IO6 in aqueous solution; Crouthamel et al.131, by pH
measurements and spectrophotometric studies, and Siebert 141,
by measurement of Raman spectra, have demonstrated the
decomposition of H4IO60 and the presence of the anion
I 0 4 0 ; Kustin and Lieberman[5l have studied the kinetics of
the decomposition H4106@= IO40 2 H 2 0 in detail by the
temperature-jump method and have found that on addition
of alkali the anion 104O is converted into the anion H3IO6Z0
with addition of water. In agreement with these findings,
crystalline salts are known that contain this anion, e.g.
Na~H3106,whereas salts of the type M1H4106 have not
hitherto been prepared.
+
In favorable circumstances the dilatometric indicator method
thus makes it possible to observe addition or loss of water
directly in aqueous solutions.
Received: June 16th, 1967
[Z 544 1El
German version: Angew. Chern. 79, 690 (1967)
By K . F. Jahr and E. Gegner[*l
Recently we showed that the volume-contraction or -dilatation of a solution that occurs during a titration can be measured directly and used for indication of the end point. In
neutralization of acids that proceeds normally one always
observes a dilatation that has the same value for almost all
strong acids. However, o n neutralisation of free periodic
acid HsIO6, we observed an anomalous course: a very strong
dilatation up to the first equivalence point (consumption of
1 OHQ) is followed by a strong contraction up to the second
equivalence point (consumption of 2 OH@)(see Fig. 1).
We interpret the shape of this titration curve as due to the
peculiarity of I(vII), which can adopt various coordination
numbers towards oxygen, and we assume that the neutralization to the first equivalence point:
I
I
[*I
Prof. Dr. K. F. Jahr and Dr. E. Gegner
Institut fur Anorganische Chemie der Freien Universitat
Fabeckstr. 34/36
1 Berlin 3 3 (Germany)
[**I In a paper published while this communication was at the
press, H. Siebert (Fortschr. chem. Forsch. 8, 478 (1967)) formulates, instead of H3IO;O, the binuclear ion H2120:?, whose
formation from 107, however, also involve; addition of water.
[ll E. Cegner, Dissertation, Freie Universitat Berlin, 1966; K . F.
Jahr, E. Gegner, G. Wiese, and J. Fuchs, Angew. Chem. 78, 304
(1966); Angew. Chem. internat. Edit. 5, 310 (1966).
[2] H . Siebert, 2. anorg. allg. Chem. 303, 162 (1960).
[3] C. E. Crouthamel, A . M . Hayes, and D . S. Martin, J. Amer.
chem. SOC.73, 82 (1951).
[4] H . Siebert, Z. anorg. allg. Chem. 273, 21 (1953).
[ 5 ] K . Kustin and E. C. Lieberman, J. physic. Chem. 68, 3869
(1964).
707
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