close

Вход

Забыли?

вход по аккаунту

?

Novel Iminosulfur Oxydifluorides.

код для вставкиСкачать
Novel Iminosulfur Oxydifluorides
By Konrod Seppelt and Wolfgang Sundermeyer [ * I
As a rule, silicon-nitrogen bonds are readily attacked and
completely cleaved by non-metallic halides and halogens []I.
However, we have now been able t o prepare compound ( I ) ,
trimethylsilyliminosulfur oxydifluoride, one of the few
exceptional cases in which a n Si-N bond and a n elementhalogen bond are resident a s immediate neighbors in the
same molecule a n d do not interact with each other either
inter- or intramolecularly. (Z) was prepared from tris(trimethy1silyl)amine and sulfur oxytetrafluoride according to
the following equation:
[(CH3)3Sil3N
+ SOF4
F
->
+ 2 (CH3)3SiF
(CH3)jSi -N=S=O
F
(1 )
T h e reaction was carried out in a n autoclave; the starting
materials react above room temperature with moderate
liberation of heat t o give ( I ) in 85 % yield.
Compound ( 1 ) can also be obtained by reaction of sulfur
oxydifluoride with N-halogenobis(trimethylsilyl)amines,
the most favorable synthesis (87 ”/, yield) being that from
N-iodobis(trimethylsilyl)amine [21:
The reaction equation was confirmed by quantitative determination and by identification of by-products.
(Z) is a water-clear liquid and only slightly sensitive to
hydrolysis: m.p. -92 “C, b.p. 85.5 OC. It was purified by
preparative gas chromatography a n d identified by elemental analysis and mass spectrometryr31 [ m / e = 173
(R3SiNSOFz 1.8%), 158 (R2SiNSOFz SO%), 128 (SiNSOF2
2.7:<), 81 (NSOF or RSiFz 90%), and 77 (RZSIF) 100%)
along with other typical fragments; 75 eV]. Both the most
important absorptions in the I R spectrum [gaseous: 1495
(vs, vSO), 1275 (s, vNS), 852 (vs, vas SF), and 819 cm-1
(vs, vs SF)] and the corresponding Raman linesf31 (liquid:
1480, 1275, 853, a n d 810cm-1) as well a s the 19F-NMR
spectrum (6 = -55.9 ppm against CFC13 as internal standard a t 20 “C) give supporting evidence for structure ( I )
rather than for that of the isomeric compound
(CH3)3Si-O-SF2
E N , which was previously considered
the more probable o n the grounds of stability. In a heated
autoclave, compound { l ) starts t o decompose a t 250OC;
a t 4OO0C decomposition t o (CH3)3SiF, SOF2, Nz, SOz,
and S is complete.
Further evidence for the given structure is afforded by the
reaction of ( 1 ) with mercury(rr) fluoride in methylene
chloride; this reaction leads to quantitative formation of
mercury bis(imidosu1fur oxydifluoride) (2).
2 (CH3)3Si-NSOF2
+ HgF2
->
Hg(NSOF2)z
+ 2 (CH3)3SiF
(2)
This reaction parallels the synthesis of Hg(NS0)z [4l.The
colorless crystals of (2) (m.p. 108°C; sublimable in high
vacuum at 130°C) a r e only slightly sensitive t o hydrolysis[sl. In air, (2) starts t o decompose a t 17OOC; the sole
gaseous products formed o n pyrolysis in high vacuum a t
400-600 “C are S02, N S F a n d a little SiF4 (from the glass)
alongside Hg, HgF2, S, a n d SN-polymers. Compound (2)
is very soluble in ether, moderately soluble in methylene
chloride, sparingly soluble in chloroform, a n d insoluble in
petroleum ether. Its identification followed from elemental
analysis and mass spectrometry131 [nt’e = 398-404
(Hg(NSOF& 4.2%), 298-304
(HgNSOFz 6.1 %), and
198-204 (Hg 100%) along with weaker signals; 75eVl.
T h e I R and Raman spectroscopic data [IR, Nujol: 1397
(vs, vasSO), 1362 (s, v,SO), 1231 (s, v,,SN), a n d 1198 cm-1
(s, v,SN); Raman, solid: 1396s, 1365s, 1235 vs, and
1191 cm-1 m], as well as the 19F-NMR spectrumr” (8 ==
Angew. Chetn. internat. Edit. / Vol. 9 (1970)
/ No.
11
-58.7 ppm in methylene chloride, against CFCI3 as external
standard) a r e consistent with the structure given.
T h e imidosulfur oxydifluorides (1) and (2) react with
halogens and halogen compounds in the manner described
by us in a previous communication 161.
Received: July 31, 1970
German version: Angew. Chem.
[ Z 284 IE]
82,931 (1970)
-
[*] Dr. K. Seppelt and Prof. Dr. W. Sundermeyer
Anorganisch-Chemisches Institut der Universitat
69 Heidelberg, Irn Neuenheimer Feld 7 (Germany)
[11 For a summary see: 0.1. Sclrerer, Organometal. Chem.
Rev. A 3, 281 (1968).
[2] Cf. K. Seppelt, Dissertation, Universitat Heidelberg 1970.
[3] Thanks are due to Dr. R . Geist (Heidelberg) for the recording of the mass spectra, to Dr. H . Ejsel (Heidelberg) for
the Raman spectra, and to Doz. Dr. H. P . Latscha (Heidelberg)
and Prof. Dr. E . Fluck (Stuttgart) for the IDF-NMR spectra.
[4] W . Verbeek and W . Sundermeyer, Angew. Chem. 81, 330
(1969); Angew. Chem. internat. Edit. 8, 376 (1969).
151 X-ray structure analysis: M . Ziegler, unpublished.
[6] W . Verheek and W . Siindermeyer, Angew. Chem. 81, 331
(1969); Angew. Chem. internat. Edit. 8, 376 (1969).
Crystal and Molecular Structure of
Zn,O,(CH,),, - a Dimbane[**]
By Manfred L. Ziegler a n d Johannes W e i s s [ * ]
Cuates a n d RidleyrII obtained from the reaction of dimethylzinc and methanol t h e compound Zn404(CH3)8, which,
according to X-ray investigations by Shearer and Spencer [21,
has a cubane structure.
As Eisenhuth a n d van Warer[31 were able t o show, this
methanolysis also leads t o the formation of a product
having the composition Zn708(CH3)14. According to N M R
spectroscopic measurements this latter substance has a dicubane structure.
T h e triclinic unit cell (a = 10.08, b = 8.76, c = 10.61 A; cc =
115.4, /3 = 117.3, y = 92.1 O ; space group Ci-Pi) contains
o n e formula unit Zn708(CH3)14. Since this substance is
extremely sensitive to hydrolysis the crystals used for measurements must be sealed in a Mark tube.
The intensities of 1225 independent reflections obtained
from Weissenberg photographs (“multiple film” method)
about the a-axis were estimated visually a n d corrected in
the usual manner. N o corrections were carried o u t for absorption and extinction.
Since only one formula unit is found in the unit cell for a
two-fold general equivalent position the molecule itself
must be centrosymmetric, one of the zinc atoms being
situated a t the center of symmetry. T h e positions of the
zinc atoms were determined by a three-dimensional Patterson synthesis; Fourier syntheses afforded the positions of
the remaining atoms. Final refinement of the structural
Table
Zn3
Zn4
0’
0 2
03
0 4
C’
C2
CA
Cd
Ci
C‘!
c7
z
Y
X
Znl
Zn’
1. Atomic coordinates.
0
0.2594 (4)
-0.0103 (4)
0.2328 (4)
0.0198 (17)
0.2409 (12)
0.2320 (19)
--0.0032 (18)
-0.0636 (3 1 )
0.3460 (36)
0.3154 (33)
0.1027 (32)
0.4085 (36)
-0.1441 (38)
0.3233 (33)
0
0.3167
(3)
0.1282 (3)
-0.0558 (3)
0.2338
0.0733
0.1838
-0.0972
(15)
(9)
(17)
(16)
0.3535 (26)
0.0440 (32)
0.2777 (28)
-0.2658 (27)
0.5488 (30)
0.1579 (34)
-0.2438 (29)
0
0.1221 (3)
-0.2375 (3)
-0.1274 (3)
-0.0033 (14)
0.1009 (8)
--0.1 I34 (14)
-0.2274 (14)
0.0477 (25)
0.2305 (23)
-0. I562 (27)
-0.3720 (24)
0.3016(31)
-0.4255 ( 2 5 )
-0.2021 (25)
905
Документ
Категория
Без категории
Просмотров
1
Размер файла
141 Кб
Теги
iminosulfur, novem, oxydifluorides
1/--страниц
Пожаловаться на содержимое документа