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Fluorosulfinylimidosulfur Oxide Difluoride.

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bicyclopropyl (Alas= 2.3-2.5 eV) is of approximately the same
magnitude as the interaction of the orbitals of the double
bonds in butadiene (A1 =2.45 eV), while the substituent effects
in the 1,l '-disubstituted sterically fixed bicyclopropyl derivatives considerably reduce this interaction.
It follows from the energies ofthe Walsh orbitals of unsubstituted bicyclopropyl and 1,l '-dimethylbicyclopropyl calculated
as functions of the dihedral angle 4 by the MIND0/2
method['' (i) that in unsubstituted bicyclopropyl the splitting
Alas= I (a&)- I(oJ should be somewhat larger for the cis-conformation than for the trans-conformation, (ii) that for dihedral
angles between 0 and 80", in keeping with the angular dependence of the resonance integral b, the splitting is given by
the relation
Alas = AI:s cos 6
Received: January 9, 1976;
revised: February 19, 1976 [Z 424 IE]
German version: Angew. Chem. 88, 343 (1976)
CAS Registry number:
Bicyclopropyl, 5685-46-1
and (iii) that in the cis-conformation alkyl substitution, as
in the butadiene system, effects both a general destabilization
of all orbitals and a reduction of Alas by about 0.4eV.
pis reduced by a total amount of about 0.45 eV by the inductive
effect of the substituents and by a lengthening of the central
CC bond. As in the case of substituted butadienes['"I, a perturbational treatment of the substituent effect accordingly fails
to give consistent
It is striking that in contrast to butadiene the interaction
energies H R S = <c:ppO determining the orbital splitting are
different for the cis- and trans-forms of bicyclopropyl:
H R ~ ( c ~ s )-1.25eV
and HRS(trans)= - 1.16eV (for comparison: H R S = - 1.23eV for butadiene).
Photoelectron Spectra of Organic Compounds, Part 10.-Part 9: P.
Asmus and M . Klessinger, Justus Liebigs Ann. Chem. 1975, 2169.
A. de Meijere, W Liirrke, and F . Heinrich, Justus Liebigs Ann. Chem.
1974, 306; and references cited therein.
E. Heilbronner, R . Gleirer, 7: Hoshi, and A. d e Meijere. Helv. Chim.
Acta 56, 1594 (1973).
P. Asmus and M . Klessinger, Tetrahedron 30, 2477 (1974).
0. Bastiansen and A. d e Meijere, Angew. Chem. 78, 142 (1966); Angew.
Chem. Int. Ed. Engl. 5, 125 (1966); K . Hagen, G . Haqen, and M . Traerteberg, Acta Chem. Scand. 26, 3649 (1972).
We are grateful t o Prof. A. de Meijere, Gottingen, for a sample of,
and discussions about, bicyclopropyl.
M. J . S . Dewar and E. Haselbach, J. Am. Chem. SOC. 92, 590 (1970).
a) M . Beetz, G. Bieri, H . Bock, and E. Heilbronner, Helv. Chim. Acta
56, 1028 (1973): b) P. Bruckmann and M . Klessinger, Chem. Ber. 107,
1108 (1974).
P . Hemmersbach, Diplomarbeit, Universitat Munster 1975.
Values of b= - 1.64 and - 1.73eV [3] for the cis-form are obtained
with 1,l'- and 2,2'-disubstituted derivatives, respectively, as compared
with the above value of /I=
14 eV
Fluorosulfinylimidosulfur Oxide D i f l u o r i d e [ * * ]
By Hans-Joachim Krannich and Wolfgang Sundermeyer"]
Sulfinyl pseudohalides tend to disproportionate into the
corresponding sulfenyl and sulfonyl compounds, which are
in turn frequently unstable['. '1. In contrast, halosulfinyl pseu-'
dohalides appear to resist decomposition of this kindL3].From
the hitherto unknown series of the halosulfinylimidosulfur
oxide difluorides, X-SO(NSOF2), we have now prepared
the fluorine compound ( 3 ) , X = F , as the first representative
by reaction of sulfinyl chloride fluoride (l)C4l with mercury
bis(imidosu1fur oxide difluoride) (2)['l.
Fig. 1. PE spectrum of bicyclopropyl: above, recorded with a Perkin-Elmer
PS 16 instrument (Xe/Ar calibration); below, calculated for gaucheirrans
z 60 :40.
In Figure 1 the spectrum predicted on the basis of MIND0/2
results and the assumption of Lorentz curves of 0.5eV halfwidth for a mixture of conformers having the given composition is compared with the measured PE spectrum. Agreement
is so good as to apparently justify the assignments given.
These data yield a splitting of Alas(trans)=2.32eV for the
trans-conformation of unsubstituted bicyclopropyl, corresponding to a HMO resonance integral = - 1.74 eV, which
fits very well into the series of values of f l = -2.45 eV for
trans-butadiene[8al and p= - 2.1 eV for the trans-form of vinylcyclopropane[8b! With the aid of the cosine relation the value
AIas (cis)% 2.5 eV is calculated from Alas (gauche) =2.00 eV ;the
corresponding value of p is ca. - 1.9 eV. Comparison with
the sterically fixed 1,I '-disubstituted bicyclopropyls shows that,
as for the exo-dimethylene compounds[g], the magnitude of
Angew. Chem. Inr. Ed. Engl.
/ Vol. 15 (1976) No. 5
In a vacuum system, compound ( 1 ) (12g) is condensed
onto (2) (6.5g) and the suspension stirred for 1 h at room
temperature. The volatile components are again condensed
onto the same quantity of (2) and the mixture once more
allowed to react for 1 h. Distillation of the volatile components
drawn off affords ( 3 ) (8.5 g, 78 %) as a water-clear liquid
boiling at 64°C.
[*] Prof. Dr. W. Sundermeyer and Dip1.-Chem. H.-J. Krannich
Anorganiscb-chemisches Institut der Universitat
Im Neuenheimer Feld 270, 6900 Heidelberg 1 (Germany)
[**I This work was supported by the Deutsche Forschungsgemeinschaft
and the Fonds der Chemischen Industrie. We are grateful t o Priv.-Doz.
Dr. K . Seppelr for his help in interpreting the NMR spectrum.
The existence of (3) is confirmed by elemental analysis
and the mass spectrum (70eV): m/e= 167 molecular ion (rel.
int. 36.7 %), 148 OS-NSOF2 (9.8), 100 NSOFz (1.7), 86 SOF2
(S), 70 SF'? (3.3), 67 SOF (IOO), 65 NSF (1.9), 62 NSO (5.3),
51 SF (3.1), 48 SO (10.5), 46 NS (9.1), 32 S (2.5), and 30?
(6.6).-The IR spectrum contains bands at 1425 (vs, vS0,
NSOF'), 1271 (m, vSO), 1182 (vs, vNS), 872 (vs, vSF), 735
(w), 698 (w), 655 (w), 490 (m), and 450 cm-' (m).
Compound ( 3 ) gives an unusual "F-NMR spectrum.
Instead of the expected doublet and triplet it contains a quartet
at -57.98 ppm (SOF) and an octet at -52.48ppm (ABX
type), i. e. the fluorine atoms ofthe NSOF2 group are diastereotopic and couple with each other as well as with the fluorine
atom attached to the unsymmetrically substituted sulfur atom
8 ~=
of the sulfinyl group: 8x= -57.98, 8 ~ -52.54,
52.43 ppm; JAB= 193.6, JAX= 8.3, JBX= 8.3 HZ (Fx-SONSOFAFB).
+ 2 C&Li
2 R,N-Si-N-R'
- 2 LiF. - 2 C4H,,
R = Si(CH3),, R' = C(CH3),
However, if a fluorine atom of tert-butylaminodifluorosilane
is replaced by an aryl groupf4]the reaction takes an unusual
course: The product obtained is an unsymmetrically substituted cyclic dystem whose formation can be attributed to
a nucleophilic 1,3-rearrangement at silicon (comparable with
the known methyl shift in a carbon skeleton) and also be
regarded as evidence for generation of a silicon ylide. The
absence of oligomerization products of type (1) shows the
steric influence of the nitrogen atoms alone to provide insuficient stabilization of such a species with silicon having the
coordination number 3[']. Instead, the expected extremely
high reactivity of this intermediate leads to intramolecular
nucleophilic substitution with migration of a methanide ion
and ring closure to give ( 2 ) .
Received: February 24, 1976 [Z 428 IE]
German version: Angew. Chem. 88,338 (1976)
CAS Registry numbers:
(I), 14177-25-4; ( 2 ) , 31618-64-1 ; (3), 58816-64-1
C4H9Li (0.11 mol, as 15 % solution in hexane) is added
dropwise at room temperature to monoalkylaminofluorosilane
(0.1 mol) with stirring. An exothermic reaction ensues, liberating lithium fluoride and butane, which is condensed in a
cold trap. After boiling for 12h the hexane is distilled of
in uacuo and the residue vacuum sublimed.
[l] P. W Schenk and H . Blocking, Chem. Ber. 92,2333 (1959).
[2] W Lidy, Dissertation, Universitat Heidelberg 1974.
[3] H . - J . Krannich and W Sunderrneyer, Angew. Chem. 88.88 (1976); Angew.
Chem. Int. Ed. Engl. IS, 110 (1976).
[4] H. S . Booth and F . C . Mericola, J. Am. Chem. SOC.62, 640 (1940).
[5] K . Seppelt and W Sunderrneyer, Angew. Chem. 82, 931 (1970); Angew.
Chem. Int. Ed. Engl. 9, 905 (1970).
- :CH3
1/2 (CH,),Si-N-Si-N-R
R-N-Si -N-Si(CH3),
R = C(CH3)3
Nucleophilic 1,SRearrangement at Silicon-Indirect
Evidence for a Silicon-Nitrogen Y l i d e c * * ]
The composition of the new compounds was confirmed
by elemental analysis and vibrational spectroscopy:
By Uwe Klingebiel and Anton Meller"]
Apart from bimolecular ring closure reactions of halosilanes
with amines or ammonia['], stable monoalkylaminofluorosilanes['] can be cyclized directly by the action of n-butyllithiumc3I,the reaction mechanism being interpretable in intramolecular or intermolecular terms:
I ,3-Di-tert-butyl-2,4-di[bis (trimethylsilyl)amino] -2,4-difluorocyclodisilazane (1)
[*] Prof. Dr. A. Meller and Dr. U. Klingebiel
Anorganisch-chemisches Institut der Universitat
Tammannstrasse 4, 3400 Gottingen (Germany)
p * ] This work was supported by the Deutsche Forschungsgemeinschaft
and the Fonds der Chemischen Industrie.
Yield 65%; m.p. 204°C; MS (70eV): m/e=556 (rel. int.
3%, M'); 'H-NMR (in CH,CI,, TMS int. standard): -0.15,
-0.31 [(Me3Si)'N, cisltrans isomers; JHF=0.9Hz] - 1.29 ppm
(tBu); "F-NMR (with C6F6 as internal standard): -56.25,
- 57.33 ppm.
Yield 88%; m.p. 57°C; MS (70eV): m/e=320 (rel. int.
3 %, MC);'H-NMR (in CH2CI2,TMS int. standard): -0.38,
Angew. Chem. Int. Ed. Engl.
/ Vol. 15 (1976) N o . 5
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oxide, difluoride, fluorosulfinylimidosulfur
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