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N-Halogenoimidosulfur Difluorides and N N-Dihalogenosulfur Diimides.

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[l] K. Dimroth and W. Stiide, Angew. Chem. 80, 966 (1968);
Angew. Chem. internat. Edit. 7, 881 (1968).
[2] K. Dimroth, N . Gr&& H . Perst, and F. W. Steuber, Angew.
Chem. 79, 58 (1967); Angew. Chem. internat. Edit. 6, 85 (1967).
[3] K. Dimroth, N . Greif, W. Stade, and F. W. Steuber, Angew.
Chem. 79, 725 (1967); Angew. Chem. internat. Edit. 6,711 (1967).
[4] (1. Thewalt, Angew. Chem. 81, 783 (1969); Angew. Chem.
internat. Edit. 8, 770 (1969).
Electron Transfer from an Excited Electron Donor
in the Triplet State to an Acceptor Molecule
By G . Briegleb and H. Scliuster[*]
We have investigated the influence of electron donor-acceptor
(EDA) complex formation on the triplet-triplet (TT) absorppossibilities of electron transition (energy level scheme, see
tion spectrum of the electron donors (D) naphthalene (f)
Figure). Comparison of the observed and estimated Gm*
and phenanthrene (2) in complexes with the electron accepvalues shows that G C T ~ does not correspond to the measured
tors (A) tetrachlorophthalic anhydride (3) and pyromellitic
CT*-absorption bands. No distinction can be made between
dianhydride ( 4 ) .The TT absorption spectra were recorded in
GCT; and GCT:
within the limits of accuracy of estimation.
n-propyl ether,glass at T = 96 to 118°K by flash spectroA superposition of both transitions is conceivable, thus
photometryrll. The triplet state of ( 1 ) and ( 2 ) in the cornproviding a possible explanation inter aliu for a diffuse
plex IDA/ with (3) or ( 4 ) was excited by irradiation within
broadening of the CT* band in the case of the phenanthrene
the frequency of the charge transfer (CT) absorption bands
complex ( 2 1 4 3 ) .
ria the singlet excited state lD-'A-\: of the complex with
Received: July 28, 1969
[Z 72 IEl
German version: Angew. Chem. 81, 790 (1969)
subsequent "intersystem crossing" energy transfer
A-1:
+ ID+A[. This excitation mechanism was possible since the
[*I Prof. Dr. G. Briegleb and Dr. H. Schuster
condition Epj+A-jz > FD;AI. or in the case of complexes
Institut f u r Physikalische Chemie der Universitat
with donor-triplet excimers ED..jD+d.-Ix > ~ D D ~ A I ,
87 Wurzburg, Markusstrasse 9-11 (Germany)
was fulfilled. The triplet state had to be excited via the C T
[ l ] H . T. Witt, R . Moraw, and A. Miiller, 2. physik. Chem. N . F.
singlet state in order to prevent a triplet excitation of the free
20,193 (1959); G. Porter, Angew. Chem. 73,7 (1961); in A . Weissdonor molecules not bonded in the complex.
berger: Technique of Organic Chemistry. Interscience, New York
The TT absorption spectra of complexed ( 1 ) and (2) in the
1963, Vol. VI11/2, p. 1055; J . S. Brinen, J. chem. Physics 49, 586
frequency range 20 t o 25 Y lo3 crn-1 exhibit characteristic
(1968).
changes compared t o the TT absorption spectra of the free
[ 2 ] G. Briegleb and H . Schuster, Chem. Physics Letters 4 , 51
donors ( I ) and (2) 121. The triplet lifetime is also reduced by
(1969).
complex formation, i.e. the probability of the T + So transiI31 hVcTf "_ hvcT - ED(S0 TI) ;JWX; 2 hvcTj f E A ( S 1 7 S 2 ) ;
tion is increased. The TT spectrum of complexed triplet exhvCT5 2 hvCTT f ED+ + D+*; for further details see: G. Brregleb
cimers of (f) and (2) was measured at slightly higher
and H . Schuster, Z. Naturforsch. a, to be published.
temperatures (106-113 OK) and/or in the presence of an excess of donor. It was also possible to detect the excimers in
the phosphorescence spectrum by irradiation within the
frequency of the CT band at T = 100 t o 120'K and in the
N-Halogenoimidosulfur Difluorides
presence of an excess of the donor [21.
ID^'
-
and N,N'-Dihalogenosulfur Diimides
The ionization energy of the triplet excited donor bonded in
the complex lD+AI is reduced by the energy required for
T1 + SO excitation. Hence CT* absorption bands corresponding to transition of an electron f r o m the rriplet excited donor
to an unoccupied energy level of the acceptor in frequency
ranges of relatively long wavelength could be expected. We
first found CT* bands of this kind in complexes IDFA[ of
triplet excited ( I ) and (2) with ( 3 ) and ( 4 ) after the population of IDFA1 had been increased by flash excitation in the
frequency range of the C T bands of the complexes IDA1 in
the ground state in solutions in n-propyl ether glass at 96 to
118'K.
By K . Seppelt and W. Sundermeyer[*I
N-Halogenoimidosulfur difluorides (2) have previously been
prepared by reaction of halogens with N-fluoroformylimidosulfur difluoriderll, FC(O)NSFz, in the presence of cesium
fluoride or by reaction of halogens with bis(difluorosu1fur(1v)imido)mercury 121, Hg(NSF&.
We have recently investigated the cleavage of N-halogenobis(trimethylsily1)amines( I ) with non-metallic halides 131 and have
found a further route to compounds (2) by reaction of ( I )
(X = CI, Br) with sulfur tetrafluoride.
The experimentally determined C T * frequencies of the CT*
band maxima are given in the Table, as are the CT* freGcT;,
and G C T ~ for a transition of the DT
quencies GcT!,
electron 1 or 2 of theT1-excited donor to various energy
levels of the acceptor calculated (31 assuming the various
VCT:,,,
[Naphthalenelj.
IPhenanthreneIj.
1
i9-20
Ibl
I
1
Angew. Chem. internat. Edit.
GCT;
6.5
6.4
[a]
11
GCT; [a]
C C T [a]
~
18.4
18.5
18.4
15.4
1 Vol. 8 (1969) 1 No. 10
X-N[Si(CH3)312 iSF4
x
=
(lb), X
=
(la),
GCT&
1
16.5
16.0
'I
GCT;
[a]
+
X-N=SFz
CI
Br
II
GCT;
+ 2 (CH3)jSiF
(2)
[a]
GCT; [a]
15.7
15.7
15.4
12.4
77 1
The physical and spectroscopic data found for the products
( 2 ) are identical with those found by earlier workersrl.21.
This new method of preparation of (2) confirms the assumption that these compounds are N-halogenoimidosulfur difluorides and not the isomeric difluoronitridosulfur halides,
N E S F ~ X Previous
.
evidence for the structure (2) was based
mainly o n the occurrence of nitrogen-halogen fragments in
the mass spectrum; however, the possibility of these fragments arising from recombination could not be ruled out.
The analogous reaction of N-iodobis(trimethylsily1)amine
( I c ) with sulfur tetrafluoride does not lead to the still unknown N-iodoimidosulfur difluoride (cf. [21) but (presumably
via this compound as unstable intermediate) to N,N’-diiodosulfur diimide (3).
2 I-N[Si(CH3)312
+ SF4
(Icl
->
I -N=S=N-I
Anorganisch-chemisches Institut der Universitat
69 Heidelberg, Tiergartenstrasse 2 (Germany)
[11 J . K . Ruff, Inorg. Chem. 5, 1787 (1966).
[21 0. Glemser, R . Mews, and H . W. Roesky, Chem. Ber. 102,
1523 (1969).
[3] K . Seppelt and W. Sundernzeyer, Naturwissenschaften 56,
281 (1969).
141 We thank Dr H. Seidl, Badische Anrlin- und Soda-Fabrik,
for the recording and discussion of the mass spectrum.
[51 We are grateful to Dr. H . Eysel, Universitat Herdelberg, for
the recording and discussion of the Raman spxtrum.
Synthesis and Reactions of a 2H-Azirine
Unsubstituted on C-3
f 4 (CH&SiF
(3)
A solution of S F 4 in 1,2-dichloroperfluoroethaneis added
dropwise at about 0 O C t o a solution of ( I c ) in the same solvent. A n orange-red crystalline precipitate forms that can be
recrystallized from methylene chloride. Compound ( 3 ) melts
and simultaneously explodes a t 106 “C. Similarly to S 4 N 4 , it
explodes o n impact and a distinct smell of SO2 is noticeable;
on ignition it deflagrates with simultaneous emission of
violet iodine vapor. The crystals are almost insensitive to
hydrolysis and are only slightly soluble in organic solvents
such as methylene chloride, carbon tetrachloride, and benzene. Compound (3) was identified by elemental analysis and
by mass spectrometryr41 [m/e = 314 (INSNI loo%), 187
(INSN 6%), 173 (INS 4 7 3 , 141 (IN 2.5 %), 127 (I 11 %), 60
(NSN 3.5%),46 (SN 7.573, and 32 (S 2%) together with a
few recombination fragments such as 12 and IS; 13 eV]. The
I R spectrum (KBr) contains bands at 1094 (s), 1047 (vs), 950
(s), 631 (s), 465 (m), 327 (m), and 297 cm-1 (m).
( 4 ) can be
N,N’-Dibromosulfur diimide Br-N=S=N-Br
prepared under the same experimental conditions. Compound (4) is much more soluble in the above mentioned
solvents than is ( 3 ) . The pale yellow crystals of ( 4 ) melt at
+0.5 O C with partial decomposition; they are more sensitive
t o impact than the crystals of ( 3 ) .
The mass spectrum [m/e = 218, 220, 222 (BrNSNBr 33%),
139, 141 (BrNSN 3 7 3 , 125, 127 (BrNS 1273, 93, 95 (BrN
14%), 79, 81 (Br 38%), 60 (NSN 273, 46 (SN loo%), and
32 (S 39%); 70 eV], the I R spectrum (nujol) 11127 (s), 1035
(vs), 921 (s), 657 (s), 603 (m), 519 (m), 417 (m). and 370 (w)].
and the Raman spectrurnr51 [1133 (w), 926 (vs), 662 (m), 608
(m), 533 (s), 426 (w), 379 (m), 198 (m), and 88 (w)] are in
agreement with the assumed structure (4). Attempts t o
prepare the homologous chlorine derivative of ( 3 ) and ( 4 )
have so far failed.
[Z 73 IE]
Received: August 5, 1969
German version: Angew. Chem. 81, 785 (1969)
Cornp
[*I Dip1.-Chem. K . Seppelt and Prof. Dr. W. Sundermeyer
By W. Bnuer and K . Hafner[*l
Thermolysis (11 or photolysis 121 of 1-alkyl or I-aryl-vinyl
azides ( I ) (R1 = R 2 = H, aryl, alkyl; R3 = aryl, alkyl)r3l
leads t o the formation of 2H-azirines with a substituent at C-3
(2) and to ketenimines (3). However, the decomposition of
“terminal” vinyl azides ( I ) (R1 = R2 == H, aryl, alkyl; R3 =
H) gives only the nitriles ( 4 ) 141 and none of the expected, and
formerly unknown, 2H-azirines which lack a substituent at
the 3-position.
ir
(31
RZ
\
CH-CEN
R’1
Using the reaction scheme which is generally used for the
synthesis of substituted fulvenes from 6-fulvenyl tosylates we
have been able to prepare the “terminal” vinyl azide 9(azidomethy1ene)fluorene ( 5 ) [51 from 9-fluorenylidenemethyl
tosylate and sodium azideL61 and t o study its reactions.
Whilst ( 5 ) reacts with triphenylphosphine to give the corresponding iminophosphorane[71 (yield 77 %, yellow prisms,
m.p. 206-207 “C), the thermally rather unstable spiro[2Hazirine-2,9’-fluorene] (7) could be prepared as the first C-3
unsubstituted 2H-azirine by photochemical decomposition
of ( 5 ) in anhydrous diethyl ether at -15
(UV lamp Type
Q 81, Original Hanau, Duran glass, irradiation time 1 h) and
careful work-up (isolation at -70 O C , recrystallization at
-50 “C). Presumably the initial formation of the nitrene (6)
Yield
IR (cm-1)
( %)
-
~~
~
~~
74
83-85 (decomp.)
yellowish needles
(n-hexane)
234 (4.31), 260 (4.19), 270 (4.43), 284 (4.10)
(dioxane)
10
113-1 15 (subl.)
colorless needles
(petroleum ether)
224 (4.34). 231 (4.18), 267 (4.28), 279 (4.15),
292 (3.44), 302 (3.16) (dioxane)
21
325-327 red needles
(ethyl acetate)
237 (4.72). 263 (4.71), 304 (4.06). 332 (4.18).
439 (4.27), 453 (4.28) (dioxane)
36
215-217 colorless needles 227 (4.28), 236 (4.12). 270 (4.21). 293 (3.66),
305 (3.67) (dioxane)
(ethyl acetate)
21
139- I41
yellow platelets
(methanol)
225 ( 4 . 3 9 , 233 (4.16), 270 (4.24), 293 (3.72),
305 (3.74) (dioxane)
1.3 (1 H/broad), 1.61 (lH/m),
2.31-2.83 (8H/m), 3.91 ( I H/d)
([Dd-DMSO)
1.99 ( 1 H/s), 2.18-2.9 (8H/ni),
4.82 (1 H/s), 6.28(3H/s)
(CDCI3)
la1 TMS as internal standard.
772
Angew. Chem. internat. Edit.
/ Vol. 8 (1969) / No. 10
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