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Determination by ESR Spectroscopy of the Constitution of the Phosphorus Radicals Formed on Oxidation of Phosphorins.

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one obtains the electronegativity XNSF, = 3.3. If one plots
the mean P F frequency of the phosphoryl halides against the
sum of the electronegativities, one obtains a linear dependence, whence the electronegativity of the NSF2 group again
appears as 3.3.
Compound (4) IS a clear liquid of b.p. 7 2 ° C and m.p.
-70 "C and, as expected, is more stable than sulfur difluoride
(fluorosulfony1)imide. The compound was characterized by
elemental analysis and by its IR, IgF-NMR, and mass
spectra.
The mass spectrum shows, besides the molecular ion at
m ' e = 183, the typical fragments M - F (164), FS02N (97),
SOF2 (86), FS02 (83), FSO (67), S F (51), and SO (48).
The 19F-NMR spectrum shows a doublet at -45.4 and a
triplet at -60.1 referred to CC13F as external standard; the
coupling constant is JFF = 8 Hz.
The IR spectrum (gas) in the NaCl region shows strong bands
at 1475, 1450, 1245, 888, 821, 740, and 716 cm-1, which are
t o be ascribed t o stretching virations.
Compound ( 3 ) is added dropwise to an excess of PCls with
stirring and with passage of dry nitrogen (molar ratio 1 : 1.2)
at such a rate that the temperature does not rise above 50 "C.
The mixture is then filtered under nitrogen from the excess
of PCls and fractionated in a vacuum (yield 70 %; b.p.
45 "C,0.4 mm).
Compound (4) can also be prepared, in a n impure form,
from ( I ) and sulfur dichloride.
The IR spectrum of (4) contains bands at 1425, 1210, 1125,
805, 712, 582, 537,480, and 442 cm-1, which are provisionally
allotted t o the following vibrations: vas(SO) 1425, vs(SO),
v(N=S) 1210, 1125, v(SF) 805, v(SN) 712, and v(SCI) and
deformation vibrations. The mass spectrum shows many
fragments as well as the molecular ion at mie = 199 and 201
(isotopic ratio).
Sulfur dichloride (fluorosulfony1)imide ( 4 ) is a colorless
liquid, that is hydrolysed immediately by water. It reacts
with V2A steel at room temperature with decomposition.
Received: June 21st, (1967)
[Z 547 IE]
German version: Angew. Chem. 79, 723 (1967)
[*I Prof. Dr. 0.Glernser, Dr. H.W. Roesky, and
Dip1.-Chern. P. R. Heinze
Anorganisch-Chernisches Institut der Universitat
Hospitalstr. 8/9
34 Gottingen (Germany)
[l] E. A. Robinson, Canad. J. Chern. 40, 1729 (1962).
[2] Cf. 0. Glernser, H. W . Roesky, and P . R . Heinze, Angew.
Chem. 79,153 (1967); Angew. Chem. internat. Edit. 6,179 (1967).
[3] vs = very strong, s = strong, m = medium.
[4] A. Miiller, E. Niecke, and 0 . Glernser, Z . anorg. allg. Chem.
350, 252 (1967).
Preparation of Sulfur Oxide (Fluorosu1fonyl)imide
and Sulfur Dichloride (Fluorosulfony1)imidefll
By H . W. R o e s k y [ * ]
Fluorosulfonamide ( I ) , which can be prepared by hydrolysis
of fluorosulfonyl isocyanate 121 by concentrated formic acid,
reacts with thionyl chloride (2) t o give sulfur oxide (fluorosulfony1)imide (3).
FSOlNHz ( I ) [3]
FSOzN-S=O (3)
FSOzN=SClz ( 4 )
1 1 1 1
-57.0
-59.2
-61.4
Triplet
Singlet
Singlet
6
I
[a] Referred t o CCI3F or (CH&Si as external standard
Received: June 15th, 1967
[ Z 550 IE]
German version: Angew. Chem. 79, 724 (1967)
[*I Dr. H.W. Roesky
Anorganisch-Chemisches Institut der Universitdt
Hospitalstr. 8/9
34 Gottingen (Germany)
[l] Part IV of Sulfur-Nitrogen Compounds. - Part 111: H. W .
Roesky and A. HoH, Chem. Ber., in the press. - Part 11: 0.Glemser, H . W . Roesky, and P . R . Heinre, Angew. Chern. 79, 153
(1967); Angew. Chem. internat. Edit. 6, 179 (1967).
[2] I thank Farbwerke Hoechst for the supply of chlorosulfonyl
isocyanate.
[3] H . Jonas and D . Voigt, Angew. Chern. 70, 572 (1958).
Determination, by ESR Spectroscopy, of the
Constitution of the PhosphorusRadicals formed on
Oxidation of Phosphorins
By K . Dimroth, N . Greif, W. Stade, and F. W . Sfeuber[*l
Thionyl chloride (0.75 mole) is added t o the amide ( I ) (0.5
mole), and the whole is heated under reflux, with stirring,
for 48 h, then distilled under vacuum (oil-pump). The product
(3) is collected in a cold trap (-10°C; ice;salt) and distilled
b.p. 20 OC/O.3 mm, 32 "Cjl5 mm]. Partial
[yield, 42 g (57
decomposition sets in at higher pressures.
Compound (3) is a yellow liquid that reacts explosively with
water at room temperature. At -20 OC its reaction with water
regenerates the amide and sulfur dioxide. The mass spectrum
of (3) contains the molecular ion peak at m/e = 145 and
peaks for the fragments FSOz (83), SO? (64), SO (48), and
NS (46). The IR spectrum (capillary film) in the NaCl and
KBr region shows bands at 1435,1260,1210,1125, 830,700,
628, 615, 595, 538, 482, and 460 cm-1; these are provisionally
allotted to the following vibrations: vas(SO) 1435, vs(SO),
v(SO), v(N=S) 1260, 1210, 1125, v(SF) 830, v(SN) 700, and
deformation vibrations.
Reaction of the imide (3) with phosphorus pentachloride
gives sulfur dichloride (fluorosulfony1)imide (4).
x);
As part of a study of the radicals formed on oxidation of
2,4,6-triarylphosphorins ill we have prepared the new
phosphorins (2) listed in the table. These compounds, which
were prepared by Markl's method 121 from the corresponding
pyrylium salts ( I ) , were oxidized by 2,4,6-triarylphenoxyIs,
lead(1v) acetate or benzoate, mercury(r1) acetate, or other
oxidizing agents t o the phosphorus radical cations ( 3 ) , which
are very stable in solution.
R4&R2
xo
L
R5 P
R'
J
(3)
Angew. Chem. internat. E d i t .
Vol. 6 (1967)1 No. 8
71 1
R'
R2
R3
R4
RS
H
H
H
C6Hj
C6H5
H
H
H
H
H
H
H
H
H
H
H
GHj
H
H
H
H
H
H
H
H
H
H
H
H
H
H
H
H
H
M.p. ( "C)
168-171
I67
188.5-189.5
216-217
166- 167
181-182
110.5-112
161.5- 163
134-1 36
132- 133
155-156.5
148-150.5
163-164
87.5-88.5
104-105
116-1 16.5
88
Radical
>.ma,
(nm) in
n-hexane
~ ~ 1 0 - 4 cation (3)
218
278
271
264
28 1
285
283
287
29 1
29 1
28 1
293
272
267
288
300
263
5.2
4.2
3.7
3.13
4.3
5.4
3.7
3.78
3.78
3.78
3.75
2.93
4.72
3.06
1.8
2.16
0.5
a p (gauss)
23.2
23.2
24.8
26.0
22.6
22.4
21.6
21.7
21.6
22.3
22.3
23.7
23.3
26.9
[a] These phosphorin derwatives were recently prepared by G. Mdrkl er al. [31 by another method. Material discrepancies in melting
point occur only for (2c) and (2di. These may be due, as for tetra- and penta-phenylbenzene derlvatives, t o formation of different
crystal modifications.
[b] From 2,4,6-tri-t-butylpyrylium tetrafluoroborate, m. p. 216°C ( K . Dimrorh and W.Mack, unpublished)
The ESR spectra of all these radicals are very similar in type:
They contain a doublet that is due t o interaction of the free
electron with the phosphorus. The phosphorus coupling
constant u p : lies between 21.5 and 27 gauss (see table)
according t o the nature of the substituents. The doublet has
hyperfine structure owing to coupling with the protons.
There are about 70 lines in the spectrum of the 2,4,6-triphenylphosphorin radical. However, if the three phenyl
groups in 2-, 4-, and 6-position are replaced by pentadeuteriophenyl, then, exactly as with 2,4,6-tri(pentadeuteriophenyl)phenoxyl[41, the spectrum is greatly simplified by
the small magnetic moment and the larger nuclear spin of
the deuterium. Only the two protons in the central nucleus
lead t o resolution to hyperfine structure. One obtains a triplet
1:2:1, which, by phosphorus coupling (lapl=23.2 gauss) appears twice, (Fig. la). The hyperfine structure coupling
constant l a ~ lamounts t o about 2.4 gauss. In the NMR
spectrum tris - (pentadeuteriopheny1)phosphorin (2.)
gives
signals only for the two protons in the central ring (doublet
at 6 = -8.1 2 ppm, J = 6Hz).
Every group of lines in the ESR spectrum of the oxidation
product of 2,6-bis(pentadeuteriophenyl)-4-phenylphosphorin
(26) consists of a sextet with approximate intensities
1:5:10:10:5:1 (Fig. lb), analogously t o the spectrum of the
correspondingly substituted phenoxyl[41. The coupling
constants of the protons in positions 3 and 5 of the central
ring, and of the two ortho-protons and the para-proton of
the phenyl group, are about equal in size (2.4 gauss), but
the meta-protons on this phenyl ring have significantly lower
coupling constants, so that no further resolution is observed.
The spectrum can be unequivocally reconstructed.
It is thus proved that the new radicals retain the intact
phosphorin ring. The s a n e conclusion is reached on comproportionation of one molecule of the radical formed
on oxidation and one of that formed o n reduction of 2,4,6triphenylphosphorin 151, which regenerates 2,4,6-triphenylphosphorin.
The phosphorins (20) to (2.) are the first compounds of this
type containing aliphatic groups. They too give very simple
ESR spectra because the coupling constants of the t-butyl
groups are small. Figure l c shows the spectrum of 2,6-di-t-butyl-4-phenylphosphorin cation radical (lap, = 23.7 gauss,
~ U H ! = 2.5 gauss). For 2,6-di-t-butyi-4-(p-methoxyphenyl)phosphorin cation radical the sextet of lines becomes a
quintet, since here the coupling with the para-proton on the
phenyl ring at C-4 is absent.
Received: June Zlst, 1967
[Z 548 IE]
German version: Angew. Chem. 79, 725 (1967)
lOGauss
,
,,
Fig, 1. ESR spectra of the cation radicals from (a) 2,4,6-tris(pentadeuteriopheny1)phosphorin (2a), (b) 2,6-bis(pentadeuteriophenyl)-4(2p).
phenylphosphorin (2b), and (c) 2.6-di-t-butyl-4-phenylphosphorin
712
[*I Prof. K. Dimroth, Dr. N. Greif,
Dip1.-Chem. W. Stade, and Dr. F. W. Steuber
Institut fur Organische Chemie der Universitat
Bahnhofstr. 7
355 Marburg (Germany)
[l] K . Dimroth, N . Greg, H. Perst, and F. W . Steuber, Angew.
Chem. 79, 58 (1967); Angew. Chem. internat. Edit. 6 , 85 (1967).
[2] G . Markl, Angew. Chem. 78,907 (1966); see also K . Dimroth
and P. Hoffmann, Angew. Chem. 76, 433, 512 (1964); Angew.
Chem. internat. Edit. 3, 384 (1964); Chem. Ber. 99, 1325 (1966).
131 G . Markl, F. Lieb, and A. Merz, Angew. Chem. 79, 475
(1967); Angew. Chem. internat. Edit. 6 , 458 (1967).
[4] K . Dimroth, A . Berndt, F. Bar, R . Volland, and A . Schweig,
Angew. Chem. 79, 69 (1967); Angew. Chem. internat. Edit. 6 ,
74 (1967).
[5] K . Dimroth and F. W . Steuber, Angew. Chem. 79,410 (1967);
Angew. Chem. internat. Edit. 6 , 445 (1967).
Angew. Chem. internat. Edit.
Vol. 6 (1967)
I No. 8
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phosphorite, constitutions, spectroscopy, oxidation, esr, determination, radical, former, phosphorus
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