Synthesis and structures of triorganochalcogenium (Te, Se, S) dinitramides

Article abstract of DOI:10.1002/ejic.200800565

The syntheses of the triorganochalcogenium dinitramide salts [Ph ₃Te][N(NO₂)₂] (1), [Me₃Te][N(NO ₂)₂] (2), [Ph₃Se]-[N(NO₂) ₂] (3), [Me₃Se][N(NO₂)₂] (4), [Ph₃S][N(NO₂)₂] (5), and [Me ₃S][N(NO₂)₂] (6), their characterization by multinuclear NMR spectroscopy, vibrational spectra, and single-crystal structures are described. The syntheses of the compounds were achieved with the help of [Ag(py)₂][N(NO₂)₂] and [Ag(NCCH ₃)][N(NO₂)₂] as dinitramide transfer reagents. Whereas in the crystal structure of 1 different coordination modes to dinitramide moieties are present, the crystal structure of 3 shows only a single intermolecular contact to the dinitramide moiety. Wiley-VCH Verlag GmbH & Co. KGaA, 2008.

Full text of DOI:10.1002/ejic.200800565

FULL PAPER
DOI: 10.1002/ejic.200800565
Synthesis and Structures of Triorganochalcogenium (Te, Se, S) Dinitramides
Thomas M. Klapötke,*[a] Burkhard Krumm,[a] and Matthias Scherr[a]
Keywords: Tellurium / Selenium / Sulfur / Dinitramide / NMR spectroscopy / Crystal structure
The syntheses of the triorganochalcogenium dinitramide
salts [Ph3Te][N(NO2)2] (1), [Me3Te][N(NO2)2] (2), [Ph3Se]-
[N(NO2)2] (3), [Me3Se][N(NO2)2] (4), [Ph3S][N(NO2)2] (5), and
[Me3S][N(NO2)2] (6), their characterization by multinuclear
NMR spectroscopy, vibrational spectra, and single-crystal
structures are described. The syntheses of the compounds
were achieved with the help of [Ag(py)2][N(NO2)2] and
[Ag(NCCH3)][N(NO2)2] as dinitramide transfer reagents.
Whereas in the crystal structure of 1 different coordination
modes to dinitramide moieties are present, the crystal struc-
ture of 3 shows only a single intermolecular contact to the
dinitramide moiety.
(© Wiley-VCH Verlag GmbH & Co. KGaA, 69451 Weinheim,
Germany, 2008)
pound Ag[N(NO2)2].[21,45] The acetonitrile adduct is re-
ported to consist of [Ag(NCCH3)4][Ag3{N(NO2)2}4] in the
solid state.[21] Although the reactions work with both silver
dinitramide adducts, the use of [Ag(NCCH3)][N(NO2)2] is
preferable than [Ag(py)2][N(NO2)2], not only because pyr-
idine is a stronger base, but also because it is easier to re-
move acetonitrile in high vacuum than pyridine. In the
course of our investigations, the molecular structure of the
pyridinium dinitramide salt [pyH][N(NO2)2] as a byproduct
was obtained.[46] Because of the ease of formation of this
pyridinium salt even in aprotic solvents, the use of the ace-
tonitrile adduct is preferable. The disadvantage of the aceto-
nitrile adduct is, that according to elemental analyses, the
composition compared to reported [Ag(NCCH3)4]-
[Ag3{N(NO2)2}4] differs in the majority of cases. However,
in order to add the exact stoichiometric amount of dinitra-
mide to the starting materials, the latter composition had
to be achieved before use.
Introduction
The dinitramide anion was first discovered by Russian
chemists in 1971,[1] but was kept secret until it was indepen-
dently rediscovered in the late 1980s in the USA.[2] After-
wards, the Russian work was summarized in a series of pub-
lications,[1,3–10] new aspects were added by different
groups,[11–25] and also theoretical aspects of the dinitramide
anion have been reported.[26–28] An overview of structural
trends and variations in dinitramide salts has been
given,[10,29,30] and potential applications for various dinitra-
mide salts have been discussed.[31–33]
Within the last decades, triorganochalcogenium pseu-
dohalides have been well investigated.[34–41] Our own contri-
butions afforded a variety of triorganotelluronium/sele-
nonium halides and pseudohalides,[42–44] among them the
ionic azide compounds [R3Te]N3 and [R3Se]N3 (R = Me,
Ph).[43,44] Continuing our efforts to explore the chemistry
of main group elements with energetic substituents, in this
contribution we report the first syntheses and crystal struc-
tures of triorganochalcogenium dinitramide salts.
The synthesis of triorganochalcogenium dinitramides 1–
6 was achieved by reaction of the corresponding triorgano-
chalcogenium halogenides with the dinitramide transfer
reagent in dichloromethane or water (Scheme 1).
Results and Discussion
The precursors for the syntheses of the triorganochalcog-
enium dinitramides [R3Ch][N(NO2)2] (Ch = Te, Se, S; R =
Me, Ph) are the corresponding triorganochalcogenium ha-
lides. As dinitramide transfer reagents, the silver salts
[Ag(py)2][N(NO2)2] (py = pyridine) and [Ag(NCCH3)]-
[N(NO2)2] were chosen, as both can easily be prepared and
are considerably safer to handle than the solvate-free com-
Scheme 1. Preparation of triorganochalcogenium dinitramides.
The triphenyltelluronium(1)/selenonium(3) dinitramides
are pale-yellow solids that decompose very slowly at ambi-
ent temperature over a period of two weeks, but are storable
in the dark at temperatures below +4 °C for several months.
In contrast to the products with the phenyl substituent, sol-
vent evaporation of the compounds with the methyl group,
[Me3Te][N(NO2)2] (2) and [Me3Se][N(NO2)2] (4), yielded
[a] Department of Chemistry and Biochemistry, Ludwig-Maximil-
ian University of Munich
Butenandtstr. 5-13(D), 81377 Munich, Germany
Fax: +49-89-2180-77492
E-mail: tmk@cup.uni-muenchen.de
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© 2008 Wiley-VCH Verlag GmbH & Co. KGaA, Weinheim
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T. M. Klapötke, B. Krumm, M. Scherr
FULL PAPER
oily products, which decompose more rapidly relative to the Finally, we were not able to identify the products of the
compounds with the phenyl substituent. In case the pyr- reaction of [Me3O][BF4] with silver dinitramide, but likely
idine silver dinitramide transfer reagent is used for synthe- can exclude the formation of the protonated species
sis, present pyridine in the compounds can be removed by HN(NO2)2, as it was found with HN3 for the corresponding
exposure to high vacuum at ambient temperature for two reaction with silver azide.
days.
According to the preparation of the telluronium and sele-
Spectroscopic Data
nonium salts, the corresponding sulfonium salts,
[Ph3S][N(NO2)2] (5) and [Me3S][N(NO2)2] (6), have also
been prepared. In contrast to the viscous methyl-substituted
compounds 2 and 4, both organosulfonium dinitramides
could be isolated as colorless solids. Compounds 5 and 6
are less stable relative to the corresponding organotelluron-
ium and organoselenonium salts and decompose slowly at
ambient temperature. However, both compounds can be
stored at temperatures below –32 °C for several weeks with-
out decomposition according to 14N NMR spectroscopy.
The reaction of trimethyloxonium tetrafluoroborate with
silver dinitramide was also performed, but no evidence for
the formation of the desired trimethyloxonium dinitramide
was found. According to the 14N NMR spectrum of the
solution, several resonances were found [major resonances:
δ = –22 (NO2 group) and –181 ppm], which could not be
assigned properly. The simultaneous performed reaction of
[Me3O][BF4] with silver azide furnished, according to 14N
NMR spectroscopy, HN3 as main product [δ = –136 (Nβ),
–177(Nγ), –324(Nα) ppm; CH3CN solution]. Related to this
finding, the main product of the reaction with silver dinitra-
mide could possibly furnish dinitramine HN(NO2)2. How-
ever, no evidence for this compound could be found. In
order to find evidence for the formation of HN(NO2)2, the
reaction of CF3SO3H with KN(NO2)2 in dichloromethane
as solvent was performed. The 14N NMR spectrum of the
solution yielded several resonances, whereas no resonance
of the compared reaction of [Me3O][BF4] with Ag(py)2-
N(NO2)2 could be found. Instead N2O [δ = –148 (NNO),
–232 (NNO) ppm] and HNO3 (δ = –41 or –51 ppm) as main
products, likely the decomposition products of generated
HN(NO2)2, could be identified by 14N NMR spectroscopy.
The salt-like nature of 1–6 could be confirmed by spec-
troscopic characterization (overview Table 1). In the 14N
NMR spectra two resonances were observed for the anion.
Whereas a sharp resonance for the nitro group appears be-
tween δ = –11 and –14 ppm; the resonance for the amino
nitrogen atom is found as a broad resonance in the range
between δ = –55 and –59 ppm. This is comparable with lit-
erature values of the alkali salts of dinitramide (nitro group
δ = –12 to –14 ppm, amino nitrogen atom δ = –58 to
–62 ppm; all measured in D2O)[24] and leads to the conclu-
sion that in solution all compounds are completely dissoci-
ated. In the 125Te NMR spectrum the resonance of the tri-
phenyltelluronium cation in 1 is detected at δ = 788 ppm
(CDCl3), whereas the resonance of the trimethyltelluronium
cation in 2 is shifted to higher field (δ = 439 ppm, D2O).
The same trend is observed for the selenonium cations in
their 77Se NMR spectra (3: δ = 498 ppm, CDCl3; 4: δ =
260 ppm, [D6]acetone/δ = 256 ppm, CD3CN). As expected,
Table 1. NMR resonances of triorganochalcogenium dinitramides
(δ in ppm).
14N [N(NO2)2/
N(NO2)2]
Compound
Solvent
125Te
77Se
[Ph3Te] [N(NO2)2] (1) CDCl3
[Me3Te] [N(NO2)2] (2) D2O
788
439
–13/–56 (br.)
–14/–58 (br.)
–12/–56 (br.)
–11/–58 (br.)
–11/–55 (br.)
–11/–58 (br.)
–10/–55 (br.)
–14/–59 (br.)
[Ph3Se] [N(NO2)2] (3)
CDCl3
498
260
256
[Me3Se] [N(NO2)2] (4) [D6]acetone
CD3CN
CDCl3
[D6]acetone
D2O
[Ph3S] [N(NO2)2] (5)
[Me3S] [N(NO2)2] (6)
Table 2. Assignments of the observed IR and Raman bands for the dinitramide anions of 1–6 in cm–1 (ip = in phase, oop = out of phase).
1
2
3
4
5
6
Raman
1575
IR
Raman
1569
IR
Raman
1574
IR
Raman
IR
Raman
1579
IR
Raman
IR
νas(NO2)ip
1582 (w)
1572 (m)
1499 (vs)
1441 (vs)
1319 (s)
1196 (vs)
1171 (vs)
1009 (vs)
991 (vs)
919 (s)
822 (m)
747 (vs)
738 (vs)
478 (m)
471 (s)
1572 (m)
1579 (m)
νas(NO2)oop
1425
1406
1421
1499 (vs)
1421 (vs)
1320 (s)
1196 (vs)
1170 (vs)
1009 (vs)
991 (vs)
918 (s)
1426
1328
1528 (vs)
1431 (vs)
1343 (s)
1448
1504 (vs)
1425 (s)
1346 (s)
1174 (vs)
1424
1505 (vs)
νsym(NO2)ip
νsym(NO2)oop
1335
1168
1329
1191
1331
1162
1328
1185
1332
1189
1334 (m)
1198 (vs)
1206 (w)
1179 (vs)
νas(N3)
1022
828
1024
827
1024
825
1022 (vs)
979 (s)
908 (w)
828 (m)
761 (s)
1025
827
1064 (m)
993 (s)
923 (m)
830 (m)
743 (vs)
1044
1045 (m)
νs(N3)
912 (s)
952
828
940 (s)
826 (m)
755 (vs)
δsciss(NO2)ip
δrock(NO2)ip/oop
δsciss(NO2)oop
δwag(NO2)ip
822 (m)
738 (vs)
825
483
751 (vs)
464
473
477 (m)
470 (s)
471
478 (m)
470 (s)
470 (w)
471
478 (m)
470 (s)
476
477 (m)
470 (s)
δwag(NO2)oop
457 (m)
456 (m)
457 (m)
457 (m)
457 (m)
4414
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© 2008 Wiley-VCH Verlag GmbH & Co. KGaA, Weinheim
Eur. J. Inorg. Chem. 2008, 4413–4419

Triorganochalcogenium (Te, Se, S) Dinitramides
all resonances of the cations are very similar to the reso-
nances of the starting materials ([Ph3Te]Cl δ = 759 ppm,
CDCl3; [Me3Te]Cl δ = 441 ppm, D2O; [Ph3Se]Cl δ =
481 ppm, CDCl3; [Me3Se]I δ = 251 ppm, D2O) and also
comparable to known chalcogenium compounds such as
the previously reported azides [Ph3Te]N3 (δ = 795 ppm,
CDCl3), [Me3Te]N3 (δ = 456 ppm, D2O),[43] [Ph3Se]N3 (δ =
510 ppm, CDCl3), and [Me3Se]N3 (δ = 251 ppm, D2O).[44]
1
The 13C and H NMR spectra have also been recorded for
all compounds and display the expected resonances for
phenyl and methyl-substituted compounds, respectively (for
assignments see Exp. Sect.).
Compounds 1–6 were also characterized by their IR and
Raman spectra. For all compounds the characteristic bands
for the dinitramide anion were found and listed in Table 2.
Some fundamental vibrations show splittings, caused by
slight distortions and asymmetry of the structural variable
nitro groups. Moreover, the vibrational spectra of the solids
are dependent on the counterion. The comparison of the
experimental detected bands with previously reported ob-
served and calculated values[12,10] leads to an overall reason-
able agreement.
Figure 1. ORTEP plot of the molecular structure of 1; H atoms
omitted for clarity; selected bond lengths [Å] and angles [°]: Te1–
C1 2.112(4), Te1–C7 2.121(4), Te1–C13 2.112(4), Te1···O3 3.493(3),
Te1···O4 2.952(6), C1–Te1–C7 98.83(14), C1–Te1–C13 93.59(15),
C7–Te1–C13 97.67(14), O3···Te1···O4 38.03(7).
lurium–carbon bonds into account, a typical trigonal-py-
ramidal arrangement (AX3E) around the central tellurium
atom is formed. Besides the mentioned contacts to the di-
nitramide moiety of the asymmetric unit, two further inter-
molecular contacts to symmetry generated dinitramide
anions exist, which also have to be considered. The contacts
are shown in Figure 2 and exhibit Te···O distances of
3.414(1) [Te1···O1(i)/Te1(ii)···O1(iii)] and 3.089(9) Å
[Te1···O3(ii)/Te1(ii)···O3].
Crystal Structures
The potential coordination modes for the dinitramide
anion have been reported earlier and include monodentate
coordination to the central nitrogen atom of the dinitram-
ide skeleton, monodentate coordination to one oxygen
atom of the nitro groups, and bidentate coordination to two
oxygen atoms of the terminal nitro groups (Scheme 2).[11]
Scheme 2. Potential coordination modes for the dinitramide anion
(analogue to ref.[11]).
Recently we presented an example for monodentate co-
ordination mode to the central nitrogen atom and also for
chelate-type coordination by two oxygen atoms in
[pyH][N(NO2)2] and Li[N(NO2)2]·2H2O, respectively.[46]
Compound 1 crystallizes in the monoclinic crystal system,
space group P21/n with four molecules in the asymmetric
unit. The molecules exist in the first order as cation–anion
pairs with bidentate coordination of two oxygen atoms of
the dinitramide anion (Figure 1).
The intermolecular Te···O distances are 3.349(3) and
2.952(6) Å and are significantly shorter than the sum of the
tellurium–oxygen van der Waals radii (vdWr TeO 3.6 Å[47]).
The tellurium–carbon bond lengths are in the range be-
tween 2.11 and 2.12 Å and are together with the resulting
bond angles in good agreement with previously reported
Figure 2. Crystal structure of 1 showing all intermolecular contacts
(dashed lines) of the tellurium atoms; H atoms omitted for clarity;
selected distances [Å]: Te1···O1(i)/Te1(ii)···O1(iii) 3.414(1),
Te1···O3(ii)/Te1(ii)···O3 3.089(9), with i = 1 – x, –y, 1 – z; ii = –x,
triphenyltelluronium cations.[39,43] Taking only the tel- –y, 1 – z; iii = –1 + x, y, z.
Eur. J. Inorg. Chem. 2008, 4413–4419
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T. M. Klapötke, B. Krumm, M. Scherr
FULL PAPER
This leads to a distorted capped octahedral coordination the nitro groups are 2.585 Å (for 1) and 2.551 Å (for 3),
around the tellurium atom (coordination number seven) respectively (see Table 3). These values are comparable to
without taking the free valence electron pair of the tel- the structure of the ammonium salt of the dinitramide
lurium atom into account. In addition to the aforemen- anion (ADN).[13]
tioned bidentate contacts to the dinitramide moiety mono-
dentate contacts also exist to two additional dinitramide
moieties, which lead to a 3D layered structure.
In contrast to telluronium salt 1, selenonium salt 3 con-
sists of isolated cation–anion pairs with only monodentate
chalcogen–oxygen contacts (Figure 3). The compound also
crystallizes in the monoclinic crystal system and in the same
space group (P21/n) relative to the analogous telluronium
compound.
Table 3. Selected twist and torsion angles for the dinitramide ion
(for definitions, see refs.[13,30]).
Parameter
Te (1)
Se (3)
Twist (N2)
Twist (N3)
Bend (N2)
Bend (N3)
O···O
33.9
14.9
6.6
5.8
2.585
45.9
23.5
19.7
6.2
5.4
2.551
41.2
Torsion
In the course of our investigations we determined that
our previously reported crystal system for [Ag(py)2]-
[N(NO2)2] is not triclinic,[21] but monoclinic with cell axes
a = 6.1066(8) Å, b = 15.8561(16) Å, c = 13.934(2) Å and
an angle of 99.250(12)° [V = 1331.7(3) Å3], which could be
achieved by transforming the reported b axis. This leads to
the common space group P21/c with four molecules in the
asymmetric unit.
As a consequence of the herein reported successful syn-
theses of organochalcogenium dinitramides, the attempted
preparation of covalent organochalcogen dinitramide com-
pounds is currently underway and will be part of a future
publication.
Figure 3. ORTEP plot of the molecular structure of 3; H atoms
omitted for clarity; selected bond lengths [Å] and angles [°]: Se1–
C1 1.927(4), Se1–C7 1.930(4), Se1–C13 1.919(4), Se1···O4 2.979(4),
C1–Se1–C7 98.02(16), C1–Se1–C13 103.41(16), C7–Se1–C13
101.03(16).
Experimental Section
The selenium–carbon bond lengths are in the range be-
tween 1.92 and 1.93 Å and comparable to the previously
reported [Ph3Se]N3 [1.915(4) Å].[48] The intermolecular sele-
nium–oxygen distance is with 2.979(4) Å significantly
shorter than the sum of the selenium–oxygen van der Waals
radii (vdWr SeO 3.4 Å). This intermolecular contact leads
General Remarks: All manipulation of air- and moisture-sensitive
materials were performed under an inert atmosphere of dry argon
by using flame-dried glass vessels or oven-dried plastic equipment
and Schlenk techniques.[49] The solvents dichloromethane and ace-
tonitrile were dried by standard methods, stored under an atmo-
to a distorted trigonal–bipyramidal coordination (AX4E) sphere of N2, and freshly distilled prior to use. The telluronium/
selenonium/sulfonium salts,[50–54,37,55,56,43,57] and the silver di-
around the selenium atom. No further intermolecular con-
nitramide salts[12,21] were prepared according to literature pro-
cedures. All reagents were used as received (Sigma–Aldrich, Acros
Organics, Fluka, ABCR) if not stated otherwise. Preparation and
usage of the silver salts was performed under exclusion of light.
tacts below the sum of the van der Waals radii of the ele-
ments are present. This is in contrast to the structure of
telluronium salt 1 and likely an effect of the smaller size of
a selenium atom compared to a tellurium atom. The same
Infrared spectra were recorded with Perkin–Elmer Spektrum One
behavior has been reported previously for the comparable
FTIR or Nicolet 520 FTIR spectrometers (as neat liquids/solids or
azide salts [Ph3Te]N3 and [Ph3Se]N3.[43,48] Whereas in the
crystal structure of the telluronium salt various intermo-
Nujol mulls between KBr plates), Raman spectra were recorded
with a Perkin–Elmer 2000 NIR FT spectrometer fitted with a Nd-
lecular Te···N contacts are present, the structure of the sele-
YAG laser (1064 nm) as neat solids or liquids. Mass spectra were
nonium salts consists of isolated cation–anion pairs with no recorded with a Finnigan MAT 95Q or a JEOL MStation JMS
700 spectrometer. Multiisotope-containing fragments refer to the
isotope with the highest abundance (for example 130Te, 80Se). Ele-
mental analyses C, H, N were performed with a Netsch STA 429
simultaneous thermal analyzer by the analytical service of the De-
partment of Chemistry and Biochemistry, LMU. NMR spectra
were recorded with a JEOL Eclipse 400 instrument, and chemical
shifts were determined with respect to external Me4Si (1H,
399.8 MHz; 13C, 100.5 MHz), MeNO2 (14N/15N, 28.9/40.6 MHz),
Me2Se (77Se, 76.3 MHz), and Me2Te (125Te, 126.1 MHz). Due to
the temperature dependence of the 77Se/125Te NMR resonances, all
significant interactions.
In both crystal structures the dinitramide anions exhibit
the expected geometry with no intramolecular symmetry,
that is, C1 symmetry. The only known examples for intra-
molecular symmetry are to the best of our knowledge
Li[N(NO2)2],[13] Li[N(NO2)2]·2H2O[46] (both imposed C2
symmetry), and 3,3-dinitroazetidinium[17] (imposed mirror
plane). The nitro twist angles in 1 and 3 range from 19.7 to
33.9°, and the nitro bend angles are in the range between
5.4 and 6.6°, whereas the minimum O···O contact between samples were recorded at 25 °C. Yields of compounds 1–6 do not
4416 Eur. J. Inorg. Chem. 2008, 4413–4419
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© 2008 Wiley-VCH Verlag GmbH & Co. KGaA, Weinheim

Triorganochalcogenium (Te, Se, S) Dinitramides
depend on the employed dinitramide transfer reagent and are in
the range 90–98%. Elemental analyses could not be performed sat-
isfactorily for all compounds and are therefore only reported where
appropriate.
232 (44), 193 (27) cm–1. IR (KBr): ν = 3447 (br.), 3092 (s), 3058
˜
(s), 1582 (w), 1572 (m), 1499 (vs), 1441 (vs), 1319 (s), 1282 (m),
1196 (vs), 1171 (vs), 1069 (m), 1056 (m), 1009 (vs), 991 (vs), 919
(s), 822 (m), 747 (vs), 738 (vs), 683 (vs), 610 (m), 478 (m), 471 (s),
457 (m) cm–1. 1H NMR (CDCl3): δ = 7.46–7.31 (m) ppm. 13C{1H}
CAUTION! Silver dinitramide and dinitramide salts in general are
potentially explosive. This necessitates meticulous safety pre-
cautions during their preparation and handling, please see ref.[58]
NMR (CDCl3): δ = 133.8 (2JC,125Te = 35 Hz, o-C), 132.2 (p-C),
1
130.6 (3JC,125 = 8 Hz, m-C), 122.4 (1JC,125 = 245, JC,123
=
Te
Te
Te
203 Hz, CTe) ppm. 14N NMR (CDCl3): δ = –13 [N(NO2)2 ], –56
–
–
–
[br., N(NO2)2 ] ppm. 15N NMR (CDCl3): δ = –12.9 [N(NO2)2 ]
X-ray Crystallography: For all compounds an Oxford Xcalibur3
diffractometer with a CCD area detector was employed for data
collection by using Mo-Kα radiation (λ = 0.71073 Å). The struc-
tures (Table 4) were solved by direct methods (SHELXS[59] or
ppm. 125Te{1H} NMR (CDCl3): δ = 788 [1JTe,13C = 245 Hz, 1∆125Te
(
12/13C) = 80.3 ppb (10.1 Hz)] ppm. MS (FAB+): m/z (%) = 359
(100) [M]+, 282 (8) [M – Ph]+, 205 (4) [M – 2Ph]+. C17H15N3O4Te
SIR97[60]
)
and refined by full-matrix least-squares on F2
(464.92): calcd. C 46.5, H 3.3, N 9.0; found C 46.6, H 3.2, N 8.8.
(SHELXL[59]). All non-hydrogen atoms were refined anisotropi-
cally. ORTEP plots are shown with thermal ellipsoids at the 50%
probability level. CCDC-682940 (for 1) and -682939 (for 3) contain
the supplementary crystallographic data for this paper. These data
can be obtained free of charge from The Cambridge Crystallo-
graphic Data Centre via www.ccdc.cam.ac.uk/data_request/cif.
Triphenylselenonium Dinitramide [Ph Se][N(NO ) ] (3): Raman: ν
˜
3
2 2
= 3146 (12), 3070 (76), 1574 (41), 1421 (11), 1331 (35), 1162 (16),
1071 (18), 1024 (53), 1002 (100), 825 (20), 672 (39), 611 (19), 471
(13), 338 (14), 316 (28), 247 (49), 217 (21) cm–1. IR (KBr): ν = 3435
˜
(br.), 3092 (s), 3058 (s), 2999 (m), 1667 (w), 1572 (m), 1499 (vs),
1421 (vs), 1320 (s), 1281 (m), 1196 (vs), 1170 (vs), 1069 (m), 1009
(vs), 991 (vs), 918 (s), 842 (w), 822 (m), 738 (vs), 683 (vs), 610 (m),
Table 4. Crystal and structure refinement data.
1
478 (m), 470 (s), 457 (m) cm–1. H NMR (CDCl3): δ = 7.60–7.40
(m) ppm. 13C{1H} NMR (CDCl3): δ = 133.3 (p-C), 131.2 (3JC,77Se
= 6 Hz, m-C), 130.4 (2JC,77Se = 16 Hz, o-C), 125.5 (1JC,77Se = 83 Hz,
[Ph3Te][N(NO2)2] (1) [Ph3Se][N(NO2)2] (3)
Empirical formula
Formula mass
Temperature [K]
Crystal size [mm]
Crystal description
Crystal system
Space group
a [Å]
C18H15N3O4Te
464.93
200
C18H15N3O4Se
416.29
200
CSe) ppm. 14N NMR (CDCl3): δ = –12 [N(NO2)2 ], –56 [br.,
–
–
N(NO2)2 ] ppm. 77Se{1H} NMR (CDCl3): δ = 498 [1JSe,
13C = 83 Hz,
1∆77Se (12/13C) = 72.5 ppb (5.5 Hz)] ppm. MS (FAB+): m/z (%) =
311 (47) [M]+, 234 (11) [M – Ph]+, 154 (100) [M – 2Ph]+.
C17H15N3O4Se (416.28): calcd. C 51.9, H 3.6, N 10.1; found C 51.8,
H 3.6, N 10.0.
0.29ϫ0.20ϫ0.09
pale-orange block
monoclinic
P21/n
9.0860(7)
14.6781(12)
13.4522(11)
97.682(7)
1778.0(2)
4
0.21ϫ0.11ϫ0.02
colorless platelet
monoclinic
P21/n
9.1178(4)
14.0576(5)
13.6553(5)
95.361(4)
1742.60(12)
4
Triphenylsulfonium Dinitramide [Ph S][N(NO ) ] (5): Raman: ν =
˜
b [Å]
c [Å]
3
2 2
3155 (8), 3067 (81), 1579 (69), 1508 (5), 1448 (6), 1328 (19), 1292
(6), 1185 (12), 1166 (12), 1078 (40), 1067 (22), 1025 (63), 1002 (100),
949 (6), 827 (12), 704 (10), 688 (21), 612 (20), 471 (7), 428 (5), 256
β [°]
V [Å3]
Z
(35), 223 (15) cm–1. IR (neat): ν = 3059 (m), 1750 (w), 1701 (w),
˜
ρcalcd. [gcm–3]
1.737
1.702
1.587
2.184
1674 (w), 1579 (m), 1504 (vs), 1474 (vs), 1444 (vs), 1425 (s), 1346
(s), 1291 (w), 1174 (vs), 1156 (vs), 1064 (m), 993 (s), 923 (m), 830
µ [mm–1]
F(000)
912
840
1
(m), 743 (vs), 702 (w), 679 (vs), 478 (m), 470 (s), 457 (m) cm–1. H
θ range [°]
4.1–26.0
3.7–26.0
NMR (CDCl3): δ = 7.69–7.58 (m) ppm. 13C{1H} NMR (CDCl3):
–10 Յ h Յ 12
–17 Յ k Յ 20
–11 Յ l Յ 18
9144
2745
3472
–11 Յ h Յ 11
–16 Յ k Յ 17
–16 Յ l Յ 7
8928
1795
3422
δ = 134.6 (p-C), 131.5 (m-C), 130.8 (o-C), 123.8 (CS) ppm. 14N
Index ranges
–
–
NMR (CDCl3): δ = –11 [N(NO2)2 ], –58 [br., N(NO2)2 ] ppm.
Reflns. collected
Reflns. observed
Reflns. unique
General Procedure for the Preparation of Trimethyltelluronium/selen-
onium/sulfonium Dinitramide: To a solution of trimethyltellu-
ronium/selenonium/sulfonium chloride/iodide (1.1 mmol) in water
(10 mL) was added [Ag(NCCH3)][N(NO2)2] or [Ag(py)2][N(NO2)2]
(1.1 mmol) at 0 °C, and the mixture was stirred for 30 min. After
additional stirring for 6 h at ambient temperature, the resulting pre-
cipitate (AgCl/AgI) was filtered off, and all volatile materials of the
remaining solution were removed in vacuo, yielding pale-yellow oils
(2 and 4) and a solid (6).
(Rint = 0.0391)
0.0350, 0.0660
0.0520, 0.0734
0.8621/0.7142
3472/0/235
1.031
(Rint = 0.0749)
0.0375, 0.0625
0.0847, 0.0724
0.957/0.755
3422/0/235
0.818
R1, wR2 (2σ data)
R1, wR2 (all data)
Max./min. transm.
Data/restr./param.
GOOF on F2
Larg. diff. peak/hole [eÅ–3] 1.293/–0.383
0.745/–0.353
Trimethyltelluronium Dinitramide [Me Te][N(NO ) ] (2): Raman: ν
˜
3
2 2
General Procedure for the Preparation of Triphenyltelluronium/Selen-
onium/Sulfonium Dinitramide: To a solution of triphenyltellu-
ronium/selenonium/sulfonium chloride/bromide (1.1 mmol) in
dichloromethane (10 mL) was added [Ag(NCCH3)][N(NO2)2] or
[Ag(py)2][N(NO2)2] (1.1 mmol) at 0 °C, and the mixture was stirred
for 30 min. After additional stirring for 2 h at ambient temperature,
the resulting precipitate (AgCl/AgBr) was filtered off, and all vola-
tile materials of the remaining solution were removed in vacuo,
yielding pale-yellow solids.
= 3031 (10), 3013 (8), 2919 (20), 1569 (34), 1425 (14), 1329 (41),
1191 (12), 1051 (15), 1024 (62), 1008 (88), 827 (28), 548 (100), 539
(97), 473 (34) 237 (11) cm–1. IR (KBr): ν = 3423 (br.), 3010 (m),
˜
2916 (m), 1631 (m), 1406 (s), 1234 (w), 1206 (w), 912 (s), 861 (w),
832 (w), 751 (vs), 539 (m), 477 (m), 470 (s), 456 (m) cm–1. 1H NMR
(D2O): δ = 2.38 ppm. 13C{1H} NMR (CDCl3): δ = 5.0 ppm. 14N
–
–
NMR (CDCl3): δ = –14 [N(NO2)2 ], –58 [br., N(NO2)2 ] ppm.
125Te{1H} NMR (D2O): δ = 439 ppm. FAB+ MS: m/z (%) = 173
(100) [M+].
Triphenyltelluronium Dinitramide [Ph Te][N(NO ) ] (1): Raman: ν
Trimethylselenonium Dinitramide [Me Se][N(NO ) ] (4): Raman: ν
˜
3 2 2
˜
3
2 2
= 3146 (10), 3063 (63), 1575 (34), 1335 (22), 1168 (12), 1022 (43),
1000 (100), 828 (18), 660 (47), 613 (13), 464 (9), 288 (30), 267 (47),
= 3035 (38), 2939 (77), 1426 (24), 1328 (51), 825 (36), 607 (74), 585
(100), 483 (22) cm–1. IR (KBr): ν = 3441 (br.), 3019 (m), 2913 (w),
˜
Eur. J. Inorg. Chem. 2008, 4413–4419
© 2008 Wiley-VCH Verlag GmbH & Co. KGaA, Weinheim
www.eurjic.org
4417

T. M. Klapötke, B. Krumm, M. Scherr
FULL PAPER
[12] K. O. Christe, W. W. Wilson, M. A. Petrie, H. H. Michels, J. C.
Bottaro, R. Gilardi, Inorg. Chem. 1996, 35, 5068–5071.
[13] R. Gilardi, J. Flippen-Anderson, C. George, R. J. Butcher, J.
Am. Chem. Soc. 1997, 119, 9411–9416.
[14] A. Martin, A. A. Pinkerton, R. D. Gilardi, J. C. Bottaro, Acta
Crystallogr., Sect. B 1997, 53, 504–512.
1629 (m), 1528 (vs), 1431 (vs), 1384 (m), 1343 (s), 1293 (m), 1179
(vs), 1022 (vs), 979 (s), 953 (m), 908 (w), 828 (m), 761 (s), 732 (s),
1
1
575 (w), 470 (w) cm–1. H NMR ([D6]acetone): δ = 2.93 ppm. H
NMR (CD3CN): δ = 2.69 ppm. 13C{1H} NMR ([D6]acetone): δ
=22.2 ppm.13C{1H}NMR(CD3CN):δ=22.4 ppm.14NNMR([D6]-
acetone): δ = –11 [N(NO2)2 ], –58 [br., N(NO2)2 ] ppm. 14N NMR
–
–
[15] R. J. Butcher, R. D. Gilardi, J. Chem. Crystallogr. 1998, 28, 95–
–
–
(CD3CN): δ = –11 [N(NO2)2 ], –55 [br., N(NO2)2 ] ppm. 77Se{1H}
NMR ([D6]acetone): δ = 260 ppm. 77Se{1H} NMR (CD3CN): δ =
256 ppm. MS (FAB+): m/z (%) = 126 (100) [M]+.
104.
[16] R. D. Gilardi, R. J. Butcher, J. Chem. Crystallogr. 1998, 28,
105–110.
[17] R. D. Gilardi, R. J. Butcher, J. Chem. Crystallogr. 1998, 28,
Trimethylsulfonium Dinitramide [Me S][N(NO ) ] (6): Raman: ν =
˜
3
2 2
163–169.
3023 (47), 2933 (100), 1511 (10), 1424 (23), 1332 (52), 1189 (9),
1044 (13), 952 (14), 828 (35), 734 (51), 658 (84), 476 (21), 291 (41)
[18] R. D. Gilardi, R. J. Butcher, J. Chem. Crystallogr. 1998, 28,
673–681.
cm–1. IR (KBr): ν = 3019 (m), 2934 (w), 1505 (vs), 1416 (s), 1349
˜
[19] R. Gilardi, R. J. Butcher, J. Chem. Crystallogr. 2000, 30, 599–
(w), 1334 (w), 1198 (vs), 1045 (m), 996 (vs), 940 (m), 826 (m), 755
604.
(s), 719 (m), 477 (m), 470 (s), 457 (m) cm–1. H NMR (D2O): δ = [20] R. Gilardi, R. J. Butcher, J. Chem. Crystallogr. 2002, 32, 477–
1
2.87 ppm. 1H NMR ([D6]acetone): δ = 3.12 ppm. 13C{1H} NMR
(D2O): δ = 27.0 ppm. 13C{1H} NMR ([D6]acetone): δ = 29.8 ppm.
484.
[21] H.-G. Ang, W. Fraenk, K. Karaghiosoff, T. M. Klapötke, P.
Mayer, H. Nöth, J. Sprott, M. Warchhold, Z. Anorg. Allg.
Chem. 2002, 628, 2894–2900.
[22] H.-G. Ang, W. Fraenk, K. Karaghiosoff, T. M. Klapötke, H.
Nöth, J. Sprott, M. Suter, M. Vogt, M. Warchhold, Z. Anorg.
Allg. Chem. 2002, 628, 2901–2906.
[23] S. Venkatachalam, G. Santhosh, K. N. Ninan, Propellants Ex-
plos. Pyrotech. 2004, 29, 178–187.
[24] B. Berger, H. Bircher, M. Studer, M. Wälchli, Propellants Ex-
plos. Pyrotech. 2005, 30, 184–190.
[25] T. M. Klapötke, P. Mayer, A. Schulz, J. Weigand, J. Am. Chem.
Soc. 2005, 127, 2032–2033.
[26] P. Politzer, J. M. Seminario, M. C. Concha, P. C. Redfern, J.
Mol. Struct. 1993, 287, 235–240.
–
–
14N NMR (D2O): δ = –14 [N(NO2)2 ], –59 [br., N(NO2)2 ] ppm.
14N NMR ([D6]acetone): δ = –10 [N(NO2)2 ], –55 [br., N(NO2)2 ]
–
–
ppm.
Attempted Preparation of Trimethyloxonium Dinitramide
[Me3O][N(NO2)2]: To a solution of trimethyloxonium tetrafluo-
roborate (0.7 mmol) in dichloromethane (3 mL) was added
[Ag(NCCH3)][N(NO2)2] or [Ag(py)2][N(NO2)2] (0.7 mmol) at 0 °C,
and the mixture was stirred for 50 min. After that period a colorless
precipitate, insoluble in common organic solvents, was obtained
and a sample of the colorless supernatant for the NMR experiment
was taken. In that sample no evidence for the formation of
[Me3O][N(NO2)2] was found.
[27] P. Politzer, J. M. Seminario, Chem. Phys. Lett. 1993, 216, 348–
352.
[28] A. M. Mebel, M. C. Lin, K. Morokuma, C. F. Melius, J. Phys.
Chem. 1995, 99, 6842–6848.
[29] J. P. Ritchie, E. A. Zhurova, A. Martin, A. A. Pinkerton, J.
Phys. Chem. B 2003, 107, 14576–14589.
[30] A. A. Pinkerton, J. P. Ritchie, J. Mol. Struct. 2003, 657, 57–74.
[31] S. Löbbecke, H. H. Krause, A. Pfeil, Propellants Explos. Pyro-
tech. 1997, 22, 184–188.
[32] J. C. Bottaro, P. E. Penwell, R. J. Schmitt, J. Am. Chem. Soc.
1997, 119, 9405–9410.
[33] A. B. Andreev, O. V. Anikin, A. P. Ivanov, V. K. Krylov, Z. P.
Pak, Russ. Chem. Bull. 2000, 49, 1974–1976.
[34] M. T. Chen, J. W. George, J. Am. Chem. Soc. 1968, 90, 4580–
4583.
[35] J.-S. Lee, D. D. Titus, R. F. Ziolo, J. Chem. Soc., Chem. Com-
mun. 1976, 501–502.
[36] R. F. Ziolo, D. D. Titus, J. Appl. Crystallogr. 1976, 9, 506–507.
[37] R. F. Ziolo, K. Pritchett, J. Organomet. Chem. 1976, 116, 211–
217.
Acknowledgments
Financial support of this work by the University of Munich, the
Fonds der Chemischen Industrie, and the Deutsche Forschungsge-
meinschaft (KL 636/10–1) is gratefully acknowledged. We wish to
thank R. Moll, M.Sc. and the research student Mr. F. Huber for
their strong commitment during the preparation of some com-
pounds presented in this study.
[1] O. A. Luk’yanov, V. P. Gorelik, V. A. Tartakovsky, Russ. Chem.
Bull. 1994, 43, 89–92.
[2] J. C. Bottaro, P. E. Penwell, R. J. Schmitt, Synth. Commun.
1991, 21, 945–949.
[3] O. A. Luk’yanov, Y. V. Konnova, T. A. Klimova, V. A. Tar-
takovsky, Russ. Chem. Bull. 1994, 43, 1200–1202.
[4] O. A. Luk’yanov, O. V. Anikin, V. P. Gorlelik, V. A. Tartakov-
sky, Russ. Chem. Bull. 1994, 43, 1457–1461.
[5] O. A. Luk’yanov, N. I. Shlykova, V. A. Tartakovsky, Russ.
Chem. Bull. 1994, 43, 1680–1683.
[6] O. A. Luk’yanov, A. R. Agevnin, A. A. Leichenko, N. M. Sere-
gina, V. A. Tartakovsky, Russ. Chem. Bull. 1995, 44, 108–112.
[7] O. A. Luk’yanov, O. V. Anikin, V. A. Tartakovsky, Russ. Chem.
Bull. 1996, 45, 433–440.
[8] O. A. Luk’yanov, I. K. Kozlova, O. P. Shitov, Y. V. Konnova,
I. V. Kalinina, V. A. Tartakovsky, Russ. Chem. Bull. 1996, 45,
863–867.
[9] O. A. Luk’yanov, S. N. Shvedova, E. V. Shepelev, O. N. Varfol-
omeeva, N. N. Malkina, V. A. Tartakovsky, Russ. Chem. Bull.
1996, 45, 1497–1498.
[10] V. A. Shlyapochnikov, M. A. Tafipolsky, I. V. Tokmakov, E. S.
Baskir, O. V. Anikin, Y. A. Strelenko, O. A. Luk’yanov, V. A.
Tartakovsky, J. Mol. Struct. 2001, 559, 147–166.
[11] S. Trammell, P. A. Goodson, B. P. Sullivan, Inorg. Chem. 1996,
35, 1421–1422.
[38] D. D. Titus, J.-S. Lee, R. F. Ziolo, J. Organomet. Chem. 1976,
120, 381–388.
[39] J.-S. Lee, D. D. Titus, R. F. Ziolo, Inorg. Chem. 1977, 16, 2487–
2492.
[40] P. Ash, J.-S. Lee, D. D. Titus, K. B. Mertes, R. F. Ziolo, J. Or-
ganomet. Chem. 1977, 135, 91–101.
[41] F. H. Musa, W. R. McWhinnie, J. Organomet. Chem. 1978, 159,
37–45.
[42] T. M. Klapötke, B. Krumm, P. Mayer, K. Polborn, O. P. Rus-
citti, J. Fluorine Chem. 2001, 112, 207–212.
[43]
T. M. Klapötke, B. Krumm, P. Mayer, H. Piotrowski, I.
Schwab, M. Vogt, Eur. J. Inorg. Chem. 2002, 2701–2709.
T. M. Klapötke, B. Krumm, P. Mayer, H. Piotrowski, K. Pol-
born, I. Schwab, Z. Anorg. Allg. Chem. 2002, 628, 1831–1834.
T. M. Klapötke, B. Krumm, M. Scherr, manuscript submitted.
T. M. Klapötke, B. Krumm, M. Scherr, Acta Crystallogr., Sect.
C 2008, 64, m17-m19.
[44]
[45]
[46]
[47]
A. Bondi, J. Phys. Chem. 1964, 68, 441–451.
4418
www.eurjic.org
© 2008 Wiley-VCH Verlag GmbH & Co. KGaA, Weinheim
Eur. J. Inorg. Chem. 2008, 4413–4419

Triorganochalcogenium (Te, Se, S) Dinitramides
[48]
[49]
[56] W. A. Herrmann, G. Brauer, F. T. Edelmann, D. K. Breitinger,
H. H. Karsch, N. Auner, Synthetic Methods of Organometallic
and Inorganic Chemistry, Thieme, Stuttgart, 1996.
[57] S. Imazeki, M. Sumino, K. Fukasawa, M. Ishihara, T. Aki-
yama, Synthesis 2004, 10, 1648–1654.
[58] T. M. Klapötke, B. Krumm, M. Scherr, R. Haiges, K. O. Chri-
ste, Angew. Chem. Int. Ed. 2007, 46, 8686–8690.
[59] G. M. Sheldrick, SHELX-97, University of Göttingen, Ger-
many, 1997.
T. M. Klapötke, B. Krumm, P. Mayer, H. Piotrowski, K. Pol-
born, I. Schwab, Z. Anorg. Allg. Chem. 2002, 628, 1831–1834.
D. F. Shriver, M. A. Drezdzon, The Manipulation of Air Sensi-
tive Compounds, Wiley, New York, 1986.
C. Lederer, Ber. Dtsch. Chem. Ges. 1911, 44, 2287–2292.
H. M. Leicester, F. W. Bergstrom, J. Am. Chem. Soc. 1929, 51,
3587–3591.
[50]
[51]
[52] H. M. Leicester, Org. Synth., Coll. Vol. 2 1957, 240–241.
[53] D. Hellwinkel, G. Fahrbach, Chem. Ber. 1968, 101, 574–584.
[54] W. H. H. Günther, J. Nepywoda, J. Y. C. Chu, J. Organomet.
Chem. 1974, 74, 79–84.
[55] N. Kuhn, P. Faupel, E. Zauder, J. Organomet. Chem. 1986, 302,
C4–C6.
[60] A. Altomare, G. Cascarano, C. Giacovazzo, A. Guagliardi,
A. G. G. Moliterni, M. C. Burla, G. Polidori, M. Camalli, R.
Spagna, SIR97, 1997.
Received: June 4, 2008
Published Online: August 25, 2008
Eur. J. Inorg. Chem. 2008, 4413–4419
© 2008 Wiley-VCH Verlag GmbH & Co. KGaA, Weinheim
www.eurjic.org
4419