Synthesis and structures of triorganotelluronium pseudohalides

Article abstract of DOI:10.1002/1099-0682(200210)2002:10<2701::AID-EJIC2701>3.0.CO;2-G

The syntheses of [(CH₃)₃Te]X {X = N₃ (1), OCN (2), SCN (3), SeCN (4), [Ag(CN)₂] (5)} and [(C₆H₅)₃Te]X {X = N₃ (6), SeCN (7), [Ag(CN)₂] (8)}, their NMR spectroscopic data, vibrational spectra and single crystal structures are described. Compounds 1-4 are the first trimethyltelluronium pseudohalides, while the known compounds 6 and 7 have been prepared for completion of their analytical and structural properties. The occurrence of intermolecular Te···N, Te···O, Te···S and Te···Se contacts is thoroughly studied. The dicyanoargentates 5 and 8 were obtained in an attempt to prepare telluronium cyanides. Low-temperature ¹³C NMR spectroscopy of the [Ag(CN)₂]^- ion in solution has been carried out, with determination of the ¹³C-^107/109Ag coupling. Wiley-VCH Verlag GmbH, 69451 Weinheim, Germany, 2002.

Full text of DOI:10.1002/1099-0682(200210)2002:10<2701::AID-EJIC2701>3.0.CO;2-G

FULL PAPER
Synthesis and Structures of Triorganotelluronium Pseudohalides
Thomas M. Klapötke,*[a] Burkhard Krumm,[a] Peter Mayer,[a][‡] Holger Piotrowski,[a][‡]
Ingo Schwab,[a] and Martin Vogt[a][‡]
Dedicated to Professor D. Naumann on the occasion of his 60th birthday
Keywords: Tellurium / Azides / NMR spectroscopy / Noncovalent interactions
The syntheses of [(CH3)3Te]X {X = N3 (1), OCN (2), SCN (3),
SeCN (4), [Ag(CN)2] (5)} and [(C6H5)3Te]X {X = N3 (6), SeCN
(7), [Ag(CN)2] (8)}, their NMR spectroscopic data, vibrational
contacts is thoroughly studied. The dicyanoargentates 5 and
8 were obtained in an attempt to prepare telluronium cyan-
ides. Low-temperature 13C NMR spectroscopy of the
spectra and single crystal structures are described. Com- [Ag(CN)2]− ion in solution has been carried out, with deter-
pounds 1−4 are the first trimethyltelluronium pseudohalides,
while the known compounds 6 and 7 have been prepared for
completion of their analytical and structural properties. The
mination of the 13C−107/109Ag coupling.
( Wiley-VCH Verlag GmbH, 69451 Weinheim, Germany,
occurrence of intermolecular Te···N, Te···O, Te···S and Te···Se 2002)
Introduction
to explore the chemistry of main-group element azides, we
report here on the first single-crystal structural determina-
tion of telluronium azides. [(CH3)3Te]N3 (1) and
[(C6H5)3Te]N3 (6) complete the series RnTe(N3)4Ϫn (R ϭ
CH3 or C6H5; n ϭ 1, 2, 3), of which both (CH3)2Te(N3)2
and CH3Te(N3)3, as well as (C6H5)2Te(N3)2 and
C6H5Te(N3)3 were recently synthesized and character-
ized.[17,18]
Pursuing the work of Ziolo, we intended to complete his
examinations of 6 and 7 with modern spectroscopic and
crystallographic methods. Moreover, the scope of telluron-
ium pseudohalides should be extended to the smallest com-
pounds, trimethyltelluronium salts. Thus, the preparation of
a series of trimethyltelluronium chalcogenocyanates 2Ϫ4
was of further interest.
Telluronium salts [R3Te]X have been known for more
than a hundred years.[1,2] Some experimental work has been
carried out since then, synthesizing telluronium cations
with various substituents. In the 1970s Ziolo reported on
the first telluronium pseudohalides [(C6H5)3Te]X (X ϭ N3,
CN, OCN, SCN, SeCN),[3,4] with no NMR spectroscopic
characterization, but single-crystal X-ray data for
[(C6H5)3Te]OCN and [(C6H5)3Te]SCN.[5Ϫ7]
The preparation and characterization of tris(perfluoro-
phenyl)tellurium() halides (RF)3TeCl and (RF)3TeBr
(RF ϭ C6F5, CF3C6F4) was achieved recently.[8] Their X-ray
crystallographic analysis and properties revealed structures
consistent with a rather covalent constitution.
An attempt to prepare telluronium cyanides, omitting the
use of an anion exchange resin,[4] will be reported. This
work can be seen in context with a very recent report,
dealing with structural investigations of several triphenyltel-
luronium transition metallates.[19]
Telluronium halides and pseudohalides bearing nonfluor-
inated substituents are in most cases widely ionic and show
strong electrolyte behavior in solution.[9,10] Dihalotelluranes
R2TeX2 feature intermolecular interactions in the solid
state, whose distances lie between those of the sum of cova-
lent and van der Waals radii.[11Ϫ13] Similar secondary inter-
actions[14] have also been found in telluronium salts.[15,16]
To the best of our knowledge, no trimethyltelluronium
pseudohalide has been reported, and continuing our efforts
Results and Discussion
Synthesis
[‡]
Suitable precursors for the synthesis of telluronium com-
pounds [R3Te]X are the corresponding telluronium halides.
These can be obtained either by the reaction of Grignard
reagents with tellurium tetrachloride,[2] or the aqueous ha-
X-ray structure analyses
[a]
Department Chemie, Ludwig-Maximilians-Universität,
Butenandtstr. 5Ϫ13 (D), 81377 München, Germany
Fax: (internat.) ϩ 49-(0)89/2180-7492
E-mail: tmk@cup.uni-muenchen.de
Eur. J. Inorg. Chem. 2002, 2701Ϫ2709  WILEY-VCH Verlag GmbH, 69451 Weinheim, Germany, 2002 1434Ϫ1948/02/1010Ϫ2701 $ 20.00ϩ.50/0
2701

T. M. Klapötke, B. Krumm, P. Mayer, H. Piotrowski, I. Schwab, M. Vogt
FULL PAPER
logenation of tetraalkyl- or tetraaryltelluranes, generated in
situ [Equation (1)].[20]
Of further interest in this study would be a telluronium
cyanide. The only report of such a compound was also
given by Ziolo, who stated that its synthesis had succeeded
with the use of an anion exchange resin.[4] Applying the
methods mentioned before, mostly led to the formation of
an unidentified red decomposition product, after trimethyl-
or triphenyltelluronium chloride had been treated with ex-
cess of KCN and evaporated subsequently. The use of silver
cyanide produced the highly stable dicyanoargentate salts
[(CH3)3Te][Ag(CN)2] (5) and [(C6H5)3Te][Ag(CN)2] (8),
since the complex dicyanoargentate anion formed during
the reaction is more stable than the corresponding silver
halides [Equation (5)]. Although their synthesis was not an
initial goal, they were fully characterized including X-ray
crystallography.
(1)
Another method for the preparation of [(C6H5)3Te]Cl is
the FriedelϪCrafts type arylation of tellurium tetrachloride
with benzene and aluminum trichloride.[21] Some references
stated this as a method suitable for the preparation of
[(C6H5)3Te]Cl. However, it was found by tracing this reac-
tion at different temperatures up to 90 °C, that the latter
approach is somewhat slower than reported.[21] Addition-
ally, minor impurities of (C6H5)2TeCl2 are always present
in the isolated product, which was proven by 125Te NMR
spectroscopy with a resonance at δ ϭ 920 ppm.
The synthesis of trimethyltelluronium pseudohalides 1Ϫ4
is achieved by reaction of the corresponding silver
pseudohalides with trimethyltelluronium iodide in aqueous
or ethanolic solutions [Equation (2)].
(5)
Vibrational Spectra
(2)
In their IR (strong), as well as their Raman (weak) spec-
tra, the antisymmetric stretching vibration νasN3 is visible
for both telluronium azides 1 and 6. They are found in the
region of 2030Ϫ2000 cmϪ1 similar as found for the νasN3
of covalent tellurium() azides.[17,18] Since 1 and 6 exhibit
ionic character, the difference between their νasN3 frequen-
cies and that of ionic azide ion in NaN3 (νasN3 ϭ 2041
The trimethyltelluronium pseudohalides are colorless
salt-like substances which slowly release dimethyltellane as
a product of their reductive decomposition [Equation (3)].
(3)
cmϪ1, νsN3 ϭ 1344 cmϪ1 [22]
is negligible. The symmetric
)
Another method of preparation of telluronium
pseudohalides is employed for the preparation of 6 and 7.
As previously described,[4] they can be obtained by a two-
phase exchange reaction of [(C6H5)3Te]Cl with an excess of
NaN3 (6), and by simply precipitating a hot aqueous solu-
tion with excess KSeCN (7) [Equation (4)]. Since 6 and 7
are known compounds, they have been prepared for further
spectroscopic and structural characterization and in order
to compare the properties of telluronium pseudohalides
with different cations.
stretching vibration, νsN3, is visible in the Raman spectra
at 1376 cmϪ1 for 1, and 1328 cmϪ1 for 6 with medium in-
tensity and in the IR spectra with weak intensity.
Compounds 2Ϫ4 and 7 are chemically related and may
be described together. Again, comparison of their vibra-
tional spectra, namely the νasXCN vibration, shows only
minor differences from the precursors. As found for 1 and
6, the telluronium chalcogenocyanates exhibit ionic nature
as well. No coordination effects in solution have been
proven (NMR section), but the coordination in the solid
state shows a significant effect, accounting for a shift of 20
cmϪ1 on the SϪC stretching vibration of the SCNϪ moiety
in the Raman spectrum of 3 (732 cmϪ1), compared to 749
cmϪ1 in KSCN (Table 1).
(4)
Table 1. IR/Raman vibrational frequencies of trimethyltelluronium pseudohalides
[a]
1
2
3
4
ν3
2027, 1998/1999
1998[b]/[c]
2170/2135
2155[23]
2076, 2058/2058
2060/2058[24] [d]
732
2065/2065
ν3(KN3/KXCN)
ν1
ν1(NaN3/KXCN)
2071/2076[25]
[e]
Ϫ/1323
1288/1290
1342[b]
1282[23]
741/749[24] [d]
561[25]/556
[a] In cmϪ1
tions.
.
[b] See ref.[26] and references therein. [c] Inactive. [d] Refers to [Me4N]NCS. [e] Not observed due to overlapping with other vibra-
2702
Eur. J. Inorg. Chem. 2002, 2701Ϫ2709

Synthesis and Structures of Triorganotelluronium Pseudohalides
FULL PAPER
Table 2. NMR spectroscopic data
[a][b]
1
2
3
4
5
6
7
8[c]
1H
2.29
23.7
4.4
2.28
23.7
2.31
24.6
2.31
23.7
2.30
23.7
7.79Ϫ7.31
7.79Ϫ7.31
7.61Ϫ7.48
2JHϪTe
13C
128.8 (OCN), 133.7 (SCN), 120.6 (SeCN), 149.0 (CN), 134.3 (C2),
4.5 (CH3)
134.7 (C2),
131.9 (C4),
130.7 (C3),
125.9 (C1),
147.0 (CN),
134.7 (C2),
132.7 (C4),
131.1 (C3),
4.5 (CH3)
4.5 (CH3)
4.4 (CH3) 131.3 (C4),
130.2 (C3),
127.9 (C1)
117.3 (SeCN) 123.5 (C1)
1JCϪTe
158.3
147.6
21.1
147.6
147.6
150.6
249.3
30.8
247.5
31.6
245.6
33.1
2JCϪTe
1JCϪN(Se)
268.7
256.2
14N (∆ν1/2
)
Ϫ132 (Nβ, 20), Ϫ304 (10)
Ϫ266 (Nαγ, 60)
Ϫ176 (90)
Ϫ144 (140)
Ϫ106 (400) Ϫ133 (Nβ, 50), Ϫ130 (1000) Ϫ110 (Ͼ2000)
Ϫ260 (Nαγ, 20)
Ϫ144 (br)
77Se
Ϫ324
441
23.6
125Te
456
443
24.1
δ ϭ 441
23.7
441
795
759
773
2JTeϪH
24.6
23.6
[a]
[b]
1Ϫ5 in D2O, 6Ϫ8 in CDCl3. J and ∆ν1/2 in Hz. [c] 109Ag shift δ ϭ 593 ppm.
Comparison of the Raman spectra of [(CH3)3Te]- NMR resonance increases with the chemical shift. This re-
[Ag(CN)2] (5) and [(C6H5)3Te][Ag(CN)2] (8) with the Ra- flects the change in electronegativity and shielding proper-
man spectrum of crystalline K[Ag(CN)2] (νCN ϭ 2140 ties of the chalcogen atom in the chalcogenocyanate moiety.
cmϪ1 [27]
)
shows that νCN is slightly shifted to 2132 cmϪ1
An interesting temperature-dependent behavior is ob-
(5) and 2135 cmϪ1 (8). Further deviations are not detected. served for the 13C NMR resonance of [(C6H5)3Te]-
The vibrational data indicate that all compounds consist [Ag(CN)2] (8). At 25 °C, a single resonance at δ ϭ 143 ppm
of discrete ions in the solid state.
is detected for the cyano resonance. Variable-temperature
measurements of the 13C NMR spectra of 8 between Ϫ100
°C and 60 °C in [D8]THF show, that below 25 °C the CN
resonance broadens, and at ca. Ϫ80 °C two resonances be-
come visible (Figure 1a). Finally, at Ϫ100 °C, both the
NMR Spectra
The NMR spectroscopic data (Table 2) confirm the salt-
like nature of the compounds. In case of the azides, two
resonances were observed in the 14N NMR spectra at δ ϭ
Ϫ132 (Nβ) and Ϫ266 (Nαγ) ppm for 1 and δ ϭ Ϫ132 (Nβ)
and Ϫ272 (Nαγ) ppm for 6. This strongly suggests, that in
solution 1 and 6 are completely dissociated into telluronium
cations and azide anions, since for covalently bound azides,
three distinct 14N resonances are observed.[17,18] The 125Te
NMR spectra show resonances at δ ϭ 443 ppm (D2O) and
δ ϭ 456 ppm (CDCl3) for 1 and δ ϭ 795 ppm (CDCl3) for
6, which, as expected, are very similar to the shifts of the
starting materials [(CH3)3Te]I [δ ϭ 441 ppm (D2O)] and
[(C6H5)3Te]Cl [δ ϭ 759 ppm (CDCl3)], respectively. The
corresponding triorganoselenonium azides are discrete ions
in solution as well.[28]
107
109
1J13
Ag (J ϭ 183 Hz) and the 1J13
Ag (J ϭ 209 Hz)
CϪ
CϪ
coupling is resolved (Figure 1b). A similar feature has been
reported for K[Ag(CN)2] in DMF upon cooling below
Ϫ50 °C.[29]
The coupling with silver isotopes 107Ag (I ϭ Ϫ1/2,
51.82%) and 109Ag (I ϭ Ϫ1/2, 48.18%)[30] can be observed
only at low temperatures, often explained as a result of fast
exchange mechanisms.[31Ϫ34] For 8, the calculated ratio of
the coupling constants 0.876 is very close to that predicted
by the theoretical ratio of the gyromagnetic constants
γ107Ag/γ109 ϭ 0.869.
Ag
For compounds 2Ϫ5, 7, and 8, only minor variations of
the 125Te chemical shift are found, proving the negligible
effect of the counterion on the telluronium cation in solu-
Crystal Structures
As indicated earlier, the crystal structures of [Ph3Te]X
tion. This is consistent with the 125Te NMR spectroscopic (X ϭ OCN, SCN)[5Ϫ7] are known, but for X ϭ N3 (6) and
data of [(C6H5)3Te]2[MCl6] (M
ϭ
Ir, Pt) and X ϭ SeCN (7) only powder diffraction data existed.[3]
[(C6H5)3Te][AuCl4].[19]
Hence, for all compounds described in the synthesis section,
The 77Se NMR shift of [(CH3)3Te]SeCN (4) in D2O is single-crystal structure determinations have been carried
δ ϭ Ϫ324 ppm, which is very similar to that of KSeCN in out. Our focus has been set especially on the interactions
D2O (δ ϭ Ϫ340 ppm) and [(CH3)3Se]SeCN [δ(SeCN) ϭ between the telluronium cations and the different anions,
Ϫ328 ppm],[28] but notably different to that of [(C6H5)3Te]- leading to an extended coordination sphere around the tel-
SeCN (7) in CDCl3 (δ ϭ Ϫ144 ppm). This is believed to lurium centre (Table 3). The concept of secondary interac-
be mainly a solvent effect.[10] On going from cyanate 2 to tions[14] also applies for telluronium compounds[5,6,19,35,36]
thiocyanate 3 and selenocyanate 4, the linewidth of the 14
N
and was subject to a detailed study.[15,16]
Eur. J. Inorg. Chem. 2002, 2701Ϫ2709
2703

T. M. Klapötke, B. Krumm, P. Mayer, H. Piotrowski, I. Schwab, M. Vogt
FULL PAPER
and octacoordination of Te is found,[17,18] containing al-
most linear azide groups connected to the tellurium ion
˚
with TeϪC bond lengths of ca. 2.2 A. The interatomic
˚
Te···N distances are in the range of 2.7Ϫ3.5 A.
In contrast, the structures of [(CH3)3Te]N3 (1) (Figure 2)
and [(C6H5)3Te]N3 (6) (Figure 3) show almost perfectly lin-
ear azide groups connected on both sides to different layers
of telluronium cations. The azide 6 crystallizes as a chloro-
form solvate (see Table 4). In both azides 1 and 6, the NϪN
˚
bond lengths (1.15Ϫ1.18 A) differ only slightly from each
other. This is in agreement with the crystal structure of the
azide anion in [(CH3)4N]N3, and demonstrates the minor in-
fluence of the secondary bonds on the bonding situation of
the azide group.[26] The average secondary bonding Te···N
˚
distances amount to 3.0 A, which is well below the sum of
the telluriumϪnitrogen van der Waals radii (ΣvdWr TeϪN
3.61 A).[37] This leads mostly to a monocapped distorted oc-
˚
tahedral AX3Y3E environment and a complex three-dimen-
sional network of cations and anions (Figure 2).
The TeϪC bond lengths for the telluronium cations
[(CH3)3Te]ϩ (in 1Ϫ5) and [(C6H5)3Te]ϩ (in 6Ϫ8) span
˚
ranges between 2.11 and 2.14 A, and are together with the
resulting bond angles in good agreement with those of
[(CH3)3Te]I[38] and [(C6H5)3Te]SCN.[7] Regarding only
TeϪC bonds, a typical AX3E trigonal-pyramidal arrange-
ment around the tellurium centre is formed.
Similarly, the CϪN and CϪO(S)(Se) bond lengths in the
chalcogenocyanate anions of 2Ϫ4 and 7 exhibit only mar-
ginal deviations to those found in the potassium salts. The
˚
bond lengths of the cyanate anions in 2 [CϪN 1.168(4) A,
˚
CϪO 1.217(4) A] are very similar to those of
[5]
[(C6H5)3Te]OCN·1/2CHCl3
and
KOCN.[39]
For
[(CH3)3Te]SCN (3), the distances are very similar, the CϪN
˚
˚
[1.143(8) A] and CϪS [1.662(5) A] bonds being negligibly
˚
shortened when compared to KSCN [CϪN 1.15(1) A, CϪS
[40]
˚
˚
Figure 1: (a) Variable-temperature 13C NMR spectra of [Ph3Te]-
[Ag(CN)2] (8) in [D8]THF; asterisks denoting 125Te satellites; (b)
13C NMR spectrum of 8 in [D8]THF at Ϫ100 °C
1.69(1) A]. The selenocyanate ions in 4 [CϪN 1.146(7) A,
˚
˚
CϪSe 1.816(5) A] and 7 [CϪN 1.142(8)/1.148(6) A, CϪSe
1.804(5)/1.817(6) A] feature bond lengths, which also can-
˚
not be considered significantly different from those in
KSeCN.[41] As discussed for AgSeCN,[42] this is in agree-
In covalent tellurium azides, R2Te(N3)2 and RTe(N3)3, in- ment with a slightly elongated CϪN triple bond and a
cluding the free electron pair at the tellurium centre, hepta- CϪSe bond with minor multiple bond contribution.
˚
Table 3. Summary of Te···X interactions [A]
1
2
3
4
5
6
7
8
Te···N
2.938(4)
3.006(4)
3.032(3)
3.018(5)
3.037(3)
2.983(3)
3.103(3)
3.185(3)
3.252(4)
3.154(5)
3.270(5)
3.407(6)
2.772(4)
2.867(4)
2.946(4)
3.000(4)
3.027(4)
3.122(5)
3.162(4)
3.346(5)
3.501(5)
Te···O
Te···S
3.095(2)
3.390(1)
3.488(1)
Te···Se
3.4712(5)
3.5534(6)
3.4424(6)
3.5413(6)
2704
Eur. J. Inorg. Chem. 2002, 2701Ϫ2709

Synthesis and Structures of Triorganotelluronium Pseudohalides
FULL PAPER
˚
Figure 4. ORTEP plot of 2; selected bond lengths [A] and angles
[°]: TeϪC1 2.113(3), TeϪC2 2.121(3), TeϪC3 2.110(3), OϪC4
1.217(4), NϪC4 1.168(4), Te···O 3.095(2), Te···N(i) 2.983(3),
Te···N(ii) 3.103(3), C1ϪTeϪC2 94.8(1), C3ϪTeϪC1 93.3(1),
C3ϪTeϪC
2
95.4(1), NϪC4ϪO 178.5(3), Te···N(i)···Te(iii)
83.14(7), N(i)···Te···N(ii) 96.86(7); with i ϭ 11/2 Ϫ x, y Ϫ 1/2, Ϫ1/
2 Ϫ z; ii ϭ x Ϫ 1/2, 1/2 Ϫ y, 1/2 ϩ z; iii ϭ 1 Ϫ x, Ϫy, Ϫz
˚
Figure 2. ORTEP plot of 1; selected bond lengths [A] and angles
[°]: N12ϪN22 1.164(4), N22ϪN32 1.173(4), Te1ϪC11 2.112(4),
Te1ϪC21 2.114(3), Te2ϪC12 2.143(5), Te2ϪC22 2.122(3),
Te3ϪC13 2.107(5), Te3ϪC23 2.111(3), Te1···N11 3.006(4),
Te1···N12 3.032(3), Te2···N11 2.938(4), Te3···N31 3.018(5),
Te3···N32(ii) 3.037(3), N12ϪN22ϪN32 179.3(4), C11ϪTe1ϪC21
93.9(1); with i ϭ x, 1/2 Ϫ y, z; ii ϭ 1 ϩ x, y, z; iii ϭ 1 ϩ x, 1/2 Ϫ
y, z; iv ϭ Ϫx, Ϫy, Ϫz; v ϭ Ϫx, 1/2 ϩ y, Ϫz
˚
Figure 5. ORTEP plot of 3; selected bond lengths [A] and angles
[°]: TeϪC1 2.115(3), TeϪC2 2.113(4), TeϪC3 2.120(3), Te···S
3.488(1), Te···S(i) 3.390(1), Te(ii)···S 3.390(1), Te···N(iii) 3.185(3),
SϪC4 1.662(5), NϪC4 1.143(8), C1ϪTeϪC3 92.7(2), C2ϪTeϪC1
93.7(2), C2ϪTeϪC3 96.7(2), NϪC4ϪS 178.5(4), Te···S···
Te(ii)···167.83(3); with i ϭ 1 Ϫ x, 1 Ϫ y, 1/2 ϩ z; ii ϭ 1 Ϫ x, 1 Ϫ
y, z Ϫ 1/2; iii ϭ 1 Ϫ x ϩ 1/2, 2 Ϫ y, 1/2 ϩ z
torted monocapped octahedral AX3Y3E environments in-
dicate secondary bonding between cations and anions as
well. An analogous structure was reported for β-[Te-
Cl3][AlCl4], considering primary TeϪCl and secondary
Te···Cl bonds.[15] As chalcogenocyanates are ambidentate li-
gands, it is of interest, whether Te···X [X ϭ O, S, Se; ΣvdWr
˚
TeO(S)(Se) 3.58, 3.86, 3.96 A)], or Te···N contacts or both
Figure 3. ORTEP plot of 6; solvate molecules and H atoms omitted
˚
for clarity; selected bond lengths [A] and angles [°]: TeϪC
are preferred. The crystal structures show, that Te···N as
well as Te···X coordination is present. Compounds 3, 4 and
7 exhibit two Te···S(Se) and one Te···N contact each, 3 and
4 crystallize isotypically. The cyanate ion in 2, which has
the oxygen atom as its ‘‘hard end’’, shows an inverted situ-
ation. This can be explained according to the HSAB con-
cept,[43,44] considering a telluronium cation as a rather weak
2.121(4)Ϫ2.146(4), N11ϪN21 1.181(5), N21ϪN31 1.161(5),
N12(ii)ϪN22(ii) 1.184(5), N22(ii)ϪN32(ii) 1.170(5), Te1···N11
2.867(4), Te2(ii)···N12(ii) 2.772(4), Te2(ii)···N31 3.027(4), CϪTeϪC
92.6(2)Ϫ98.8(2), N11(ii)ϪN21(ii)ϪN31(ii) 179.6(5), N12ϪN22Ϫ
ϪN3x2, 1Ϫ7y9,.11(5Ϫ); zwith i ϭ Ϫx, Ϫy, 1 Ϫ z; ii ϭ Ϫ1 ϩ x, y, z; iii ϭ 1
For compounds 2Ϫ4 and 7 (Figure 4Ϫ7), similar net- acid, preferring coordination to the softer ends of the par-
work-like structures as for the azides 1 and 6 exist. Dis- ticular anions. In the solid state the N···Te contacts in 2Ϫ4
Eur. J. Inorg. Chem. 2002, 2701Ϫ2709
2705

T. M. Klapötke, B. Krumm, P. Mayer, H. Piotrowski, I. Schwab, M. Vogt
FULL PAPER
are oriented staggered in an angle of 75° to each other, al-
ternately coordinated to telluronium cations. In the phenyl
derivative 8, the corresponding angle is 84° (Figure 9). The
coordination sphere around tellurium consists of two
shorter and one longer Te···N contacts, the latter being only
˚
0.1 A below the sum of the van der Waals radii of TeϪN
˚
3.61 A. This again can be regarded as a distorted mono-
capped octahedral AX3Y3E arrangement.
˚
Figure 6. ORTEP plot of 4; selected bond lengths [A] and angles
[°]: Te1ϪC11 2.107(3), Te1ϪC21 2.124(4), Te1ϪC31 2.121(4),
C1ϪN1 1.146(7), Se1ϪC1 1.816(5), Te1···N1(ii) 3.252(4), Te1···Se1
3.5534(6), Te1···Se1(i) 3.4712(5), C11ϪTe1ϪC21 93.5(2),
C11ϪTe1ϪC31 93.3(2), C31ϪTe1ϪC21 96.6(2), N1ϪC1ϪSe1
178.0(4); with i ϭ 1 Ϫ x, 1 Ϫ y, Ϫ1/2 ϩ z; ii ϭ 1 Ϫ x, Ϫy, Ϫ1/2
ϩ z; iii ϭ 1 Ϫ x, 1 Ϫ y, 1/2 ϩ z
˚
Figure 8. ORTEP plot of 5; selected bond lengths [A] and angles
[°]: TeϪC3 2.102(5), TeϪC4 2.100(5), TeϪC5 2.109(6), C1ϪN1
1.098(6), C2ϪN2 1.143(7), Ag1ϪC1 2.074(5), Ag2ϪC2 2.055(6),
Te···N1 3.270(5), Te···N2 3.407(6), Te···N2(i) 3.154(5), Ag1···Ag2
3.1670(3), C4ϪTeϪC3 95.9(2), C4ϪTeϪC5 95.1(3), C3ϪTeϪC5
93.6(3), C1ϪAg1ϪC1(iii) 180.000(1), C2ϪAg2ϪC2(ii) 180.000(1),
N1ϪC1ϪAg1 178.3(5), N2ϪC2ϪAg2 178.6(5), C1ϪAg1Ϫ
Ag2ϪC2 Ϫ74.9(2); with i ϭ Ϫx, Ϫy, 1 Ϫ z; ii ϭ 1 Ϫ x, Ϫy, 2 Ϫ
z; iii ϭ Ϫx, Ϫy, 2 Ϫ z
Figure 7. ORTEP plot of 7; only Te-bonded atoms of phenyl
˚
groups shown; selected bond lengths [A] and angles [°]: Te1ϪC11
2.126(5), Te1ϪC12 2.139(5), Te1ϪC13 2.137(4), Te2ϪC14 2.128(5),
Te2ϪC15 2.120(5), Te2ϪC16 2.128(5), N1ϪC1 1.148(6), N2ϪC2
1.142(8), Se1ϪC1 1.804(5), Se2ϪC2 1.817(6), Te1···N2(i) 3.122(5),
Te2···N1 2.810(5), Te1···Se1 3.4424(6), Te1···Se1(i) 3.5413(6),
Te2···Se2 3.4321(7), C11ϪTe1ϪC12 94.8(2), C11ϪTe1ϪC13
93.4(2), C13ϪTe1ϪC12 99.9(2), C14ϪTe2ϪC15 97.5(2),
C14ϪTe2ϪC16 94.8(2), C15ϪTe2ϪC16 95.3(2), N2ϪC2ϪSe2
179.2(6), N1ϪC1ϪSe1 177.6(5); with i ϭ 1 Ϫ x, Ϫy, 1 Ϫ z
and in 7 are always shorter than the Te···O/S/Se contacts.
The latter have approximately the same distance as reported
for Te···Se contacts in [R3Te][SeR].[36] The coordination
sphere of azide 1, and the other pseudohalides 2Ϫ4 and 7
are very similar, with all anions being threefold coordinated
(e.g. in 1: Te1···N11, Te2···N11, Te3···N31 (Figure 2)].
The crystal structures of the dicyanoargentates
[(CH3)3Te][Ag(CN)2] (5) and [(C6H5)3Te][Ag(CN)2] (8) con-
˚
tain short Ag···Ag contacts that account for 3.167 A and
˚
2.985 A, respectively, which is at the lower distance limit of
[45Ϫ47]
˚
known Ag···Ag contacts (2.99Ϫ4.2 A),
but no signi-
˚
Figure 9. ORTEP plot of 8; selected bond lengths [A] and angles
ficant effect on the bonding parameters of both the tellu-
ronium cation and the dicyanoargentate anion are found.
The rod-like dicyanoargentate anions are able to mediate
interactions between ions in the crystal which are far away
from each other. In the structure of the methyl derivative 5
(Figure 8), infinite chains of two crystallographically inde-
[°]: TeϪC11 2.119(5), TeϪC12 2.121(5), TeϪC13 2.120(5), N1ϪC1
1.142(6), N2ϪC2 1.138(7), Ag1ϪC1 2.055(5), Ag2ϪC2 2.069(6),
Te···N1 3.346(5), Te1···N1(i) 3.162(4), Te···N2 3.501(5), Ag1···Ag2
2.9847(1), C11ϪTeϪC13 94.4(2), C11ϪTeϪC12 99.5(2),
C13ϪTeϪC12 96.0(2), N1ϪC1ϪAg1 174.8(5), N2ϪC2ϪAg2
173.7(5), C1ϪAg1ϪC1(ii), 180.0, C2ϪAg2ϪC2(i) 175.9(3),
TeϪN1ϪTe(i)
92.8(1)
Ag1ϪAg2ϪAg1(i)
170.63(2),
C1ϪAg1ϪAg2ϪC2 91.6(2); with i ϭ 1 Ϫ x, y, 1/2 Ϫ z; ii ϭ 1 Ϫ
pendent perfectly linear [Ag(CN)2]Ϫ ions (CϪAgϪC 180°) x, 1 Ϫ y, 1 Ϫ z
2706
Eur. J. Inorg. Chem. 2002, 2701Ϫ2709

Synthesis and Structures of Triorganotelluronium Pseudohalides
FULL PAPER
corded using 3-nitrobenzyl alcohol (NBA) as matrix. Elemental
analyses: in-house.
Conclusion
The syntheses, spectroscopic, and structural studies of
triorganotelluronium azides, pseudohalides, and dicyanoar-
X-ray Crystallography: For compounds 1Ϫ4 and 8 a Nonius Kappa
CCD, and for 5Ϫ7 a STOE IPDS area detector device was em-
gentates have been described. Multinuclear NMR spectro- ployed for data collection using Mo-Kα radiation. All structures
were solved by direct methods using SIR97[49] (1؊4, 7, 8) and
scopy established that total dissociation occurs in solution.
Variable-temperature 13C NMR studies of the [Ag(CN)2]Ϫ
SHELXS (5, 6) and refined by means of the full-matrix least-
squares procedures using SHELXL-97[50] (Table 4). CCDC-184294
ion in solution revealed discrete couplings of 13C to both
(1), -184288 (2), -184289 (3), -184293 (4), -184290 (5), -184295 (6), -
silver isotopes (107Ag and 109Ag). In the crystal structures
of all compounds, secondary interactions, Te···N(O)(S)(Se),
are present between cations and anions.
184291 (7) and -184292 (8) contain the supplementary crystallo-
graphic data for this paper. These data can be obtained free of
charge at www.ccdc.cam.ac.uk/conts/retrieving.html or from the
Cambridge Crystallographic Data Centre, 12, Union Road, Cam-
bridge CB2 1EZ, UK [Fax: (internat.) ϩ 44-1223/336-033; E-mail:
deposit@ccdc.cam.ac.uk].
Experimental Section
CAUTION! Silver azide is potentially explosive. This necessitates
General Remarks: Commercially available chemicals (TeCl4, 1.6 
meticulous safety precautions during its preparation and handling.
MeLi in diethyl ether, 1.8  PhLi in cyclohexane/diethyl ether) were
Although both azides 1 and 6 reported in this section are ionic,
used without further purification. The silver salts AgX (X ϭ N3,
they do exhibit a noticeable fizzling when exposed to heat!
OCN, SCN, SeCN) were obtained by precipitation of aqueous solu-
Trimethyltelluronium Azide, [Me3Te]N3 (1): Into a solution of 3
mmol of trimethyltelluronium iodide in 40 mL of H2O, was added
tions of silver nitrate with the corresponding Na/K pseudohalides.
[Me3Te]I was prepared according to a standard procedure,[20,48]
4.2 mmol of moist AgN3 in one portion. After stirring for 4 h at
[Ph3Te]Cl by a similar reaction or according to ref.[21] IR:
ambient temperature, the mixture was filtered and the solvent re-
PerkinϪElmer Spektrum One FT-IR or Nicolet 520 FT-IR Spek-
moved from the filtrate in vacuo. After recrystallization from eth-
trometer (as KBr pellets or between KBr plates). Raman:
anol/diethyl ether, 1 was obtained as colorless, hygroscopic powder
PerkinϪElmer Spectrum 2000 NIR FT-Raman (Nd:YAG laser,
(84%), m.p. 110 °C. IR (KBr): ν˜ ϭ 3009 s, 2027 vs/1998 s (νasN3),
1064 nm, 200 mW). NMR spectroscopy: JEOL Eclipse 400 and
1416 m, 1376 m, 1216 w, 1115 vs, 1054 s, 906 s, 618 s, 594 w, 543
EX400 instruments; chemical shifts are reported with respect to
m, 439 w cmϪ1. Raman: ν˜ ϭ 3023 (5), 2924 (20), 1999 (5, νasN3),
(CH3)4Si (1H, 399.8 MHz; 13C, 100.5 MHz), CH3NO2 (14N, 28.9
1990 (5), 1414 (5), 1323 (35, νsN3), 1225 (5), 1042 (5), 546 (100),
MHz), (CH3)2Se (77Se, 76.3 MHz), aqueous AgNO3 109Ag, 18.6
(
528 (90), 226 (10), 135 (25) cmϪ1. FABϩ MS: m/z (%) ϭ 328 (10)
[Me3Teϩ ϩ NBA], 175 (100) [Me3Teϩ]. C3H9N3Te (214.72): calcd.
C 16.8, H 4.2, N 19.6; found C 16.5, H 4.1, N 18.3.
MHz), (CH3)2Te (125Te, 126.1 MHz). The 77Se and 125Te spectra
were recorded at 25 °C. All chemical shifts are presented in Table 2.
MS: JEOL MStation JMS 700 Spektrometer. Multi-isotope con-
taining fragments refer to the isotope with the highest natural
abundance (for example 130Te). The FAB mass spectra were re-
Trimethyltelluronium Cyanate, [Me3Te]OCN (2): Into a solution of
1 mmol of trimethyltelluronium iodide in 50 mL of H2O, was added
Table 4. Crystal data and structure refinements
1
2
3[a]
4[b]
5
2(6·CHCl3)[c]
7
8
Empirical formula
Formula mass
C3H9N3Te
214.72
C4H9NOTe
214.72
C4H9NSTe
230.79
C4H9NSeTe
277.68
C5H9AgN2Te C37H31Cl3N6Te2 C19H15NSeTe C21H16AgCl3N2Te
332.61
200(2)
921.23
200(3)
463.89
200(2)
638.19
200(2)
Temperature [K]
Crystal size [mm]
200(2)
200(2)
200(2)
200(2)
0.56 ϫ 0.24 ϫ
0.20
orthorhombic
Pnma
0.17 ϫ 0.15 ϫ 0.24 ϫ 0.11 ϫ 0.16 ϫ 0.10 ϫ 0.36 ϫ 0.18 ϫ 0.18 ϫ 0.18 ϫ
0.33 ϫ 0.26 ϫ 0.31 ϫ 0.17 ϫ
0.07
monoclinic
P21/n
0.09
0.02
0.06
0.08
0.20
0.13
Crystal system
Space group
orthorhombic orthorhombic monoclinic
triclinic
orthorhombic orthorhombic
¯
Pna21
Pna21
11.6595(2)
6.6326(1)
10.1745(2)
90
P21/n
P1
Pbca
Pbcn
˚
a [A]
11.2220(1)
9.7746(1)
19.2919(3)
90
6.5637(2)
10.6046(3)
9.6477(3)
93.288(1)
670.43(3)
4
11.5352(3)
6.5142(2)
10.0654(2)
90
6.3340(6)
15.331(1)
9.622(1)
98.79(1)
923.4(2)
4
12.1279(9)
15.7423(9)
20.363(1)
21.668(1)
90
31.0459(5)
12.4486(2)
11.8989(2)
90
˚
b [A]
12.620(1)
˚
c [A]
13.648(1)
β [°]
114.408(9)
3
˚
V [A ]
2116.14(4)
12
756.34(3)
4
786.82(2)
4
1856.0(3)
6945.8(7)
16
4598.7(1)
8
Z
2
ρcalcd. [g cmϪ3
]
2.022
2.127
2.027
2.344
2.393
1.649
1.774
1.844
µ [mmϪ1
]
4.116
4.334
4.106
8.307
5.208
1.823
900
3.805
2.478
F(000)
1200
400
432
504
608
3552
2448
θ range [°]
Index ranges
3.5Ϫ27.5
Ϫ14 Յ h Յ 14
3.65Ϫ23.99
Ϫ7 Յ h Յ 7
3.53Ϫ30.03
3.5Ϫ27.5
2.52Ϫ24.00
2.14Ϫ28.0
1.89Ϫ24.0
3.27Ϫ24.0
Ϫ15 Յ h Յ 16 Ϫ15 Յ h Յ 15 Ϫ7 Յ h Յ 7
Ϫ14 Յ h Յ 14
Ϫ18 Յ h Յ 18 Ϫ33 Յ h Յ 35
Ϫ23 Յ k Յ 23 Ϫ14 Յ k Յ 12
Ϫ24 Յ l Յ 24 Ϫ13 Յ l Յ 10
Ϫ12 Յ k Յ Յ 12 Ϫ12 Յ k Յ 12 Ϫ9 Յ k Յ 9
Ϫ8 Յ k Յ 8
Ϫ16 Յ k Յ 17 Ϫ16 Յ k Յ 16
Ϫ24 Յ l Յ 25
Ϫ11 Յ l Յ 10 Ϫ14 Յ l Յ 14 Ϫ13 Յ l Յ 13 Ϫ11 Յ l Յ 11 Ϫ17 Յ l Յ 17
6166
1054
Reflections collected 28232
Reflections unique
7241
2203
15675
1808
5065
1379
16215
8276
42898
5451
23151
3607
2569
(Rint ϭ 0.0714)
0.0250, 0.0580
0.0282, 0.0595
0.4377/0.2811
2569/0/116
1.153
(Rint ϭ 0.0422) (Rint ϭ 0.0526) (Rint ϭ 0.0524) (Rint ϭ 0.0426) (Rint ϭ 0.0470)
0.0155, 0.0353 0.0251, 0.0521 0.0213, 0.0442 0.0199, 0.0406 0.0338, 0.0607
0.0177, 0.0359 0.0333, 0.0546 0.0235, 0.0455 0.0302, 0.0420 0.0673, 0.0663
0.7464/0.4819 0.7109/0.4377 0.8184/0.2956 0.7469/0.3413 0.9017/0.7383
(Rint ϭ 0.0718) (Rint ϭ 0.0667)
0.0277, 0.0596 0.0355, 0.0794
0.0454, 0.0624 0.0570, 0.0893
0.5321/0.4589 0.7628/0.5196
R1, wR2 (2σ data)
R1, wR2 (all data)
Max./min. transm.
Data/restr./param.
GOOF on F2
1054/0/101
1.120
2203/1/65
1.056
1808/1/64
1.071
1379/0/85
0.965
8276/0/557
0.831
5451/0/397
0.938
3607/0/255
1.061
Larg. diff.
0.906/Ϫ1.086
0.749/Ϫ0.494
1.133/Ϫ0.805
0.765/Ϫ0.415
0.476/Ϫ0.572
0.559/Ϫ0.633
0.530/Ϫ1.130
0.832/Ϫ0.746
3
˚
peak/hole [e/A ]
[a]
[b]
[c]
Flack parameter: Ϫ0.01(3). Racemic twin, volume fraction from refinement: 0.40(1). Compound 6: α ϭ 95.58(1)°, γ ϭ 97.96(1)°.
Eur. J. Inorg. Chem. 2002, 2701Ϫ2709
2707

T. M. Klapötke, B. Krumm, P. Mayer, H. Piotrowski, I. Schwab, M. Vogt
FULL PAPER
2 mmol of freshly precipitated AgOCN in one portion. After stir-
ring for 1 d at ambient temperature, the mixture was filtered and 735 m, 688 w cmϪ1. Raman: ν˜ ϭ 3145 (10), 3058 (70), 1989 (25,
the solvent removed from the filtrate in vacuo. After recrystalliza- νasN3), 1574 (35), 1478 (10), 1328 (40), 1240 (5), 1188 (10), 1160
tion from ethanol/diethyl ether, 2 was obtained as colorless powder (10), 1056 (15), 1020 (55), 1001 (100), 655 (50), 614 (10), 464 (5),
(93%), m.p. 141 °C. IR (KBr): ν˜ ϭ 3011 m, 2916 w, 2170 vs/2138 365 (10), 284 (45), 269 (40), 258 (70), 233 (40), 134 (70) cmϪ1
vs/1993 s (νasN3), 1572 w, 1478 w, 1434 w, 1182 w, 1055 w, 996 w,
.
s/2113 m (νasOCN), 1414 s, 1318 w, 1301 s, 1288 s, 1269 w, 1249
FABϩ MS: m/z (%) ϭ 361 (100) [Ph3Teϩ], 284 (10) [Ph2Teϩ], 207
m, 1237 m, 1224 w, 1206 vs, 1185 w, 907 vs, 900 vs, 831 m, 822 m,
(5) [PhTeϩ]. C18H15N3Te·1/2CHCl3 (460.62): calcd. C 48.2, H 3.4,
662 w, 638 s, 628 s, 623 s, 580 w, 546 s, 537 s cmϪ1. Raman: ν˜ ϭ N 9.1, Cl 11.6; found C 48.7, H 3.4, N 9.0, Cl 11.3.
3025 (15), 2930 (35), 2135 (20, νasOCN), 1428 (5), 1290 (15), 1203
Triphenyltelluronium Selenocyanate, [Ph3Te]SeCN (7): Into a solu-
tion of 0.5 mmol of triphenyltelluronium chloride in 10 mL of H2O,
was added 1 mL of a hot aqueous solution of 2 mmol of KSeCN
in one portion. After stirring for 15 min at 50 °C, filtration of the
(10), 551 (85), 540 (100), 234 (15) cmϪ1. FABϩ MS: m/z (%) ϭ 328
(10) [Me3Teϩ ϩ NBA], 175 (100) [Me3Teϩ]. C4H9NOTe (214.72):
calcd. C 22.1, H 4.2, N 6.5; found C 22.4, H 4.2, N 6.5.
residue and subsequent rinsing with diethyl ether yielded 7 as a
colorless powder (98%), m.p. 164.5Ϫ165.5 °C (ref.[4] 164.5Ϫ165.5
°C). IR (KBr): ν˜ ϭ 3048 w, 2960 m, 2077 vs/2062 vs (νasSeCN),
1572 m, 1477 s, 1436 vs, 1331 w, 1313 w, 1262 s, 1180 w, 1160 w,
1096 vs, 1064 s, 1056 s, 1017 vs, 995 s, 802 vs, 746 s, 730 vs, 685 s,
467 m, 452 m, 403 m cmϪ1. Raman: ν˜ ϭ 3142 (10), 3053 (8), 2079
(75, νasSeCN), 1574 (35), 1479 (10), 1332 (40), 1271 (5), 1188 (10),
1162 (10), 1056 (15), 1020 (55), 1000 (100), 657 (50), 613 (10), 570
(5), 550 (5), 470 (5), 452 (5), 281 (95), 270 (60), 255 (90), 228 (75),
179 (30), 117 (45) cmϪ1. FABϩ MS: m/z (%) ϭ 361 (100) [Ph3Teϩ],
284 (10) [Ph2Teϩ], 207 (5) [PhTeϩ]. C19H15NSeTe (463.89): calcd.
C 49.2, H 3.3, N 3.0; found C 49.0, H 3.2, N 3.0.
Trimethyltelluronium Thiocyanate, [Me3Te]SCN (3): Into a solution
of 1 mmol of trimethyltelluronium iodide in 15 mL of H2O, was
added 2 mmol of freshly precipitated AgSCN in one portion. After
stirring for 4 h at ambient temperature, the mixture was filtered
and the solvent removed from the filtrate in vacuo. After recrystal-
lization from ethanol/diethyl ether, 3 was obtained as colorless
powder (89%), m.p. 86Ϫ88 °C. IR (KBr): ν˜ ϭ 3004 m, 2916 w,
2076 s/2058 vs (νasSCN), 1793 w, 1759 w, 1631 m, 1515 w, 1412 s,
1385 m, 1262 m, 1251 m, 1228 m, 1214 s, 1096 m, 1022 m, 937 m,
925 m, 894 vs, 822 m, 804 m, 730 s, 544 s, 534 s, 468 m, 463 m
cmϪ1. Raman: ν˜ ϭ 3018 (5), 2936 (5), 2058 (30, νasSCN), 1405 (5),
1251 (5), 1232 (5), 1216 (5), 932 (10), 732 (10), 545 (100), 534 (98),
215 (10), 112 (10) cmϪ1. FABϩ MS: m/z (%) ϭ 328 (10) [Me3Teϩ
ϩ NBA], 175 (100) [Me3Teϩ]. C4H9NSTe (230.79): calcd. C 20.8,
H 3.9, N 6.1, S 13.9; found C 20.7, H 4.0, N 5.9, S 13.2.
Triphenyltelluronium Dicyanoargentate, [Ph3Te][Ag(CN)2] (8): Into
a solution of 1 mmol of triphenyltelluronium chloride in 40 mL of
H2O, was added 1.5 mmol of KI in one portion. The resulting
precipitate was collected and washed with water and diethyl ether.
To a suspension of this precipitate in 50 mL of H2O was added 2
mmol of AgCN. After stirring for 20 h at 50 °C, the mixture was
filtered and the solvent removed from the filtrate in vacuo. Recrys-
tallization from chloroform/hexane yielded 8 as colorless crystals
(42%), m.p. 130Ϫ132 °C. IR (KBr): ν˜ ϭ 3055 w, 2921 w, 2126 s/
1999 s (νCN), 1573 s, 1477 w, 1436 s, 1384 m, 1250 m, 1182 w,
1149 w, 1042 m, 1016 s, 994 s, 958 s, 915 m, 817 s, 732 s, 6685 s,
649 s, 502 m cmϪ1. Raman: ν˜ ϭ 3056 (55), 2135 (30), 1575 (40),
Trimethyltelluronium Selenocyanate, [Me3Te]SeCN (4): Into a solu-
tion of 1 mmol of trimethyltelluronium iodide in 100 mL of H2O,
was added 2 mmol of freshly precipitated AgSeCN in one portion.
After stirring for 8 h at ambient temperature, the mixture was fil-
tered and the solvent removed from the filtrate in vacuo. After
recrystallization from methanol/chloroform/diethyl ether, 4 was ob-
tained as slightly pinkish powder (58%), m.p. 106Ϫ109 °C. IR
(KBr): ν˜ ϭ 3421 (br), 3011 m, 2065 vs/2018 m (νasSeCN), 1757 w,
1640 w, 1503 w, 1409 s, 1385 m, 1249 m, 1226 m, 1215 s, 890 vs,
826 w, 816 m, 540 s, 530 s, 414 m cmϪ1. Raman: ν˜ ϭ 3014 (5),
2918 (15), 2065 (40, νasSeCN), 1217 (5), 542 (85), 531 (100), 227
(br, 10), 120 (br, 5) cmϪ1. FABϩ MS: m/z (%) ϭ 328 (10) [Me3Teϩ
ϩ NBA], 175 (100) [Me3Te]ϩ. C4H9NSeTe (277.68): calcd. C 17.3,
H 3.2, N 5.0; found C 17.5, H 3.3, N 4.9.
1020 (45), 1000 (100), 658 (55), 613 (20), 263 (50), 231 (50) cmϪ1
.
FABϩ MS: m/z (%) ϭ 361 (100) [Ph3Teϩ], 284 (10) [Ph2Teϩ], 207
(5) [PhTeϩ]. FABϪ MS: m/z (%)
ϭ
427 [Ag3(CN)4Ϫ], 292
[Ag2(CN)3Ϫ], 159 [Ag(CN)2Ϫ].
Acknowledgments
Trimethyltelluronium Dicyanoargentate, [Me3Te][Ag(CN)2] (5): Into
a solution of 1 mmol of trimethyltelluronium iodide in 100 mL of Financial support of this work by the University of Munich and
H2O, was added 2 mmol of AgCN in one portion. After stirring
for 20 h at 50 °C, the mixture was filtered and the solvent removed
from the filtrate in vacuo; 5 was obtained as slightly grayish crystals
(85%), m.p. 118Ϫ122 °C. IR (KBr): ν˜ ϭ 3007 m, 2962 m, 2929 m,
2873 m, 2135 s/2126 s (νCN), 1728 m, 1563 m, 1416 m, 1290 m,
the Fonds der Chemischen Industrie is gratefully acknowledged.
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was poured in one portion a solution of 20 mmol of NaN3 in 50
mL H2O. After stirring for 45 min at ambient temperature, the
chloroform extract was separated and dried with anhydrous
MgSO4. After removal of the solvent, recrystallization from chloro-
form or 2-propanol yielded 6 as colorless crystals (82%), m.p. 155
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