Synthesis of tellurasila cycles containing an annelated dicarba-closo-dodecaborane(12) unit: Structure of a 1,4-ditellura-2,3- disilacyclohexane derivative

Article abstract of DOI:10.1002/ejic.201201124

Insertion of tellurium into C-Li bonds of dilithiated 1,2-dicarba-closo- dodecaborane(12) gave 1,2-dicarba-closo-dodecaborano(12)-1,2-ditellurolate [(1,2-C₂B₁₀H₁₀)Te₂Li ₂](Et₂O) which, after reaction with 1,2- dichlorotetramethyldisilane, afforded a six-membered heterocycle containing the Te-Si-Si-Te unit with an annelated carborane moiety, characterized by multinuclear magnetic resonance and X-ray structural analysis. As a byproduct, a five-membered ring containing a Si-Si-Te unit was formed, which was obtained as a major product, using conditions favouring partial insertion of tellurium into C-Li bonds. Treatment of [(1,2-C₂B₁₀H₁₀) Te₂Li₂](Et₂O) with dichlorodimethylsilane led to a five-membered heterocycle as a major product containing a Te-Te-Si unit. Various decomposition/hydrolysis/oxidation products could be identified by multinuclear magnetic resonance, among them most notably 1,2-di(hydrotelluro)-1, 2-dicarba-closo-dodecaborane(12). The reactions of 1,2-dicarba-closo- dodecaborano(12)-1,2-ditellurolate with chlorosilanes afforded five-membered silatellura heterocyles containing the TeSiSi or TeTeSi moiety linked with the C₂ unit of 1,2-dicarbadodecaborane(12) in addition to the six-membered heterocycle containing the TeSiSiTe fragment. Copyright

Full text of DOI:10.1002/ejic.201201124

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DOI:10.1002/ejic.201201124
Synthesis of Tellurasila Cycles Containing an Annelated
Dicarba-closo-dodecaborane(12) Unit: Structure of a
1,4-Ditellura-2,3-disilacyclohexane Derivative
Bernd Wrackmeyer,*[a] Elena V. Klimkina,[a] and Wolfgang Milius[b]
Keywords: Main group elements / Boron / Tellurium / Lithium / Silicon / Carboranes / Heterocycles
Insertion of tellurium into C–Li bonds of dilithiated 1,2-di-
carba-closo-dodecaborane(12) gave 1,2-dicarba-closo-dode-
caborano(12)-1,2-ditellurolate [(1,2-C2B10H10)Te2Li2](Et2O)
which, after reaction with 1,2-dichlorotetramethyldisilane,
afforded a six-membered heterocycle containing the Te–Si–
Si–Te unit with an annelated carborane moiety, characterized
by multinuclear magnetic resonance and X-ray structural
analysis. As a byproduct, a five-membered ring containing a
Si–Si–Te unit was formed, which was obtained as a major
product, using conditions favouring partial insertion of tel-
lurium into C–Li bonds. Treatment of [(1,2-C2B10H10)Te2Li2]-
(Et2O) with dichlorodimethylsilane led to a five-membered
heterocycle as a major product containing a Te–Te–Si unit.
Various decomposition/hydrolysis/oxidation products could
be identified by multinuclear magnetic resonance, among
them most notably 1,2-di(hydrotelluro)-1,2-dicarba-closo-do-
decaborane(12).
Introduction
The chemistry of 1,2-dithio- and 1,2-diselenolato-1,2-di-
carba-closo-dodecaborane(12) dianions [1,2-(1,2-C2B10H10)-
E2]2– (E = S, Se), prepared in situ as the dilithium salts[1–4]
(sodium,[5a,5b] potassium[5b,5c] or ammonium[5c,5d] salts),
has been exploited in transition-metal chemis-
try[1,3a,3b,4a,4b,5a,6–11] and, more recently, also in main-
group-element chemistry.[1,3a,12–18] In contrast, the heavy
congener [1,2-(1,2-C2B10H10)Te2]2– has received much less
attention.[4a,19] It appears that its synthesis is less straight-
forward and its reactivity is less predictable than in the
cases of the sulfur and selenium analogues. The most no-
table derivatives are 1 and 2, isolated in low yield and char-
Starting from the parent ortho-carborane 3, careful prep-
acterized in the solid state by X-ray structural analysis,[19] aration of 4 and 5 enabled the synthesis of diselenasila cy-
however, without relevant solution-state NMR spectro- cles in good yield and high purity,[4c] as shown for 6 in
scopic data.
Scheme 1. Such diselenasila cycles turned out to be useful
Scheme 1. Synthesis of the 1,2-diselenolato-1,2-dicarba-closo-dodecaborane(12) dianion, and its conversion into a diselenadisila cycle.
[a] Anorganische Chemie II, Universität Bayreuth,
starting materials for the synthesis of other novel heterocy-
95440 Bayreuth, Germany
cles, since the Si–Se bonds are readily split in exchange reac-
Fax: +49-921-552157
E-mail: b.wrack@uni-bayreuth.de
Homepage: www.ac2.uni-bayreuth.de
[b] Anorganische Chemie I, Universität Bayreuth,
95440 Bayreuth, Germany
tions with various element halides.[20–22]
In the present work, we have set out to prepare the 1,2-
ditellurato-1,2-dicarba-closo-dodecaborane(12)
dianion,
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[1,2-(1,2-C2B10H10)Te2]2– (7), and to study its reactivity
Models from B3LYP/LANL2DZ calculations suggest a
towards chlorosilanes. Considering the favourable NMR nonplanar six-membered ring, in which the SiMe groups
spectroscopic properties of 125Te (I = 1/2; natural abun- should be different. At room temperature, inversion of the
dance 6.99 %),[23] it was hoped that 125Te NMR spec- ring appears to be fast on the NMR spectroscopy timescale,
troscopy could play a similarly important role as 77Se NMR since only single 1H(SiMe) and 13C(SiMe) NMR spec-
spectroscopy in comparable selenium chemistry.
troscopy signals were observed, similar to the situation in
6.[4c] The 13C, 29Si and 125Te NMR spectra of 8 are instruc-
tive (Figure 1); they show numerous satellites owing to
spin–spin coupling, splitting owing to isotope-induced
chemical shifts (13C NMR spectrum, Figure 1, A), and re-
Results and Discussion
Synthesis and NMR Spectroscopy
In addition to the usual precautions to exclude air and markable, for I = 1/2 nuclei, differences in line widths. The
13
moisture, the tellurium compounds are thermally less stable
C
NMR spectroscopy signal is shifted towards low fre-
carb
than their selenium analogues and they are sensitive to day- quencies relative to other carborane derivatives,[4a,24] typical
light. In Scheme 2, the seemingly simple route to disilane of those in the neighbourhood of heavy tellurium. The iso-
derivative 8 is shown. A small amount of an impurity was tope-induced chemical shift 1Δ10/11B(13Ccarb) is similar in
present in the reaction solution, later on identified as het- magnitude to that of other carboranes.[25] The spin–spin
erocycle 9 (see below). Disilane 8 is sparingly soluble in tol- coupling constant J(125Te,13C) has been measured here for
1
uene, and therefore, it can be separated from impurities and the first time for this type of carbon atom. Its magnitude
1
isolated in a pure state.
follows the trend found for J(77Se,13C).[4c,26] The magni-
Samples of 8 could not be kept for prolonged periods of tude of J(125Te,29Si) is in the usual range for Te–Si bonds,
time, neither in solution nor in the solid state. Decomposi- as has been reported for numerous examples.[27,28] In the
tion, noticeable by elimination of elemental tellurium, took disilane unit, two-bond couplings 2J(126Te,Si,13C) and
place readily. However, mass spectra, all relevant solution- 2J(29Si,Si,13C) are observed, the latter proving unambigu-
state NMR spectroscopic data (see the Exp. Sect., Table 1 ously the presence of the Si–Si bond. The considerable line
and Figure 1), and suitable crystals for X-ray structural width of the 125Te NMR spectroscopy signal can be traced
1
analysis were obtained (see below).
to relaxation by chemical-shift anisotropy, typical for heavy
Scheme 2. Synthesis of [1,2-(1,2-C2B10H10)Te2]2– as dilithium salt 7 and conversion into disilane derivative 8.
Table 1. 13C, 29Si and 125Te NMR spectroscopic data[a] of the ortho-carborane derivatives 7, 8, 9, 11, 14, and 21 (solvent: [D8]toluene).
7[b]
8[c]
9
11
14
21
δ13C[Ccarb
]
41.5 (br)
35.8 [415.5]
{–8.8}
32.3 (CTe) [383.0]
{–10.0}
75.0 (CSi) [18.0] (48.5)
{–11.1}
60.3 (CH)
65.3 (CSi) (39.5)
{–9.5}
25.2 (CTe) [380.2] [14.8]
{–8.0}
82.1 (CSi) (49.5) [24.1]
{–11.1}
28.0 (CTe) [507.4]
{–9.3}
75.7 (CSi)
{–11.2}
–1.4 (MeSiCcarb)
(48.4) (6.1)
3.1 (MeSiCl)
(49.7) (7.0)
0.3 (MeSiCcarb)
/101.0/ (48.4) (7.1)
21.4 (MeSiCl)
/101.0/(49.6)
1038.9
δ13C[SiMe2]
δ29Si
–
–
–2.1 (43.3) (5.4) –2.4 (MeSiCcarb
[28.8]
)
–1.9 (48.6) (5.3)
3.1 (54.1) [7.5]
(48.9) (5.6)
–0.7 (MeSiTe)
(45.2) (4.5) [12.6]
2.0 (SiTe) Ͻ283.4Ͼ
/78.7/ (45.3) (5.8)
17.2 (SiCcarb) /78.7/
(48.9) Ͻ19.5Ͼ (4.5)
549.9 Ͻ285.0Ͼ
–8.7 Ͻ285.7Ͼ
(43.3) (5.4)
–3.3 (48.7) (39.5) 22.3 Ͻ329.5Ͼ
(54.0)
δ125Te
540 (br.)
h1/2 ≈ 5500 Hz
615.9 Ͻ285.0Ͼ
h1/2 ≈ 60 Hz
–
878.3 Ͼ2315Ͻ
h1/2 ≈ 50 Hz
h1/2 ≈ 60 Hz
h1/2 ≈ 50 Hz
–208.8 Ͼ2315Ͻ Ͻ329.5Ͼ
h1/2 ≈ (23Ϯ1) Hz
n
n
n
[a] Coupling constants J(125Te,13C) are given in brackets [Ϯ0.5 Hz]; J(29Si,13C) given in parentheses (Ϯ0.5 Hz), J(125Te,29Si) given in
Ͻ…Ͼ ϽϮ0.5 HzϾ; 1J(29Si,29Si) are given between slashes /…/ /Ϯ0.5 Hz/; 1J(125Te,125Te) are given between Ͼ…Ͻ ϾϮ0.5 HzϽ;
1Δ10/11B(13Ccarb)Ϯ0.5 ppb are given in braces {Ϯ0.5 Hz}; isotope-induced chemical shifts 1Δ are given in ppb, and the negative sign
denotes a shift of NMR spectroscopy signal of the heavy isotopomer to lower frequency. [b] Other δ13C data: 15.0 (CH3 from Et2O),
66.3 (OCH2 from Et2O) ppm. [c] δ123Te: 615.5 ppm.
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Figure 1. 2,2,3,3-Tetramethyl-5,6-[1,2-dicarba-closo-dodecaborano(12)]-1,4-ditellura-2,3-disilacyclohexane (8). (A) 125.8 MHz 13C{1H}
n
NMR spectrum of 8 (in [D8]toluene, at 23 °C). The 29Si satellites for J(29Si,13CMe) are marked by filled circles; the 125Te satellites for
1
nJ(125Te,13C) are marked by arrows. The typical isotope-induced chemical shift Δ10/11B(13Ccarb) was observed.[25] (B) 157.9 MHz 125Te
NMR spectrum of 8 (in [D8]toluene, at 23 °C). The 29Si satellites for 1J(125Te,29Si) are marked by ٌ. (C) 99.4 MHz 29Si{1H} NMR
1
n
spectrum of 8 (in [D8]toluene, at 23 °C). The 125Te satellites for J(125Te,29Si) are marked by ٌ; the 13C satellites for J(29Si,13CMe) are
marked by filled circles.
nuclei in unsymmetrical surroundings and high-field NMR spectroscopic data set is reported in the present work (see
spectroscopy measurements.[29] Clearly, this has conse- Table 1 and the Exp. Sect.), and its identity matched the
quences for the line widths of 125Te satellites in 13C or 29Si material reported in the literature[31] as evident by X-ray
NMR spectra. Fast 125Te nuclear spin relaxation gives rise structural analysis.
to short-lived spin states representing the spin–spin cou-
pling interaction, noticeable by broadening of the respective proposed structure (Table 1, Figure 2). The presence of the
satellite signals.
Si–Si bond is evident from one-bond 29Si,29Si spin coupling,
All NMR spectroscopic data of 9 strongly support the
In Scheme 3 (A), we demonstrate the complex and un- shown by satellites in the 29Si NMR spectrum. One silicon
predictable behaviour of the starting dianion 7 (see also atom is attached to tellurium (29Si NMR spectroscopy sig-
ref.[19]) when it was prepared from 4 under slightly different nal with 125Te satellites), whereas the other one is not. The
conditions. Again, 8 was formed in the reaction with 1,2- information from 13C NMR spectroscopy signals, together
dichlorotetramethyldisilane, however, not as the major with their 29Si and 125Te satellites, is consistent with the 29Si
product. Instead 9, the minor species mentioned above and 125Te NMR spectra.
(Scheme 2), is now the major product, and one other het-
What appeared to be a fairly simple task at first glance,
erocycle, 10,[30] could be indentified in the reaction mixture. namely, the synthesis of silane 13 by the reaction of dianion
One may speculate that the Te insertion into the C–Li 7 with Me2SiCl2, turned out to pose a formidable problem.
bonds in 4 was incomplete (see relevant experiments for in- Apparently, 13 was not even formed as a minor product in
sertion of Se)[18] prior to the following reaction. This was appreciable quantity when we studied the reaction solutions
investigated in more detail as shown in Scheme 3 (B). Het- by NMR spectroscopy with spectra recorded immediately
erocycle 10 has been prepared independently, studied for its after the reactions had been performed. In each of several
NMR spectroscopy parameters and characterised by X-ray attempts, solely the cyclic ditellane 14 was formed together
structural analysis.[30] Compound 11 has been synthesised with side products, and was identified by NMR spectro-
previously in another context, and its solid-state structure scopic data. The results are summarized in Scheme 4. A fi-
has been determined.[31] However, a more complete NMR nal attempt to prepare 13, starting from 8, by exchange with
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Scheme 3. Preparation of dianion 7 under slightly different conditions gives rise to the formation of a mixture of heterocycles.
Figure 2. (A) 99.4 MHz 29Si{1H} NMR spectrum of the mixture of 8, 9, 10 and 11 (in [D8]toluene, at 23 °C). The 125Te satellites for
n
nJ(125Te,29Si) are marked by ٌ; the 13C satellites for J(29Si,13C) are marked by filled circles; the 29Si satellites for 1J(29Si,29Si) are marked
by asterisks. (B) Part of the 125.8 MHz 13C{1H} NMR spectrum (SiMe groups) of the mixture of 8 and 9 (in [D8]toluene, at 23 °C). The
n
2
29Si satellites for J(29Si,13CMe) are marked by filled circles; the 125Te satellites for J(125Te,13C) are marked by arrows.
Me2SiCl2 (analogously to experiments in selenium chemis- might help to stabilise the desired product as a seven-mem-
try)[4c] also failed completely. When we used (Me2SiCl)2O bered ring, we only identified the tellurium-free known cy-
in the reaction with 7, hoping that a different ring size clic disiloxane 15.[30]
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Scheme 4. Reactivity of dianion 7 towards Me2SiCl2 and (Me2SiCl)2O.
Figure 3. 3,3-Dimethyl-4,5-[1,2-dicarba-closo-dodecaborano(12)]-1,2-ditellura-3-silacyclopentane (14). (A) 100.5 MHz 13C{1H} NMR
spectrum of 14 (in [D8]toluene, at 23 °C). The 29Si satellites for nJ(29Si,13CMe) are marked by filled circles; the 125Te satellites for
1
nJ(125Te,13C) are marked by arrows. The isotope-induced chemical shift Δ10/11B(13Ccarb) observed for 14.[25] (B) 126.2 MHz 125Te NMR
1
1
spectrum of 14 (in [D8]toluene, at 23 °C). The 29Si satellites for J(125Te,29Si) are marked by ٌ; the 125Te satellites for J(125Te,125Te) are
marked by asterisks. (C) 99.4 MHz 29Si{1H} NMR spectrum of 14 (in [D8]toluene, at 23 °C). The 125Te satellites for J(125Te,29Si) are
1
marked by ٌ; the 13C satellites for J(29Si,13CMe) are marked by filled circles.
n
Cyclic ditellane 14 deserves interest, since the comparable worthy is the large magnitude of the coupling constant
diselane was also observed quite unexpectedly as a side 1J(125Te,125Te) = 2315 Hz, much larger than in noncyclic
product in connection with the synthesis and reactivity of ditellanes,[32] which is reminiscent of 1J(77Se,77Se)
=
the diselena analogue to 13.[4c] Since a pure sample of 14 313 Hz[4c] in the corresponding cyclic diselane, also signifi-
could not be isolated, all relevant NMR spectra (Table 1 cantly larger than in noncyclic diselanes.[33]
and Figure 3) were measured from solutions containing 14.
The 13C, 29Si and 125Te NMR spectra with important infor-
mation on mutual spin–spin couplings provide convincing
Reactivity of the Cyclic Tellurasilanes
When unsealed samples of 8 were kept at room tempera-
evidence for the proposed structure. Perhaps, most note- ture in toluene (Scheme 5) slow hydrolysis took place, ac-
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Scheme 5. Slow hydrolysis/oxidation of 8 in toluene.
companied by formation of small amounts of elemental tel- troscopic characterisation proved possible (Table 2). The re-
lurium. After several days, the solutions contained the action of 8 with PhBCl2 at room temperature proceeded
known ditellane 1, as a result of partial hydrolysis and surprisingly slowly, indicated by formation of Me2(Cl)Si-
oxidation, the parent carborane 3, and the known[27a] Si(Cl)Me2 (29Si NMR spectroscopy). The desired borane 17
cyclic siloxane derivative 16 (δ29Si = 1.1 ppm), both due to might have been present in low concentration as indicated
hydrolysis. According to 29Si NMR spectra, small by a broad 11B NMR spectroscopy signal at δ11B =
amounts of other oligomers (Me2SiSiMe2O)n (n Ͼ 2; δ29Si 39.4 ppm. However, after three weeks, the major reaction
= 1.5, 1.6, 2.7 ppm) were also present in the mixture. In pathway leads to various decomposition products, of which
spite of the formation of elemental tellurium, there was no 2, 18, 19 and 20 could be identified. Among these, ditellurol
NMR spectroscopic evidence for the presence of hetero- 18 is of interest since it is apparently sufficiently stable in
cycle 9.
solution for further transformations, as already shown here
Exchange reactions of 8 with an excess amount of di- by its oxidation products 19 and 2. The presence of 18 fol-
methyldichlorosilane and dichlorophenylborane (Scheme 6) lows conclusively from the characteristic NMR spectra
were studied. In the former case, the expected product 13 (Figure 4). Simple slow hydrolysis/oxidation of 2 afforded
(see Scheme 4) was not observed. Instead, after several ditellane 1 together with elemental tellurium.
days, telluranes 1 and 2 were formed. Since these com-
Similarly to 8, heterocycle 9 reacted only slowly at room
pounds were formed in various reactions, their NMR spec- temperature with PhBCl2 (Scheme 7). Compounds with Te–
Scheme 6. Attempted exchange reactions of 8 with Me2SiCl2 and PhBCl2.
Table 2. 13C and 125Te NMR spectroscopic data[a] of the ortho-carborane derivatives 1, 2, 17, 18, and 19 (solvent: [D8]toluene).
1[b]
2[b]
17[c]
18
19
δ13C[C(carb)]
δ125Te
30.3 (CTe), 66.3 (CH) 30.3 (CTe)
n.o.
1074.2 [br.]
h1/2 ≈ 700 Hz
40.8
790.2 (≈ 45.0)
h1/2 ≈ 90 Hz
37.7, 39.0
1071.1
1093.5
743.1 (≈ 50.0) (TeH)
h1/2 ≈ 75 Hz
1102.2 (Te–Te)
–0.48 (54.0)
δ1H (TeH)
–
–
–
–0.38 (46.0) (8.2)
n
n
[a] Coupling constants J(125Te,13C) are given in brackets [Ϯ0.5 Hz]; J(125Te,1H) in parentheses (Ϯ1 Hz); [br] denotes broad 125Te reso-
nances of boron-bonded tellurium atoms; n.o.: not observed. [b] Ref.[22] [c] δ11B = 39.4 ppm.
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Figure 4. 157.8 MHz 125Te NMR, 500.13 MHz 1H and 1H{125Te} NMR spectra of 1,2-di(hydrotelluro)-1,2-dicarba-closo-dodecabor-
ane(12) (18) (23 °C, in [D8]toluene).
B bonds could not be identified with certainty. Instead the Table 3. Selected bond lengths [pm] and angles [°] of the ortho-
carborane derivative 8 and 6.
parent carborane 3, triphenylboroxine 20 and the ditellane
8
6[a]
E = Se
derivative 21 were major products.
E = Te
C(1)–E(1)
C(2)–E(2)
C(1)–C(2)
E(1)–Si(1)
E(2)–Si(2)
Si(1)–Si(2)
C(1)–E(1)–Si(1)
C(2)–E(2)–Si(2)
E(1)–Si(1)–Si(2)
E(2)–Si(2)–Si(1)
E(1)–C(1)–C(2)
E(2)–C(2)–C(1)
C(3)–Si(1)–C(4)
213.8(4)
214.3(4)
168.4(5)
253.54(12)
253.35(12)
236.22(18)
99.02(11)
99.62(11)
106.59(5)
108.73(5)
121.6(2)
120.8(2)
108.6(2)
109.7(2)
0.0
193.8(4)
193.5(4)
171.4(5)
232.37(14)
232.84(15)
235.94(18)
103.68(13)
104.03(13)
106.18(6)
106.31(7)
120.3(2)
120.1(3)
109.3(3)
111.4(3)
0.7
Scheme 7. Attempted exchange reaction of 9 with PhBCl2.
X-ray Structural Analyses of the Six-Membered Ring 8
Containing the Te–Si–Si–Te Unit
C(5)–Si(2)–C(6)
The molecular structure of 8 is shown in Figure 5, and
relevant structural parameters are given in Table 3, together
with those for the analogous selenium derivative 6 for com-
parison.
Plane E(1)–C(1)–C(2)–E(2)
Plane E(1)–Si(1)–Si(2)–E(2)
Distance of Si(1) from the plane
E(1)–C(1)–C(2)–E(2)
Distance of Si(2) from the plane
E(1)–C(1)–C(2)–E(2)
2.1
224.4
1.5
199.8
219.8
197.1
[a] Ref.[4c]
E–Si[27] and E–C as well as the bond angles at Te and Se,
which are more acute in the case of E = Te. Intra- and
intermolecular Te–Te distances in solid 8 are slightly
shorter than the sum of van der Waals radii, which may
account for the instability with respect to formation of ele-
mental tellurium.
Figure 5. ORTEP plot (50 % probability; hydrogen atoms are omit-
ted for clarity) of the molecular structure of the 2,2,3,3-tetramethyl-
5,6-[1,2-dicarba-closo-dodecaborano(12)]-1,4-ditellura-2,3-disilacy-
clohexane (8) (for selected distances and angles see Table 3).
Conclusion
The preparation of the 1,2-ditellurato-1,2-dicarba-closo-
The main structural features of 8 and 6 are similar. As dodecaborane(12) dianion [1,2-(1,2-C2B10H10)Te2]2– as its
expected, the major differences concern the bond lengths dilithium salt 7 is more difficult and less reproducible than
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stable in the absence of light at –30 °C. 1H{11B} NMR (399.8 MHz,
[D8]toluene, 25 °C): δ = 1.22, 3.56 (t, q, ca. 20 H, OEt2), 2.65, 3.05,
3.25, 3.35 (br. m, 10 H, HB) ppm. 11B{1H} NMR (128.3 MHz,
[D8]toluene, 25 °C): δ = –0.9 (br., 10 B) ppm.
its lighter congeners. Moreover, in the case of tellurium, the
dianion itself and the products appear to be light sensitive
and decompose readily. However, disilane derivative 8, pre-
pared by the reaction of 7 with 1,2-dichlorotetramethyldisil-
ane, containing a six-membered ring, could be isolated in a
pure state in reasonably good yield, and may well serve for
further transformations. In this study, two interesting five-
membered rings 9 and 14, containing the Si–Si–Te and the
Si–Te–Te unit, respectively, were also identified by using
multinuclear magnetic resonance spectroscopy. Clearly, this
tellurium chemistry is less predictable than the correspond-
ing selenium chemistry. However, this is also a stimulating
fact, inspiring further activity.
2,2,3,3-Tetramethyl-5,6-[1,2-dicarba-closo-dodecaborano(12)]-1,4-di-
tellura-2,3-disilacyclohexane (8): Freshly prepared [(1,2-C2B10H10)-
Te2Li2](2Et2O) 7 (692 mg, 1.26 mmol) was cooled to –20 °C, and
was dissolved in toluene (20 mL); the suspension was cooled to
–40 °C, and Me2Si(Cl)–Si(Cl)Me2 (237 mg, 0.235 mL, 1.26 mmol)
was injected slowly through a syringe. After stirring the reaction
mixture for 1.5 h at –30 °C and 30 min at room temp., insoluble
materials were separated by centrifugation, and the clear liquid was
collected. The remaining insoluble materials were washed with tol-
uene (10 mL) and centrifuged. The centrifuged solutions were com-
bined, and volatile materials were removed under vacuum to give
a yellow-brown solid (447 mg). The resulting mixture thus obtained
contained 8 (ca. 70 %), 9 (ca. 20 %) and side product 11 (10 %)
(from 29Si and 13C NMR). The remaining insoluble materials were
washed with toluene (30 mL) and centrifuged. Compound 8 was
only sparingly soluble in both hexane and toluene. Yellowish single
crystals of 8 for X-ray analysis were grown from [D8]toluene solu-
tion after 1 week at –30 °C; m.p. 155–165 °C (decomposition).
Compound 8 decomposes under Ar as a solid at room temp., also
slowly in [D8]toluene at –30 °C as well as in the presence of light
with formation of black elemental tellurium. 1H{11B} NMR
(500.13 MHz, [D8]toluene, 25 °C): δ = 0.30 (s, 12 H, CH3Si), 2.69
[br. s, 2 H, HB for δ(11B) = –6.1 ppm], 2.81 [br. s, 2 H, HB for
δ(11B) = –6.1 ppm], 3.09 [br. s, 2 H, HB for δ(11B) = –0.5 ppm],
3.21 [br. s, 4 H, HB for δ(11B) = –6.1 ppm] ppm. 11B{1H} NMR
(160.5 MHz, [D8]toluene, 25 °C): δ = –6.1 (8 B), –0.5 (2 B) ppm.
Experimental Section
General: All syntheses and the handling of the samples were per-
formed by observing necessary precautions to exclude traces of air
and moisture. Carefully dried solvents and oven-dried glassware
were used throughout. The deuterated solvent CD2Cl2 was distilled
from CaH2 under an atmosphere of argon. All other solvents were
distilled from Na metal under an atmosphere of argon. [(1,2-
C2B10H10)Li2](2Et2O)[4c] (4) was prepared according to the pub-
lished procedure. The starting materials were purchased from Ald-
rich {butyllithium (1.6 m in hexane), Me2SiCl2, [Me2(Cl)Si]2,
[Me2(Cl)Si]2O, tellurium (powder, 200 mesh, 99.8 % metals basis),
PhBCl2 (97 %)}, and KatChem. (ortho-carborane 3), and used
without further purification. NMR spectroscopy measurements:
Bruker DRX 500: 1H, 11B, 13C, 125Te, and 29Si NMR [refocused
INEPT[34] based on 2J(29Si,1H) = 6–7 Hz]; Varian INOVA 400: 1H,
11B, 13C, 125Te, 29Si NMR; chemical shifts are given relative to
Me4Si [δ1H (CHDCl2) = 5.33 ppm, δ1H (C6D5CD2H) = 2.08
(Ϯ0.01) ppm; δ13C (CD2Cl2) = 53.8 ppm, (C6D5CD3) = 20.4 (Ϯ0.1)
ppm]; external BF3–OEt2 [δ11B = 0 (Ϯ0.3) ppm for Ξ(11B) =
32.083971 MHz], neat Me2Te [δ125Te = 0 ppm for Ξ(125Te) =
1
11B NMR (160.5 MHz, [D8]toluene, 25 °C): δ = –6.1 [d, J(11B,1H)
= 157 Hz, 8 B], –0.5 [d, 1J(11B,1H) = 147 Hz, 2 B] ppm. EI-MS
(70 eV) for C6H22B10Si2Te2 (513.7): m/z (%) = 514 (20) [M+], 499
(5) [M+ – CH3], 445 (5) [M+ – HSi(CH3)2], 387 (7) [M – Te], 372
(18) [M – CH3 – Te], 357 (15) [C3H9Te2Si2], 326 (5) [M –
TeSi(CH3)2], 245 (20) [C4H11TeSi2], 188 (40) [TeSi(CH3)2], 73 (100)
[Si(CH3)3].
1
31.549802 MHz]. Assignments of H and 11B NMR spectroscopy
Reaction of 4 with Tellurium and Me2Si(Cl)–Si(Cl)Me2: 2,2,3,3-
Tetramethyl-4,5-[1,2-dicarba-closo-dodecaborano(12)]-1-tellura-2,3-
disilacyclopentane (9): (A) Degassed elemental tellurium (1130 mg,
8.85 mmol) was added to freshly prepared [(1,2-C2B10H10)Li2](2-
Et2O) 4 (1305 mg, 4.46 mmol). The mixture was cooled to 0 °C,
and Et2O (30 mL) was added. The suspension was stirred for 1 h
at 0 °C and for 1 h at room temp. The formation of a green precipi-
tate was observed, which was separated using a centrifuge. The
yellow supernatant liquid was decanted. The residue after centrifu-
gation was dried under vacuum (1 h, 8ϫ10–3 Torr) to give a yellow-
green powder (2654 mg). The solid was cooled to 0 °C, and was
dissolved in toluene (40 mL); the suspension was cooled to –30 °C,
and Me4Si2Cl2 (800 mg, 0.796 mL, 4.27 mmol) was injected slowly
through a syringe. After stirring the reaction mixture for 1.5 h at
signals are based on 1H{11B} selective heteronuclear decoupling
experiments.[35] Mass spectra (EI, 70 eV): Finnigan MAT 8500 with
1
direct inlet (data for 12C, H, 11B, 28Si, 130Te). Melting points (un-
corrected) were determined using a Büchi 510 melting point appa-
ratus. Owing to the extreme sensitivity of compounds 8 and 9 ele-
mental analysis was not performed. All preparative work as well as
handling of the samples was performed in the dark to shield sam-
ples as much as possible from light. Thus, reaction flasks and NMR
spectroscopy sample tubes were wrapped in aluminium foil. All
tellurium-containing compounds studied here decompose under Ar
as solids and in the solution at room temp. as well as in the presence
of light accompanied by formation of black elemental tellurium.
1,2-Dicarba-closo-dodecaborano(12)-1,2-ditellurolate
[(1,2-
C2B10H10)Te2Li2](Et2O) (7): Degassed elemental tellurium (911 mg, –20 °C, insoluble materials were separated by centrifugation at
7.14 mmol) was added to freshly prepared [(1,2-C2B10H10)Li2](2-
Et2O) (4) (1045 mg, 3.57 mmol). The mixture was cooled to 0 °C,
and Et2O (25 mL) was added in the dark. The reaction flask was
wrapped in aluminium foil, and the suspension was stirred at room
temp. (or 0 °C) for 18 h. The formation of a red oily phase and a
green precipitate was observed. The suspension was separated using
a centrifuge, and the yellow supernatant liquid was decanted. The
residue after centrifugation (oil and solid) was dried under vacuum
(4 h, 8ϫ10–3 Torr) to give 7 as a yellow-green powder (1606 mg,
82 %). Compound 7 decomposes slowly under Ar as a solid at
room temp. as well as in the presence of light and remains relatively
0 °C, and the clear yellow-brown liquid was collected. Volatile ma-
terials were removed under vacuum to give a brown solid
(1360 mg). The resulting mixture thus obtained contained 8 (ca.
35 %), 9 (ca. 55 %), 10 (ca. 5 %), 11 (ca. 5 %) and several unidenti-
fied side products (from 29Si and 13C NMR spectra). The remaining
mixture was dissolved in hexane (20 mL), and the liquid phase was
separated by centrifugation. Transparent crystals of 9 [m.p. 140–
150 °C (decomposition)] were grown from a [D8]toluene solution
after 5 days at –30 °C. Compound 9: 1H{11B} NMR (250.13 MHz,
[D8]toluene, 25 °C): δ = 0.06 (s, 6 H, CH3Si), 0.32 (s, 6 H, CH3Si),
2.18 [br. s, 2 H, HB for δ(11B) = –9.4 ppm], 2.69 [br. s, 2 H, HB for
Eur. J. Inorg. Chem. 2013, 398–408
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δ(11B) = –7.3 ppm], 2.77 [br. s, 1 H, HB for δ(11B) = 1.1 ppm], 2.91
[br. s, 4 H, HB for δ(11B) = –6.6, –3.4 ppm], 3.04 [br. s, 1 H, HB for
δ(11B) = –2.4 ppm] ppm. 11B{1H} NMR (160.5 MHz, [D8]toluene,
25 °C): δ = –9.4 (2 B), –7.3 (2 B), –6.7 (2 B), –3.4 (2 B), –2.4 (1 B),
1.0 (1 B) ppm. 11B NMR (160.5 MHz, [D8]toluene, 25 °C): δ = –9.4
[Me2(Cl)Si]2O (258 mg, 0.249 mL, 1.27 mmol) was injected slowly
through a syringe. After stirring the reaction mixture for 1.5 h at
–30 °C and 15 min at room temp., insoluble materials were sepa-
rated by centrifugation, and the clear liquid was collected. Volatile
materials were removed under vacuum to give a yellow-brown oil
1
1
[d, J(11B,1H) = 168 Hz, 2 B], –7.3 [d, J(11B,1H) = 168 Hz, 2 B], (250 mg). The resulting mixture thus obtained contained 15 (ca.
1
1
–6.7 [d, J(11B,1H) = 165 Hz, 2 B], –3.4 [d, J(11B,1H) = 155 Hz, 2 80 %)[30] and several unidentified side products (from 29Si NMR
1
1
B], –2.4 [d, J(11B,1H) = 155 Hz, 1 B], 1.0 [d, J(11B,1H) = 150 Hz,
spectra).
1 B] ppm. EI-MS (70 eV) for C6H22B10Si2Te (386.1): m/z (%) = 387
Bis[1,2-dicarba-closo-dodecaborane-1-yl]ditellane (1): A solution of
8 (50 mg, 0.097 mmol) in [D8]toluene (0.6 mL) was added to an
NMR spectroscopy tube, and stored at room temp. for 2 weeks.
The progress of the reaction was monitored by 1H, 29Si and 13C
NMR spectroscopy. The solution thus obtained contained 1, 16[27a]
and ortho-carborane 3. Compound 1: 1H NMR (500.13 MHz, [D8]-
toluene, 25 °C): δ = 2.55 (br. s, 2 H, CH) ppm. 1H{11B} NMR
(500.13 MHz, [D8]toluene, 25 °C): δ = 2.20 [br. s, 4 H, HB for
δ(11B) = –11.0 ppm], 2.36 [br. s, 4 H, HB for δ(11B) = –11.5 ppm],
2.55 (br. s, 2 H, CH), 2.57 [br. s, 4 H, HB for δ(11B) = –8.5 ppm],
2.61 [br. s, 4 H, HB for δ(11B) = –6.8 ppm], 2.79 [br. s, 2 H, HB for
δ(11B) = 0.2 ppm], 2.92 [br. s, 2 H, HB for δ(11B) = –2.2 ppm] ppm.
11B{1H} NMR (160.5 MHz, [D8]toluene, 25 °C): δ = –11.5 (4 B),
–11.0 (4 B), –8.5 (4 B), 6.8 (4 B), –2.2 (2 B), 0.2 (2 B) ppm.
(80) [M+], 372 (100) [M+ – CH3], 258 (5) [M+ – Te], 243 (6) [M+
–
Te – CH3], 223 (4), 210 (10), 198 (8) [M –Te – 4CH3], 188 (10)
[TeSi(CH3)2], 73 (70) [Si(CH3)3].
(B) Degassed elemental tellurium (516 mg, 4.04 mmol) was added
to freshly prepared [(1,2-C2B10H10)Li2](2Et2O) (4) (1185 mg,
4.05 mmol). The mixture was cooled to 0 °C, and Et2O (20 mL)
was added. The suspension was stirred for 15 h at room temp. to
give a green precipitate and a red-brown oil, both of which were
dried without separation under vacuum (3 h, 8ϫ10–3 Torr) to give
a yellow-green powder. The solid was cooled to –30 °C, and was
dissolved in toluene (50 mL); the suspension was cooled to –40 °C,
and Me4Si2Cl2 (753 mg, 0.75 mL, 4.02 mmol) was injected slowly
through a syringe. After stirring the reaction mixture for 1 h at
–40 °C and for 1 h at room temp., insoluble materials were sepa-
rated by centrifugation, and the clear yellow-brown liquid was col-
lected. The remaining insoluble materials were washed with toluene
(30 mL) and centrifuged. The centrifuged solutions were combined,
and volatile materials were removed under vacuum to give a yellow-
brown solid (1443 mg). The resulting mixture thus obtained con-
Reaction of 8 with PhBCl2: 3,4,7,8-Bis[1,2-dicarba-closo-dodecabor-
ano(12)]-1,2,5,6-tetratelluracyclooctane (2) and 1,2-Di(hydrotelluro)-
1,2-dicarba-closo-dodecaborane(12) (18): A solution of 8 (23 mg,
0.045 mmol) in [D8]toluene (0.6 mL) was added to an NMR spec-
troscopy tube, cooled to 0 °C and PhBCl2 (0.012 mL, 14.5 mg,
0.091 mmol) was added through a microsyringe. A solution was
tained 8 (ca. 20 %), 7 (ca. 60 %), 10 (ca. 5 %), 11 (ca. 15 %) and stored at room temp. for 3 weeks. The progress of the reaction was
several unidentified side products (from 29Si and 13C NMR spec-
tra). The remaining mixture was dissolved in hexane (20 mL), and
the liquid phase was separated by centrifugation. The remaining
insoluble materials were dissolved in Et2O (10 mL), centrifuged,
and the liquid phase was separated and dried under vacuum. Trans-
parent crystals of 11 for X-ray analysis[31] were grown from a [D8]-
monitored by 1H, 11B, 29Si, 125Te and 13C NMR spectroscopy. The
formation of red-orange crystals of 2 was observed. The solid of 2
was separated, and the yellow supernatant liquid was collected. The
solution thus obtained contained 18, 19 and 20 together with Me4-
Si2Cl2 and PhBCl2.
Compound 2: 1H{11B} NMR (500.13 MHz, [D8]toluene, 25 °C): δ
= 2.26 [br. s, 2 H, HB for δ(11B) = –9.3 ppm], 2.63 [br. s, 1 H, HB
for δ(11B) = –9.3 ppm], 2.68, 2.87, 3.06 [br. s, br. s, br. s, 2 H, 4 H,
4 H, HB for δ(11B) = –5.7 ppm], 3.11 [br. s, 6 H, HB for δ(11B) =
–1.1 ppm], 3.15 [br. s, 1 H, HB for δ(11B) = –9.3 ppm] ppm.
11B{1H} NMR (160.5 MHz, [D8]toluene, 25 °C): δ = –9.3 (6 B),
–5.7 (10 B), 1.1 (6 B) ppm. 11B NMR (160.5 MHz, [D8]toluene,
1
toluene solution after 3 days at –30 °C. Compound 11: H NMR
(250.13 MHz, [D8]toluene, 25 °C): δ = –0.04 (s, 12 H, CH3Si), 2.67
(br. s, 2 H, CH) ppm. 11B{1H} NMR (160.5 MHz, [D8]toluene,
25 °C): δ = –13.5 (4 B), –11.7 (4 B), –10.9 (4 B), –6.5 (6 B), –1.0 (2
B) ppm. 11B NMR (160.5 MHz, [D8]toluene, 25 °C): δ = –13.5 [d,
1J(11B,1H) = 172 Hz, 4 B], –11.7 [d, 1J(11B,1H) = 160 Hz, 4 B],
1
1
–10.9 [d, J(11B,1H) = 150 Hz, 4 B], –6.5 [d, J(11B,1H) = 150 Hz,
1
25 °C): δ = –9.3 [d, J(11B,1H) = 150 Hz, 6 B], –5.7 (2 B), 1.1 [d,
6 B], –1.0 [d, J(11B,1H) = 150 Hz, 2 B] ppm.
1
1J(11B,1H) = 145 Hz, 6 B] ppm.
1
Reaction of 7 with Me2SiCl2: 3,3-Dimethyl-4,5-[1,2-dicarba-closo- Compound 18: H{11B} NMR (500.13 MHz, [D8]toluene, 25 °C): δ
dodecaborano(12)]-1,2-ditellura-3-silacyclopentane (14): Freshly pre-
pared [(1,2-C2B10H10)Te2Li2](2Et2O) (7) (1546 mg, 2.82 mmol) was
cooled to –20 °C, and was dissolved in toluene (30 mL); the suspen-
sion was cooled to –40 °C, and Me2SiCl2 (360 mg, 0.336 mL,
2.79 mmol) was injected slowly through a syringe. After stirring the
reaction mixture for 1 h at –40 °C and 1 h at room temp., insoluble
materials were separated by centrifugation, and the clear blue li-
quid was collected. Volatile materials were removed under vacuum
to give a brown oil (825 mg). The resulting mixture thus obtained
contained 14 (ca. 50 %) and several side products (from 29Si NMR
spectra). The remaining oil was washed with hexane (10 mL), dried
under vacuum to give a brown oil (250 mg) of 14 (80 %) and several
unidentified materials (from 29Si and 13C NMR spectra). 14: 1H
NMR (399.8 MHz, [D8]toluene, 25 °C): δ = 0.37 (s, 6 H, CH3Si).
= –0.38 [s, 2 H, TeH, 1J(125Te,1H) = 46.0 Hz, 4J(125Te,1H) =
8.2 Hz], 2.56 [br. s, 1 H, HB for δ(11B) = –5.3 ppm], 2.66 [br. s, 2
H, HB for δ(11B) = –5.9 ppm], 2.87 [br. s, 1 H, HB for δ(11B) =
–7.1 ppm], 3.00 [br. s, 3 H, HB for δ(11B) = –7.2, –0.3 ppm], 3.05
[br. s, 3 H, HB for δ(11B) = –5.9 ppm] ppm. 11B{1H} NMR
(160.5 MHz, [D8]toluene, 25 °C): δ = –7.2 (2 B), –5.9 (5 B), –5.3 (1
B), –0.3 (2 B) ppm.
Compound 19: 1H NMR (500.13 MHz, [D8]toluene, 25 °C): δ =
1
–0.48 [s, 2 H, TeH, J(125Te,1H) = 53.5 Hz] ppm.
Reaction of 9 with PhBCl2: A solution of 9 (50 mg, 0.13 mmol) in
[D8]toluene (0.6 mL) was added to an NMR spectroscopy tube,
cooled to 0 °C and PhBCl2 (0.034 mL, 41.3 mg, 0.26 mmol) was
added through a microsyringe. The solution was stored at room
temp. for 2 weeks. The progress of the reaction was monitored by
1H, 11B, 29Si, 125Te and 13C NMR spectroscopy. The solution thus
obtained contained 21 together with 20, 3 and PhBCl2. Compound
Reaction of 7 with [Me2(Cl)Si]2O: 1,1,3,3-Tetramethyl-4,5-[1,2-di-
carba-closo-dodecaborano(12)]-1,3-disila-2-oxa-cyclopentane (15):
Freshly prepared [(1,2-C2B10H10)Te2Li2](2Et2O) (7) (696 mg,
1.27 mmol) was cooled to –40 °C, dissolved in toluene (20 mL) and
1
21: H NMR (500.13 MHz, [D8]toluene, 25 °C): δ = 0.30 (s, 12 H,
CH3Si), 0.37 (s, 12 H, CH3Si) ppm.
Eur. J. Inorg. Chem. 2013, 398–408
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Crystal Structure Determination of 8: Structure solutions and re-
finements were carried out with the program package SHELXTL-
97.[36] Details pertinent to the crystal structure determination are
listed in Table 4. Crystals of appropriate size were sealed under
argon in Lindemann capillaries, and the data collections were car-
ried out at 133 K.[37]
[7]
Table 4. Crystallographic data of ortho-carborane derivative 8.
[8]
[9]
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Trans. 2009, 9298–9303.
8
Formula
Crystal
C6H22B10Si2Te2
yellowish block
0.24ϫ0.19ϫ0.18
133(2)
monoclinic
P21/n
830.41(17)
1971.0(4)
1172.4(2)
98.20(3)
4
3.178
STOE IPDS II
Mo-Kα, λ = 71.073 pm,
graphite monochromator
2.04–25.65
3578
2290
numerical
Dimensions [mm3]
T [K]
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1560; b) Y.-Q. Chen, J.-Q. Wang, G.-X. Jin, J. Organomet.
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47, 7928–7933.
Crystal system
Space group
a [pm]
b [pm]
c [pm]
β [°]
Z
μ [mm–1]
Diffractometer
[10]
[11]
Measuring range (Θ) [°]
Reflections collected
Independent reflections [IՆ2σ(I)]
Absorption correction
Max./min. transmission
Refined parameters
0.6927/0.5123
181
0.0457/0.0210
wR2/R1 [IՆ2σ(I)]
Max./min. residual electron density 0.925/–0.627
[epm–3 10–6]
Acknowledgments
Support of this work by the Deutsche Forschungsgemeinschaft
(DFG) is gratefully acknowledged.
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Received: September 21, 2012
Published Online: December 5, 2012
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