Heteronoradamantanes Me2Si2 (RM)2E5 (RM=MeGe, PhSn; E=S, Se)

Article abstract of DOI:10.1016/S0022-328X(03)00226-2

The reaction of a 1:2 molar mixture of 1,2-Me₂Si₂Cl₄ and MeGeCl₃ with H₂S/NEt₃ yielded Me₂Si₂ (MeGe)₂S₅ (1), the first mixed silicon-germanium chalcogenide with a noradamantane-like structure, while the treatment of a 1:2 mixture of 1,2-Me₂Si₂Cl₄ and PhSnCl₃ with Li₂Se resulted in the formation of the first silicon- and tin-containing noradamantane Me₂Si₂(PhSn)₂Se₅ (2). Both compounds have been characterized by NMR spectroscopy (¹H, ¹³C, ²⁹Si, ⁷⁷Se and ¹¹⁹Sn). The molecular structure of 1 in the solid state is reported.

Full text of DOI:10.1016/S0022-328X(03)00226-2

Journal of Organometallic Chemistry 675 (2003) 42ꢁ47
/
www.elsevier.com/locate/jorganchem
Heteronoradamantanes Me2Si2(RM)2E5
(RMꢀMeGe, PhSn; EꢀS, Se)
/
/
Uwe Herzog a,*, Horst Borrmann b
a Institut fur Anorganische Chemie, TU Bergakademie Freiberg, Leipziger Str. 29, D-09596 Freiberg, Germany
¨
b Max-Planck-Institut fur Chemische Physik fester Stoffe, Nothnitzer Straße 40, D-01187 Dresden, Germany
¨
¨
Received 27 November 2002; received in revised form 20 January 2003; accepted 20 January 2003
Abstract
The reaction of a 1:2 molar mixture of 1,2-Me2Si2Cl4 and MeGeCl3 with H2S/NEt3 yielded Me2Si2(MeGe)2S5 (1), the first mixed
siliconꢁgermanium chalcogenide with a noradamantane-like structure, while the treatment of a 1:2 mixture of 1,2-Me2Si2Cl4 and
/
PhSnCl3 with Li2Se resulted in the formation of the first silicon- and tin-containing noradamantane Me2Si2(PhSn)2Se5 (2). Both
compounds have been characterized by NMR spectroscopy (1H, 13C, 29Si, 77Se and 119Sn). The molecular structure of 1 in the solid
state is reported.
# 2003 Elsevier Science B.V. All rights reserved.
Keywords: Disilane; Chalcogen; Adamantane; Noradamantane
1. Introduction
(tBuGe)4S4 could be isolated for Mꢀ
reactions for MꢀSi and EꢀS or Se resulted in the
cleavage of one SiꢀSi bond and the formation of
/
Ge and EꢀS,
/
/
/
Adamantane-like structures are frequently observed
in the chemistry of inorganic and organometallic
compounds [1]. Silsesquithianes [2,3] and selenanes [4]
/
noradamantanes (tBuSi)4S5 in low yield. A similar
observation was made in the reaction of 1,2-Me2Si2Cl4
with Li2Se, which exclusively yielded the noradaman-
tane (MeSi)4Se5 (4) [21], while the reaction of Me2Si2Cl4
with H2S/NEt3 yielded the tetracyclic cage compound
Me6Si6S6 formed by three disilane units [22]. In a more
straightforward reaction the treatment of a 1:2 molar
mixture of 1,2-Me2Si2Cl4 and MeSiCl3 with H2S/NEt3
resulted in the formation of (MeSi)4S5 (3) [21]. The first
silicon-containing bis-noradamantane, (RSi)4S4, was
as well as related germanium [5,6] and tin [7ꢁ
compounds (RM)4E6 (MꢀSi, Ge, Sn; EꢀS, Se) which
/
9]
/
/
usually adopt adamantane-like structures can easily be
obtained by reaction of an organotrichloro derivative
RMCl3 with either H2S/base or an alkaline chalcogenide
MI2E: Furthermore, several chalcogenosilicates [10ꢁ
germanates [13ꢁ17] and stannates [18,19] with adaman-
tane-like structures MI4[M4E10] (MIꢀ
Na, K, NR4; Mꢀ
Si, Ge, Sn; EꢀS, Se, Te) have been reported. When one
chalcogen atom is removed from the adamantane
structure the resulting cage (RM)4E5 is called norada-
mantane while removal of two chalcogen atoms results
in bis-noradamantanes (RM)4E4 (Scheme 1).
/
12],
/
/
/
/
isolated by reaction of R2Si2(NH2)4 (Rꢀ/CH(SiMe3)2)
/
with H2S [23].
However, no examples with two different Group 14
elements in the noradamantane or bis-noradamantane
cages are known so far.
Ando et al. [20] reported first examples of such cages
by reaction of 1,2-tBu2M2Cl4 (Mꢀ
/Si, Ge) with Li2E
(Eꢀ/S, Se). While the expected bis-noradamantane
* Corresponding author. Tel.: ꢂ
394058.
E-mail address: uwe.herzog@chemie.tu-freiberg.de (U. Herzog).
/
49-3731-394343; fax: ꢂ49-3731-
/
Scheme 1.
0022-328X/03/$ - see front matter # 2003 Elsevier Science B.V. All rights reserved.
doi:10.1016/S0022-328X(03)00226-2

U. Herzog, H. Borrmann / Journal of Organometallic Chemistry 675 (2003) 42ꢁ
/47
43
2. Results and discussion
The reaction of a mixture of 1,2-Me2Si2Cl4 and
MeGeCl3 with H2S and NEt3 yielded the expected
siliconꢁgermanium noradamantane (1) (see Eq. (1)):
/
ð1Þ
A similar reaction with MeSnCl3 instead of MeGeCl3
did not yield the corresponding tin-containing norada-
mantane; however, treatment of a 1:2 molar mixture of
1,2-Me2Si2Cl4 and PhSnCl3 with Li2Se in THF gave
Fig. 1. Molecular structure of 1. Thermal ellipsoids are at the 30%
probability level.
Table 1
Selected bond distances and angles of 1
yellow crystals of 2, a siliconꢁ
Eq. (2)):
/tin noradamantane (see
˚
Bond length (A)
Si1ꢀ
Si1ꢀ
Si1ꢀ
/
Si1a
2.3648(12)
2.1464(8)
2.1489(8)
2.2333(7)
2.2236(7)
2.2201(7)
1.930(2)
/S2
/S3
Ge1ꢀ
Ge1ꢀ
Ge1ꢀ
Ge1ꢀ
Si1ꢀ
/
S1
S2
/
/
S3a
C1
/
ð2Þ
Several attempts to produce the corresponding sulfur
/
C2
1.849(3)
Bond angle (8)
Si1aꢀ
Si1aꢀ
S2ꢀSi1ꢀ
Ge1ꢀS1ꢀ
Si1ꢀS2ꢀ
Si1ꢀS3ꢀ
S1ꢀ
S1ꢀ
S2ꢀ
/
Si1ꢀ
/
S2
S3
106.89(4)
105.33(4)
109.69(4)
105.10(4)
94.77(3)
compound via reactions of 1,2-Me2Si2Cl4ꢂPhSnCl3
/
/
Si1ꢀ
/
with either Li2S or H2S/NEt3 have been performed
without success. These observations show that forma-
tion of the heteronoradamantanes by these methods
strongly depends on the relative reactivities of the two
chlorocompounds used. If one of the two starting
materials reacts much faster with H2S/NEt3 or Li2E,
the expected heteronoradamantanes will not be formed.
The molecular structure of 1 was determined, as
depicted in Fig. 1. 1 crystallizes in the orthorhombic
/
/S3
/
/
Ge1a
/
/Ge1
/
/Ge1a
95.14(3)
/
Ge1ꢀ
Ge1ꢀ
Ge1ꢀ
/
S2
110.44(2)
111.54(2)
106.34(3)
/
/
S3a
S3a
/
/
˚
˚
3.512 A, S2ꢀ
/
S3a: 3.557 A, S3ꢀ
/
S2ꢀ
/
S3a: 89.818, S2ꢀ
/
S3ꢀ
/
space group Pbcn (Zꢀ
axis through S1, which intersects the bond Si1ꢀ
/
4). The molecule contains a C2
Si1a.
/
S2a: 90.188).
Both new heteronoradamantanes were characterized
by multinuclear NMR spectroscopy. Especially for 2 the
NMR spectra provide additional information about
connectivities in the noradamantane cage through the
Selected bond lengths and angles are given in Table 1.
Despite different crystal symmetry, the molecular
geometry of 1 is similar to that of 3 as reported in
Ref. [21]. Like in 3 the Si1ꢀ
than the average SiꢀSi bond length of 2.33ꢁ
disilanes like Si2Me6 or Si2Cl6 [24]. The SiꢀSꢀGe angles,
which are part of five-membered rings, are 108 smaller
than the angle Ge1ꢀS1ꢀGe1a which is only part of six-
membered rings of the noradamantane cage. The
dihedral angles S2ꢀSi1ꢀSi1aꢀS3a (1.528) and C2ꢀSi1ꢀ
Si1aꢀC2a (2.018) reveal that both five-membered rings
/Si1a bond is slightly longer
/
/
2.34 A in
occurrence of several satellites due to 1JSiSe, 2JSiSe, 2JSiSn
,
˚
1
/
/
2JSnSn and JSnSe (see Figs. 2ꢁ
/
4). As expected for a
noradamantane cage, there are two 77Se-NMR reso-
nances in a 4:1 intensity ratio, in which the lower signal
corresponds to the selenium atom which connects the
two tin atoms.
/
/
/
/
/
/
/
/
The NMR data of 1 and 2 including all observed
coupling constants are given in Table 2 and may be
compared with those of the silicon-based noradaman-
tanes Me4Si4E5 (3, 4). The NMR data of the disilane
units in 1 and 2 are similar to the values found in 3 and 4
Si2S2Ge adopt almost an envelope conformation. The
arrangement of the five sulfur atoms is approximated by
a tetragonal pyramid with S1 in the apical position. S2,
S3, S2a and S3a form an almost ideal square (S2ꢀ
/
S3:

44
U. Herzog, H. Borrmann / Journal of Organometallic Chemistry 675 (2003) 42ꢁ47
/
Fig. 2. 77Se-NMR spectrum of 2 showing the two different selenium sites. The satellites are caused by couplings with 119/117Sn and 29Si nuclei.
for the same element E. As observed previously for
tin chalco-
genides, the 29Si-NMR resonances show a low-field shift
when germanium is introduced into the ring system
instead of silicon, while a high-field shift is observed for
tin [25,26].
29Si spectra were recorded using a refocused INEPT
experiment. 77Se and 119Sn spectra were obtained
applying an IGATED pulse sequence. The assignment
of the ipso carbon atoms in the phenyl rings in 2 was
simplified by recording a 13C APT spectrum.
other mixed siliconꢁ
/
germanium and siliconꢁ
/
Mass spectra were measured on a Hewlett-Packard
The 77Se-NMR signal of the Siꢀ
shifted by about 50 ppm to higher field with respect to
53 ppm as observed in 4, while more than twice this
effect is observed for the SnꢀSe*ꢀSn linkage in com-
Si in 4. The observed JSnSe
/
Seꢀ
/
Sn linkage in 2 is
5971 (ionization energy: 70 eV, column: 30 mꢄ0.25
/
mmꢄ0.25 mm, phenylmethylpolysiloxane, column tem-
/
ꢃ
/
perature: 80 8C (3 min)/20 K minꢃ1, He flow: 0.5 ml
/
/
minꢃ1).
1
parison with Siꢀ
/
Se*ꢀ
/
coupling constants are by a factor of 9 larger than the
1
corresponding JSiSe in 4.
3.2. Crystal structure analysis
The X-ray structure analysis measurements of 1 were
performed on a Rigaku AFC7 with Mercury CCD at
room temperature. Crystal data*
/
size: 0.40ꢄ
/
0.08ꢄ
/
3. Experimental
0.05 mm3; formula weight: 421.84 g molꢃ1; space group:
˚
Pbcn (orthorhombic); unit cell: aꢀ
/
11.5972(10) A, bꢀ
/
3
˚
˚ ˚
10.7856(9) A; volume: 1503.6(2) A ;
3.1. NMR and GCꢁ
/MS measurements
12.0210(10) A, cꢀ
density (calc.): 1.863 g cmꢃ3; and linear absorption
coefficient: 4.813 mmꢃ1
/
All NMR spectra were recorded in 10-mm sample
tubes on a Bruker DPX 400 in CDCl3 solution and with
TMS as internal standard for 1H, 13C and 29Si. External
Me4Sn and Ph2Se2 (dSe 460 ppm) in CDCl3 were used as
standards for 119Sn and 77Se.
.
For data collection, unit cell refinement and data
reduction of 1, the program package Crystal Clear [27]
was used. The structure was solved using direct methods
(
SHELXS-97 [28]), refined using least-squares methods

U. Herzog, H. Borrmann / Journal of Organometallic Chemistry 675 (2003) 42ꢁ
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45
2
Fig. 3. 29Si-NMR spectrum of 2 with the satellites caused by coupling with 77Se (1JSiSe and JSiSe) and 119/117Sn (2JSiSn).
1
Fig. 4. 119Sn-NMR spectrum of 2 showing two sets of coupling satellites for 77Se (1JSnSe and JSnSe*) and satellites caused by 29Si (2JSiSn).

46
U. Herzog, H. Borrmann / Journal of Organometallic Chemistry 675 (2003) 42ꢁ47
/
Table 2
Nmr data of Noradamantanes Me2Si2(E)4(MR)2E
(Eꢀ
/
S, Se; MRꢀSiMe, GeMe, SnPh).
/
(
SHELXL-97 [28]) and drawn using DIAMOND [29]. The
carried out under argon applying standard Schlenk
techniques.
ellipsoids of non-hydrogen atoms are shown at the 30%
probability level. All hydrogen atoms were localized
from Fourier difference maps.
Absorption correction: numerical, measured reflec-
tions: 10 993, independent reflections: 1779, observed
3.4. 1,3,5,7-Tetramethyl-2,4,6,8,9-pentathia-3,7-disila-
1,5-digermatricyclo[3.3.1.03,7]nonane (1)
reflections: 1412 (I ꢀ
155h 515, ꢃ145
parameters: 62, final R1: 0.0268 (I ꢀ
data), wR2: 0.0600 (I ꢀ2sI), wR2: 0.0633 (all data),
/
2sI), Rint: 0.0316, index ranges:
k 515, ꢃ135l 512, number of
2sI), R1: 0.0431 (all
ꢃ
/
/
/
/
/
/
/
/
/
0.23 g (1.0 mmol) 1,2-Si2Me2Cl4 and 0.20 g (1.0
mmol) MeGeCl3 were dissolved in 30 ml hexane and
dried H2S was bubbled through the stirred solution
while 0.97 ml (7.0 mmol) NEt3 was slowly added. After
stirring for 1 h, the mixture was filtered from precipi-
tated HNEt3Cl and the solvent was removed in vacuo
yielding colorless crystals of 1 (0.12 g, 57%); m.p.:
176 8C. Excess 1,2-Si2Me2Cl4 reacts with H2S/NEt3 to
form Me6Si6S6 [22] which is almost insoluble in hexane
and is easily removed by filtration together with the
ammonium salt.
/
/
goodness-of-fit: 1.031, max./min. residual electron den-
ꢃ3
˚
0.267 e A
sity: ꢂ
/
0.665/ꢃ
/
.
3.3. Starting materials
H2S, Se, triethylamine, 1 M LiBEt3H in THF (Super
Hydride†), MeGeCl3, MeSnCl3 and PhSnCl3 were
commercially available. 1,2-Me2Si2Cl4 was prepared as
described previously [30]. THF was distilled from
1 GCꢁ
/
MS (m/e, rel. int.): 422 (Mꢂ, 7), 407 (Mꢃ
Me,
/
40), 347 (Me3SiGe2S4, 1), 303 (Me3Si2GeS4, 100), 288
(Me2Si2GeS4, 5), 182 (Me2Si2S3, 21), 167 (MeSi2S3, 13),
75 (MeSiS, 31); elemental analysis: C4H12Ge2S5Si2
sodiumꢁ/potassium alloy prior to use. The other solvents
were dried over KOH or sodium wire. All reactions were

U. Herzog, H. Borrmann / Journal of Organometallic Chemistry 675 (2003) 42ꢁ
/47
47
(Mꢀ
/
421.84 g molꢃ1, Calc./Found): C, 11.39/11.86; H,
References
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/
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Crystallographic data (excluding structure factors) for
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