Synthesis and Thorough Investigation of Discrete Organotin Telluride Clusters

Article abstract of DOI:10.1002/chem.201501666

Systematic experimental and theoretical investigations of reactions of R¹SnCl₃ (R¹=CMe₂CH₂C(Me)O) with (Me₃Si)₂Te allowed for the stepwise formation and single-crystalline isolation of the first tin sesquitelluride clusters with functional organic ligands. Subsequent derivatization of the latter took place under reorganization of the inorganic core, affording clusters with complex hybrid architectures.

Full text of DOI:10.1002/chem.201501666

DOI: 10.1002/chem.201501666
Full Paper
&
Cluster Compounds
Synthesis and Thorough Investigation of Discrete Organotin
Telluride Clusters
[a, b]
[a]
[a, b]
Jens P. Eußner,
Ralph O. Kusche, and Stefanie Dehnen*
Abstract: Systematic experimental and theoretical investiga-
with functional organic ligands. Subsequent derivatization of
the latter took place under reorganization of the inorganic
core, affording clusters with complex hybrid architectures.
1
1
tions of reactions of R SnCl (R =CMe CH C(Me)O) with
3
2
2
(
Me Si) Te allowed for the stepwise formation and single-
3 2
crystalline isolation of the first tin sesquitelluride clusters
1
[10]
Introduction
the C,O-chelating ligand R =CMe CH C(Me)O. Treatment of
2
2
1
the keto group at R with hydrazines yields the corresponding
hydrazones. Along with the change to the C,N-chelating li-
gands, rearrangements of the Sn/S or Sn/Se cores into new
cluster topologies were observed. Recently, we described the
The chemistry of Group 14 chalcogenides is now being elabo-
rately studied. Alongside the chemistry of silicates, research
[
1]
evolved to element combinations of higher homologous. In
particular, optoelectronic characteristics of these materials
were investigated and showed intriguing properties and po-
1
optimization of the syntheses by treating R SnCl3 (A) with
(Me Si) E (E=S, Se), which enables a directed, stepwise forma-
3
2
[2]
[11]
tential technical applications. As compared with the chemis-
try of tin sulfides and tin selenides, the chemistry of tin tellur-
ides maintains a niche existence because they were found to
be “significantly air-sensitive” and “are more difficult to prepare
tion of discrete organotin sulfide and selenide moieties.
Herein, we describe the synthesis and characterization of the
first discrete organotin telluride cage compounds, which we
obtained through stabilization by C,O- and C,N-chelating li-
gands. In the course of our systematic studies, we investigated
[
3]
4À
4À
and handle”. Binary anions like [SnTe ] , [Sn Te ]
and
4
2
6
4À
1
2À
[
Sn Te ] as well as ternary anions, such as { [HgSnTe ] }
condensation reactions between A and (Me Si) Te, yielding dif-
3 2
4
10
1
4
1
0À
and [M (m -Te)(SnTe ) ] (M=Mn, Zn, Cd, Hg), are some of the
ferent condensation products by control of the stoichiometry
of the reagents. The consecutive reaction with hydrazines
yielded clusters with different topologies, tailored by the
choice of the respective hydrazine derivative. The obtained
organo-functionalized bimetallic clusters exhibit low band-gap
energies as presented as a proof-of-principle by means of UV/
Visible spectroscopy experiments and quantum chemical inves-
4
4
4 4
[4,5]
rare known examples.
Organic decoration, however, enhances the stability of the
tin chalcogenide scaffolds. Discrete organotin telluride moiet-
ies have thus been stabilized through bulky organic substitu-
[
6]
[7]
ents, donating organometallic or organoelement ligands, or
[
8]
intramolecular heteroatom coordination of organic ligands.
The tridentate N,C,N-chelating ligand 2,6-(Me NCH ) C H re-
[
12]
tigations using density functional theory (DFT) methods, in
particular time-dependent (TD-DFT) calculations.
2
2 2
6
3
vealed a series of monoorganotin chalcogenide compounds,
II
inter alia, allowing for the stabilization of terminal Sn =Te
[
9]
bonds. In contrast with the numerous polynuclear (RSn)/S
and (RSn)/Se complexes containing a variety of organic ligands
R, no discrete organotin telluride cage compounds are known Results and Discussion
at present.
Synthesis
Previous publications of our group describe the synthesis of
organogermanium and organotin chalcogenide clusters with
Scheme 1 illustrates the synthesis of the compounds obtained
1
herein. Condensation reactions of R SnCl (A) and (Me Si) Te
3
3
2
led to the formation of compounds 1–3. DFT calculations
showed that the stepwise condensation is energetically fa-
[
a] J. P. Eußner, R. O. Kusche, Prof. Dr. S. Dehnen
Fachbereich Chemie, Philipps-Universität Marburg
Hans-Meerwein-Strasse, 35037 Marburg (Germany)
E-mail: dehnen@chemie.uni-marburg.de
vored, with the generation of Me SiCl as the driving force. De-
3
rivatization reactions at the organic substituents with different
[
b] J. P. Eußner, Prof. Dr. S. Dehnen
mono-substituted hydrazine derivatives yielded compounds 4–
Wissenschaftliches Zentrum für Materialwissenschaften (WZMW)
Philipps-Universität Marburg
Hans-Meerwein-Strasse, 35037 Marburg (Germany)
9
.
The employment of the bifunctional carbohydrazide
H N C(O)N H resulted in a complex product mixture. From
3
2
2
3
this, compounds 10–12 were isolated in single crystalline form.
All of the reactions were carried out under an inert argon at-
Supporting information for this article is available on the WWW under
http://dx.doi.org/10.1002/chem.201501666.
Chem. Eur. J. 2015, 21, 12376 – 12388
12376
ꢀ 2015 Wiley-VCH Verlag GmbH & Co. KGaA, Weinheim

Full Paper
2
À
À
nate anion [R SnCl ] and two inorganic [SnCl3]
4
anions that exhibit Sn atoms in the oxidation state of
2
À
+
II. The [R SnCl ] anion could be an intermediate
4
prior to the reductive elimination of the organic
À
[14]
ligand as one possibility to form the [SnCl ] anion.
3
The slightly altered reaction conditions for the gener-
ation of 5, namely, employment of the hydrate in-
stead of a solution of water-free hydrazine in THF,
were followed by rapid crystallization within one day;
this is in agreement with intense intermolecular inter-
actions within the crystal structure. However, the in-
creased amount of water present under these condi-
tions also accelerates the decomposition of the reac-
tion solutions to form SnTe after several days.
The reaction of phenyl hydrazine with 2 yields the
3
3
DHC
cluster
[(R Sn) Te ][SnCl ]
(6,
R =
3
4
3
CMe CH C(Me)NNHPh). In a solution of dichlorometh-
2
2
ane, the condensation reaction proceeds such that
3
the compound [(R Sn) Te ] (7) is obtained after two
4
6
weeks in a sealed NMR test tube as single crystalline
material. The generation of larger clusters comes
along with an overall energy gain, as shown for the
stepwise condensation of the keto-functionalized
clusters (see below), which rationalizes the observa-
tions. Compound 7 was also obtained directly by the
treatment of phenyl hydrazine with 3.
1
Scheme 1. Synthesis of compounds 1–12. R =CMe
2
CH
2
4
C(Me)O;
2
3
R =CMe
R ={CMe
2
CH
CH
2
C(Me)NNH
C(Me)NN}
2
; R =CMe
C(O); R =CMe
2
CH
2
C(Me)NNHPh; R =CMe
CH C(Me)NNC(O)NNH . The reactions were carried
2 2
Cl or toluene; for further experimental details see the
2 2
CH C(Me)NNC(S)NHPh;
5
6
2
2
2
2
2
2
out under inert conditions in CH
Supporting Information.
mosphere, under exclusion of light and external moisture. All
solvents were dried and freshly distilled prior to use.
Thiosemicarbazide H N C(S)NHPh reacts with 2 to form
3 2
4
4
[(R Sn) Te ] (8, R =CMe CH C(Me)NNC(S)NHPh), under reten-
2
2
2
2
The reaction of two equivalents of A with one equivalent of
tion of the inorganic core, along with two equivalents of HCl
(
Me Si) Te in toluene, and subsequent layering of the reaction
and H O as side products. The tridentate C,N,S-chelating or-
3
2
2
1
solution with n-hexane afforded [(R SnCl ) Te] (1) in 81% yield.
Ongoing condensation with another equivalent of (Me Si) Te
ganic ligand apparently disables the possibility of further con-
densation for steric reasons. Moreover, we observed the gener-
2
2
3
2
1
4
generated a four-membered Sn Te ring in [(R SnCl) Te ] (2).
ation of [{(HR )Sn} Te ] (9) as another side product when work-
2
2
2
2
4
6
This compound formed as an orange precipitate from the tolu-
ene solution in 86% yield. Dissolving the precipitate in di-
chloromethane and layering of the solution with n-hexane af-
forded 2. At low concentrations, the condensation reaction of
A with (Me Si) Te in a 1:1.5 stoichiometric ratio in dichloro-
ing in a mixture of dichloromethane and methanol. The crystal-
lization of 9 is not observed if working exclusively in dichloro-
methane solution, whereas
9 crystallizes selectively by
treatment of 3 and thiosemicarbazide in a mixture of dichloro-
methane and methanol with subsequent layering with n-
hexane.
3
2
methane and subsequent layering with n-hexane generated
1
[
(R Sn) Te ] (3) in 52% yield. Higher concentrations of reactants
Employment
of
the
bifunctional
carbohydrazide
4
6
or additional addition of (Me Si) Te led to decomposition and
H N C(O)N H links two tin atoms through multidentate organ-
3
2
3
2
2
3
5
5
6
5
6
the generation of a brown powder of SnTe.
ic HR , H R , and HR (R ={CMe CH C(Me)NN} C(O), R =
2 2 2 2
By using ESI(+) mass spectrometry in dichloromethane solu-
tion, we observed a peak with m/z corresponding to the
CMe CH C(Me)NNC(O)NNH ) substituents. The main product of
2 2 2
this reaction was 10, which crystallized after one day. After
three days, a smaller quantity of crystals of 11 and 12 formed
from the same solution. In 10 and 11, only one [SnÀTeÀSn]
unit is present. Compound 12 consists of an [Sn Te ] chain and
1
+
[13]
[
(R Sn) Te ] cation.
However, the addition of alkali metal
3
4
À
À
salts of weakly coordinating anions like [PF ] , [SbF ] , or
6
6
À
1
+
[
BPh ] to stabilize the [(R Sn) Te ] cation or careful variations
4 3 4
7
8
of the stoichiometric ratio of A and (Me Si) Te in different sol-
represents the aggregation product on the route towards
3
2
1
1
2À [15]
vents failed to promote the crystallization of a [(R Sn) Te Cl] (I)
a polymeric species, such as {[{(C H COO)Sn} Te ] }. Fur-
1 2 4 2
3
4
3
derivative, which was predicted to be stable according to DFT
calculations (see below).
ther aggregation seems to be kinetically prohibited by the
5
6
multidentate organic ligands. The generation of HR and HR li-
gands took place in situ by deprotonation of the original
ligand at the a-position of the central carbonyl unit.
The treatment of 2 in dichloromethane solution with hydra-
À1
2
2
zine (1 molL in THF) afforded [(R Sn) Te ] [R SnCl ][SnCl ] (4),
3
4 3
4
3 2
whereas the treatment of 2 with hydrazine hydrate yielded
We interpret the observation of compounds 10–12 as an in-
dication for the complex processes and dynamic behavior of
organotin tellurides in solution, and as an indication of the
rather labile SnÀTe bond, which allows for easier fragmentation
2
2
+
[
(R Sn) Te ] (5). The inorganic core of the [(R Sn) Te ] cation in
4 6 3 4
4
exhibits the defect-heterocubane (DHC) motif. The cationic
charge is compensated for by one organotetrachlorido stan-
Chem. Eur. J. 2015, 21, 12376 – 12388
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ꢀ 2015 Wiley-VCH Verlag GmbH & Co. KGaA, Weinheim

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in accordance with the DFT results. A similar observation, al-
though with an inverse Ge/E ratio of 1:2 compared with the
Sn/Te ratio of 2:1 in 10, was made with the organogermanium
tion of the clusters so far, which is in accordance with the
greater stability of the according SnÀE bonds.
All of the title compounds were obtained as single crystals
(for crystallographic details see Tables 1 and 2) and were fur-
2
À
2
[16]
telluride fragment [R GeTe ] (R =CMe CH C(Me)NNH ). No-
2
2
2
2
1
13
119
125
tably, for E=S or Se, we have not experienced any fragmenta-
ther characterized by means of H, C, Sn, and Te NMR
Table 1. Crystallographic and refinement details of (Me
3
Si)
2
Te and 1–9 at 100(2) K (MoKa radiation, l=0.71073 Š, 4·4CH
2
Cl
2
was measured at 250(2) K). For
further details, see the Supporting Information.
(
Me
3
2
Si) Te
1
2
3
2 2
4·4CH Cl
empirical formula
C
6
H
18Si
2
Te
C
12
H
22Cl
4
O
2
Sn
2
Te
C
12
H
22Cl
2
O
2
Sn
2
Te
2
C
24
H
44
O
4
Sn
4
Te
6
64
C H118Cl18N20Sn12Te12
À1
M
r
[gmol
]
273.98
705.08
yellow needle
0.45”0.13”0.12
triclinic
P1¯
10.1476(7)
10.6472(6)
11.1163(7)
77.251(5)
66.784(5)
85.427(5)
1076.54(12)
2
761.82
orange block
0.12”0.12”0.10
monoclinic
1636.95
red block
0.07”0.07”0.06
monoclinic
4761.61
red block
0.23”0.18”0.18
monoclinic
crystal color and shape
colorless block
0.40”0.30”0.20
monoclinic
C2/c
9.508(5)
11.183(6)
11.703(10)
90
103.94(5)
90
1207.7(14)
4
3
crystal size [mm ]
crystal system
space group
a [Š]
b [Š]
c [Š]
P2
1
/n
P2
1
/n
1
P2 /n
8.0853(8)
12.0453(10)
11.1735(10)
90
104.811(7)
90
1052.03(17)
2
2.405
11.8919(4)
13.2562(6)
13.2290(4)
90
92.284(3)
90
2083.78(13)
2
2.609
18.0227(5)
32.9729(12)
24.5659(7)
90
93.475(2)
90
14571.7(8)
4
2.170
a [8]
b [8]
g [8]
3
V [Š ]
Z
1
À3
calcd [gcm
]
1.507
2.603
2.175
4.145
À1
m(MoKa) [mm
]
5.344
6.511
4.739
absorption correction type
min/max transmission
numerical
0.284/0.613
5.72–53.44
4199
numerical
0.207/0.660
4.36–53.52
4757
numerical
0.394/0.405
4.60–53.54
5871
numerical
0.606/0.714
4.36–53.42
29232
numerical
0.386/0.523
2.72–50.00
74638
2
q range [8]
measured reflns
R(int)
0.0740
0.0978
0.1529
0.0988
0.0835
independent reflns
independent. reflns [I>2s(I)]
parameters/restraints
1279
1247
45/0
0.0350/0.0850
1.149
3400
3147
196/0
0.0444/0.1185
1.083
2207
2099
94/0
0.0388/0.0977
1.147
4416
3429
178/0
0.0411/0.0862
0.995
25582
10777
1112/205
0.0649/0.1785
0.810
2.40/À0.89
R
1
[I>2s(I)]/wR
2
(all data)
S (all data)
max peak/hole [e Š
À
À3
]
1.45/À2.13
1.85/À1.57
1.58/À1.86
1.15/À0.86
5
6·C
6
H
14
7·3CH
2
Cl
2
8
9·2MeOH
empirical formula
C
24
H
52
N
8
Sn
4
Te
6
C
42
H
65Cl
3
N
6
Sn
4
Te
4
C
51
H
74Cl
6
N
8
Sn
4
Te
6
C
26
H
34
N
6
S
2
Sn
2
Te
2
54 80 12 2 4 4 6
C H N O S Sn Te
2297.90
red block
0.08”0.08”0.03
monoclinic
1
P2 /c
11.2842(3)
13.4743(3)
24.4757(7)
90
102.777(2)
90
3629.30(16)
2
2.103
À1
M
r
[gmol
]
1693.10
red needle
0.24”0.01”0.01
orthorhombic
Ccca
15.5522(5)
24.9456(9)
22.7771(8)
90
90
90
8836.6(5)
8
2.545
1745.33
red needle
0.50”0.04”0.03
monoclinic
2252.24
red block
0.60”0.60”0.32
triclinic
P1¯
12.6218(8)
12.7680(8)
12.9379(8)
74.290(5)
79.858(5)
61.521(4)
1761.52(19)
1
987.29
yellow block
0.20”0.04”0.03
monoclinic
crystal color and shape
3
crystal size [mm ]
crystal system
space group
a [Š]
b [Š]
c [Š]
P2
1
/c
P2
1
/c
11.4360(5)
21.7536(7)
22.6477(9)
90
98.917(3)
90
5566.1(4)
4
2.083
8.0349(3)
10.4031(6)
20.4275(13)
90
101.565(4)
90
1672.83(16)
2
1.960
a [8]
b [8]
g [8]
3
V [Š ]
Z
1
À3
calcd [gcm
]
2.123
4.102
À1
m(MoKa) [mm
]
6.144
4.001
3.353
3.885
absorption correction type
min/max transmission
numerical
0.521/0.955
3.36–53.54
27617
numerical
0.240/0.889
2.62–53.52
44985
numerical
0.062/0.271
3.28–53.54
16048
numerical
0.603/0.895
4.08–53.64
11108
numerical
0.489/0.890
3.42–53.48
31932
2
q range [8]
measured reflns
R(int)
0.1471
0.0798
0.0826
0.0958
0.0471
independent reflns
independent. reflns [I>2s(I)]
parameters/restraints
4702
3199
209/4
11 783
7236
487/0
7443
5856
364/0
3537
2628
178/0
7688
6808
429/31
R
1
[I>2s(I)]/wR
S (all data)
max peak/hole [e Š
2
(all data)
0.0525/0.0779
0.960
1.06/À1.24
0.0307/0.0572
0.832
0.98/À0.61
0.0541/0.1425
0.976
2.07/À2.19
0.0526/0.1443
1.016
1.10/À2.30
0.0389/0.0994
1.069
1.54/À1.32
À
À3
]
Chem. Eur. J. 2015, 21, 12376 – 12388
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12378
ꢀ 2015 Wiley-VCH Verlag GmbH & Co. KGaA, Weinheim

Full Paper
Table 2. Crystallographic and refinement details of 10–12 at 100(2) K (MoKa radiation, l=0.71073 Š). Compound 12·5CH
2
Cl
2
should only viewed as a struc-
tural model. For further details see the Supporting Information.
1
0·CH
2
Cl
2
11·1.5CH
2
Cl
2
12·5CH
2
Cl
2
2 2
12·2CH Cl
empirical formula
C
14
H
25Cl
5
N
4
OSn
2
Te
C
21.5
H
37Cl
8
N
8
O
2
Sn
3
Te
C
50
H
92Cl14
N
12
O
4
Sn
7
Te
8
47 8 12 4 7 8
C H86Cl N O Sn Te
À1
M
r
[gmol
]
807.61
colorless plates
0.12”0.12”0.01
monoclinic
1206.86
yellow block
0.21”0.15”0.10
monoclinic
C2/c
34.533(2)
11.3986(4)
32.791(2)
90
139.003(3)
90
3273.29
red block
0.38”0.30”0.25
triclinic
3018.51
red block
0.20”0.18”0.12
triclinic
P1¯
15.4273(8)
16.5614(8)
19.9402(10)
66.268(4)
82.149(4)
73.093(4)
4461.2(4)
2
crystal color and shape
3
crystal size [mm ]
crystal system
space group
a [Š]
b [Š]
c [Š]
P2
1
/c
P1¯
7.2831(5)
22.8035(14)
15.2834(12)
90
91.845(6)
90
2537.0(3)
4
2.114
18.5622(9)
21.6960(8)
26.6656(10)
68.646(3)
79.599(3)
75.079(3)
9619.4(7)
4
a [8]
b [8]
g [8]
3
V [Š ]
8467.5(8)
8
1.893
Z
1
À3
calcd [gcm
]
2.260
4.597
2.247
4.772
À1
m(MoKa) [mm
]
3.635
2.967
absorption correction type
min/max transmission
numerical
0.669/0.965
3.20–50.00
14287
numerical
0.478/0.690
2.60–53.56
8946
numerical
0.284/0.406
2.68–50.00
33718
numerical
0.471/0.651
2.72–53.60
40509
2q range [8]
measured reflns
R(int)
0.1211
0.1041
0.1462
0.1137
independent reflns
independent reflns [I>2s(I)]
parameters/restraints
14287
6857
251/8
8946
3725
403/1
33718
19533
988/8
18876
10499
796/7
R
1
[I>2s(I)]/wR
S (all data)
max peak/hole [e Š
2
(all data)
0.0618/0.1437
0.805
2.14/À1.27
0.0615/0.1546
0.740
2.06/À1.38
0.1756/0.4215
2.269
8.44/À3.39
0.0509/0.1224
0.810
1.95/À1.76
À
À3
]
spectroscopy, ESI(+) mass spectrometry, IR and UV/Vis spec-
troscopy. The qualitative and quantitative elemental composi-
tion was verified by EDX spectroscopy. The thermal behavior
was investigated by means of simultaneous TGA/DSC experi-
ments. Experimental details are provided in the Supporting In-
formation.
Sn2-Cl3: 177.1(1)8). The bidentate organic ligands form intra-
molecular Lewis acid–base interactions with the central Sn
atoms generating a nearly planar, five membered Sn-C-C-C-O
ring (C1-Sn1: 2.186(5), C7-Sn2: 2.190(5), O1···Sn1: 2.440(4), O2-
Sn2: 2.463(4) Š). Within the Figures 1–8, we depict O!Sn
(below N!Sn) coordination as dashed lines to accentuate that
the O···Sn distance is considerably larger than the sum of the
covalent radii of O and Sn atoms (r (OÀSn)=2.03 Š, (r (NÀ
cov
cov
Crystal structures
[
18]
Sn)=2.11 Š). The C-Sn-O angles amount to 75.4(2) (Sn1) and
75.1(2)8 (Sn2). SnÀCl bonds to Cl substituents trans to O sub-
stituents in axial positions (Sn1ÀCl1: 2.417(1), Sn2ÀCl3:
2.413(1) Š) are slightly longer than the SnÀCl bonds in the
equatorial positions (Sn1ÀCl2: 2.384(1), Sn2ÀCl4: 2.383(1) Š)
because of the intramolecular O!Sn interaction.
We report the crystal structure of the widely used volatile re-
agent (Me Si) Te (Figure 1, top) for a profound discussion of
3
2
the obtained compounds. (Me Si) Te (monoclinic space group
3
2
C2/c with Z=4) crystallized by slow cooling from room tem-
perature to 233 K. One-half of the molecule is located in the
asymmetric unit with the central Te atom residing on a special
position bisected by a C2 axis. The SiÀTe bond length is
Compound 2 crystallizes as orange blocks in the monoclinic
space group P2 /n with Z=2 (Figure 1, bottom). The molecule
1
2
.518(1) Š and the Si-Te-Si angle is 100.92(6)8. The SiÀTe bond
possesses crystallographic inversion symmetry, thus including
a planar [Sn Te ] four-membered ring (Sn-Te-Sn: 82.43(1), Te-
length is similar to that observed in [(tBuMe Si) Te], whereas
2
2
2
2
the Si-Te-Si angle is more acute because of the reduced steric
Sn-Te: 97.57(1)8). The Sn1ÀTe1 bond length is 2.7080(5) Š, thus
[17]
ii
influence of the SiMe groups. There are no Te···Te contacts
smaller than that of Sn1ÀTe1 (2.7913(5) Š; ii=Àx, 1Ày, 1Àz).
3
below 5 Š within the crystal structure.
Compound 1 crystallizes in the triclinic space group P 1¯ with
Again, Sn atoms show trigonal biypramidal coordination,
though having O and Te atoms in the axial positions (O1-Sn1-
ii
Z=2 as yellow needles (Figure 1, center). The molecule con-
Te1 : 176.8(1)8). The replacement of Cl atoms with Te atoms
1
sists of two [R SnCl ] fragments that are connected by a m-Te
leads to an elongation of the O···Sn distance by about 0.16 to
2.596(6) Š, as a consequence of the strong trans effect induced
by the Te ligand.
2
atom. The SnÀTe bond lengths are 2.7076(5) (Sn1ÀTe1) and
2
9
.7110(4) Š (Sn2ÀTe1), and the Sn-Te-Sn angle amounts to
5.05(1)8. The tin atoms possess coordination number of 5 and
Crystals of 3 form red blocks (space group P2 /n, Z=2;
1
show trigonal bipyramidal coordination with the two axial po-
sitions occupied by O and Cl atoms (O1-Sn1-Cl1: 176.3(1), O2-
Figure 2). The cluster adopts the double-decker-type (DD) top-
1
ology with two [{(R Sn)(m-Te)} (m-Te)] units surrounding an in-
2
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Figure 2. Molecular structure of 3 without H atoms. Ellipsoids are drawn at
5
2
0%. iii=1Àx, 1Ày, Àz; Selected structural parameters [Š, 8]: Sn1ÀTe1:
.7324(7), Sn1ÀTe2: 2.7915(7), Sn1ÀTe3: 2.7168(7), Sn2ÀTe1: 2.7778(7), Sn2À
iii
Te2: 2.7168(7), Sn2ÀTe3 2.7581(7), Sn1-Te1-Sn2: 84.389(19), Sn1-Te2-Sn2:
iii
84.42(2), Sn1-Te3-Sn2 100.11(2), Te1-Sn1-Te2 95.26(2), Te1-Sn1-Te3 110.51(2),
iii
Te1-Sn1-Te3 118.78(2), Te1-Sn2-Te2 95.93(2), Te1-Sn2-Te3 113.55(2), Te2-Sn2-
Te3 118.82(2).
(
AD) topology because of the realization of a stabilizing intra-
molecular O!Sn coordination in the first case. The energy dif-
ference of the respective isomers increases along the homolo-
1
gous series of [(R Sn) E ] (E=S, Se, Te) from 14.9 (E=S)
4
6
À1
through 26.8 (E=Se) to 34.1 kJmol (E=Te); this indicates an
even more efficient O!Sn interaction in the DD topology for
E=Te as compared with the lighter congeners.
In compounds 1–3, the SnÀTe bond lengths and Sn-Te-Sn
angles are in the range of those observed in known organotin
Figure 1. Molecular structures of (Me
3
Si)
2
Te (top), 1 (center), and 2 (bottom)
7
[9a]
7
II
7
IV
7
II
tellurides like [(R BuSn) Te ], [(R Sn ) Te], [(R Sn Te)(R Sn )Te]
2
2
2
without H atoms. Ellipsoids are drawn at 50%. i=Àx, y, 0.5Àz; ii=Àx, 1Ày,
7
[9b]
8
8
[19]
(
R =2,6-(Me NCH ) C H ), [{(R ) Sn} Te ] (R =CH SiMe ), or
2 2 2 6 3 2 3 6 2 3
1
Àz. Selected structural parameters [Š, 8]: (Me
3
2
Si) Te : Si1ÀTe1 2.518(1), Si1-
1
9
2–
9
[10]
i
Te1-Si1 100.92(6); 1: Sn1ÀTe1 2.7076(5), Sn2ÀTe1 2.7110(4), Sn1-Te1-Te2
the polyanion {[(R Sn) Te ] } the polyanion (R =C H CO ).
1 2 3 2 4 2
ii
ii
9
5.05(1); 2: Sn1ÀTe1 2.7080(5), Sn1ÀTe1 2.7913(5), Sn1-Te1-Sn1 82.43(1),
As a result of our systematic studies of organotin chalcoge-
ii
Te1-Sn1-Te1 97.57(1).
1
nides with the C,O-bidentate R ligand system, the distinct in-
fluence of the different chalcogen atom types (E=S, Se, Te) be-
[
11]
version center. The nearly planar [Sn Te ] rings (sum of
comes evident. The structural consequences are, as expect-
ed, elongation of the SnÀE bonds in the order E=S!Se!Te,
along with more acute Sn-E-Sn angles.
2
2
angles=359.18) can be viewed as a fragment of 2, with similar
structural parameters of the inorganic moiety (SnÀTe :
iii
2
1
.7168(7)–2.7915(7) Š). The Sn1-Te3-Sn2 angle (100.11(2)8; iii=
Àx, 1Ày, Àz) is considerably more obtuse than the Sn-Te-Sn
The condensation reaction of various hydrazines with the
keto-groups of the C,O-chelating ligands produce C,N-chelat-
ing ligands to coordinate the Sn atoms. This induces a change
of the electronic situation at the inorganic core, because of the
more effective N!Sn interaction when compared with the
O!Sn interaction before. Different topologies and dynamic
behavior of organotin chalcogenides in solution, which is well
angles within the four rings. The organic substituents are
pushed out of the plane of four-membered ring, resulting in
both an elongation of the CÀSn and Sn···O distances (C1ÀSn1:
2
2
.207(7), C7ÀSn2: 2.203(7), Sn1···O1: 2.645(5), Sn2···O2:
.788(6) Š) and more acute C-Sn-O angles (C1-Sn1-O1: 70.8(2),
[
20]
C7-Sn2-O2: 68.5(2)8). The orientation and sterical demand of
the four organic substituents effectively prohibit further aggre-
gation or polymerization. In compounds 1–3 no significant in-
termolecular contacts are present involving Sn or Te atoms.
According to DFT calculations on such organotin sesquichal-
cogenide clusters, the DD topology is energetically preferred
portrayed in the literature. In general, the isolation of com-
pounds as crystalline material from such dynamic equilibria is
based on a lower solubility and favorable intermolecular inter-
actions within the crystal with respect to other species in solu-
tion. Accordingly, slight variations of the reaction conditions
can provoke the crystallization and isolation of other com-
pounds. The different stability/solubility of a compound with
À1
by 34.1 kJmol over the isomeric hetero-adamantane-type
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a certain molecular structure is affected by the steric demand
of the substituents, the electronic situation of the substituents,
and the tendency of aggregation within solution and/or the
crystal.
The molecular structure of 5 is shown in Figure 4. The com-
pound crystallizes in the orthorhombic space group Ccca with
Z=8. The organotin sesquitelluride cluster is another one to
be found in DD topology. The in-plane deformation of the
2
Compound 4·4CH Cl crystallizes in the monoclinic space
planar [(R Sn) Te ] ring (sum of angles=360.08) is more pro-
2
2
2
2
group P2 /n with Z=4. Compound 4 is a double salt consisting
1
2
+
2
À
of three [(R Sn) Te ] cations besides one [R SnCl ] anion and
3
4
4
À
two [SnCl ] anions within the asymmetric unit. The molecular
3
2
+
structure of one of the [(R Sn) Te ] cations is shown in
3
4
Figure 3. The inorganic part of the molecule consists of an al-
Figure 4. Molecular structure of 5 without H atoms. Ellipsoids are drawn at
5
2
2
0%. iv=0.5Àx, 1Ày, z; Selected structural parameters [Š, 8]: Sn1ÀTe1:
.7339(9), Sn1ÀTe2 2.8349(9), Sn1ÀTe3 2.7512(8), Sn2ÀTe1 2.877(1), Sn2ÀTe2
.7219(9), Sn2ÀTe4 2.7700(8), Sn1-Te1-Sn2 85.47(3), Sn1-Te2-Sn1 86.52(3),
iv
iv
Sn1-Te3-Sn1 102.92(4), Sn2-Te4-Sn2 101.53(4), Te1-Sn1-Te2 94.35(3), Te1-
Sn1-Te3 126.11(3), Te2-Sn1-Te3 103.31(3), Te1-Sn2-Te2 93.66(3), Te1-Sn2-Te4
106.60(3), Te2-Sn2-Te4 123.40(3).
Figure 3. Molecular structure of one of three crystallographically independ-
2
+
3 4
ent [(R Sn) Te ] cations in 4. Ellipsoids are drawn at 30% without H atoms.
The larger extension of the thermal ellipsoids are due to the necessity to
measure the compound at 250 K to avoid cracking of the crystals (see the
Supporting Information). Selected structural parameters [Š, 8]: Sn1ÀTe1
1
nounced here than in the case of the R -decorated analogue
2
2
2
.902(1), Sn2ÀTe2 2.757(1), Sn1ÀTe3 2.748(2), Sn2ÀTe1 2.929(2), Sn2ÀTe2
.757(1), Sn2ÀTe4 2.757(2), Sn3ÀTe1 2.953(2), Sn3ÀTe3 2.750(2), Sn3ÀTe4
.741(2). The structural parameters of the inorganic part of the other
because of the stronger N!Sn coordination as compared to
O!Sn in 3. The SnÀTe bonds in trans position to the N atoms
are elongated by about 0.05 to 0.10 Š as compared with the
other SnÀTe bonds (in 3 the O!Sn coordination leads to an
2
+
[
(R Sn)
3
Te
4
]
cations are similar. SnÀTe 2.742(1)–2.955(2), Sn-Te-Sn 79.87(4)-
8
7.36(4), Te-Sn-Te 92.10(4)-118.30(5).
elongation of 0.02 to 0.06 Š). A C axis runs through Te3 and
2
Te4; this is in agreement with a twist of the inorganic core per-
pendicular to this axis and a different relative orientation of
the organic substituents as compared to 3 (see the Supporting
Information, Figure S11). DFT calculations show that the
change of conformation has its origin on the molecular level.
ternating six-membered SnÀTe ring, which is capped by an ad-
ditional m -Te atom, thus generating a DHC scaffold. The SnÀTe
3
bond lengths within the six-membered rings are smaller (Sn-m-
Te : 2.742(1)–2.765(2) Š) than those involving the m -Te atoms
3
À1
(
Sn-m -Te: 2.891(1)–2.955(2) Š); this accords with three N!Sn
The observed conformer is more favorable by 9.1 kJmol as
3
donating C,N-chelating ligands in the trans positions to the m -
compared to the same complex in the hypothetic, not-ob-
3
Te atoms in each cluster (N···Sn: 2.34(1)–2.39(1) Š, N-Sn-m -Te:
served conformation according to 3. Contrariwise, the ob-
3
1
73.5(4)-178.5(4)8).
served molecular conformation of 3 is energetically favored by
2
+
À1
The [(R Sn) Te ] cations form intermolecular Te···Te and NÀ 7.6 kJmol over the hypothetic, not-observed conformation
3
4
H···Te as well as NÀH···N interactions with each other, generat-
ing a six-membered cationic chain (see the Supporting Infor-
mation, Figure S8). Generally, the intermolecular Te···Te distan-
ces are longer than the sum of van der Waals radii of two Te
according to 5.
A one-dimensional chain along the crystallographic a axis is
formed through intermolecular Te···Te and NÀH···Te interac-
tions (see the Supporting Information, Figure S12). The inter-
molecular Te···Te distance (3.521(1) Š) is very short and can be
[
21]
atoms (4.16 Š), except for the considerably smaller Te1···Te5
distance (4.033(1) Š). The anions are situated around the
chains and exhibit Sn···Te, Te···Cl, and NÀH···Cl interactions,
generating a complex three-dimensional network.
[
22]
attributed to secondary binding interactions. Through addi-
tional NÀH···N hydrogen bonding, a two-dimensional network
evolves in the (101) plane.
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The reactions of phenyl hydrazine with the keto-functional-
ized clusters lead to the formation of 6 and 7 (see Figure 5). As
compared with the hydrazone groups of 4 and 5, the phenyl
hydrazine group induces a larger steric demand. Again, two
different clusters were found, with DHC and DD scaffolds, re-
spectively.
distal nitrogen atoms of the hydrazone groups of the adjacent
cluster (3.303(6)–3.415(5) Š). The combination of short secon-
dary Sn···Te contacts, NÀH···Cl hydrogen bonds, and electro-
static interactions might trigger the formation and support the
stabilization of this structural motif here. An additional inter-
molecular and self-complementary Te···Te interaction between
The structural parameters of the inorganic core of the
adjacent m -Te atoms (3.9476(8) Š) leads to dimerization (see
3
3
+
[
(R Sn) Te ] cation within 6 (6·C H , monoclinic space group
the Supporting Information, Figure S14).
3
4
6
14
2
+
P2 /c, Z=4) are almost identical to those of the [(R Sn) Te ]
Although the inorganic core of 7 adopts DD topology
(7·3CH Cl , triclinic space group P 1¯ , Z=1), the molecular struc-
1
3
4
À
cations in 4. One [SnCl3] anion per formula unit is present
here to compensate for the charge; it closely interacts with the
cluster cation by occupying the defect position of the DHC.
The resulting heterocubane is naturally distorted in this direc-
tion, with additional, relatively short intermolecular Sn···Te con-
2
2
ture differs notably from the DD clusters in 3 and 5. The tin
atoms exhibit a coordination number of four and are coordi-
nated in a distorted tetrahedral fashion instead of the trigonal
bipyramidal fashion observed in 3 and 5. The bulky organic
substituents apparently prohibit a closer N···Sn approximation
À
tacts (3.7778(6)–3.8106(6) Š). The chlorine atoms of the [SnCl3]
[
23]
counterion are within short intermolecular distances from the
(N1···Sn1: 3.126(8) Š, N3···Sn2: 3.130(8) Š). Hence, the SnÀTe
bond lengths are within
very narrow range (SnÀTe :
.7461(7)–2.7567(6) Š). The organic substituents of each of the
a
2
3
[
(R Sn) Te ] units point into the same direction with regard to
2 2
the inorganic cluster core, hence providing an optimal steric
protection, which results in a kinetically inert cluster.
Notably, the aggregation of Sn/Te clusters has so far stopped
[
11]
at the stage of the organotin sesquitelluride [Sn Te ] core. In
4
6
the case of organotin sulfides, further cluster growth to
3
[
(R Sn) Sn S ] was observed, which included the generation of
4 2 10
two Sn atoms with exclusively inorganic coordination. We have
discussed the quoted aggregation as being preferred in the
[
12]
presence of bulky organic ligands. However, in the case of
E=Te, the longer SnÀTe bonds obviously comply with a larger
steric demand of the organic ligands, such that a rearrange-
ment is not necessary.
Employment of phenyl thiosemicarbazide afforded the com-
4
4
plexes [(R Sn) Te ] (R =CMe CH C(Me)NNC(S)NHPh; 8) and
[
2
2
2
2
4
{(HR) Sn} Te ] (9), see Figure 6. In 8 (monoclinic space group
4 6
P2 /c, Z=2), the central [Sn Te ] ring connects two C,N,S-tri-
1
2
2
dentate thiosemicarbazide ligands. The p-system of the thiose-
micarbazide units is delocalized, which might be represented
in the canonical thiol description.
The molecular structure of 8 is analogous to the homolo-
4
[24]
gous sulfide compound [(R Sn) S ]. Again, the tin atoms ex-
2
2
hibit a coordination number of five, in a trigonal bipyramidal
fashion with N and Te in axial positions. The stronger trans
effect of the Te atoms as compared to the S atoms leads to an
elongation of the N···Sn distance (N1···Sn1: 2.293(5) Š) com-
pared with that of the homologous complex (2.337(5) Š).
Moreover, we observed the generation of a DD-type cluster
in 9 (9·2MeOH, monoclinic space group P2 /c, Z=2). Here, the
1
thiosemicarbazone ligands are observed in the thione form,
thus acting as monodentate ligands. Like in 7, the tin atoms
are coordinated in a (distorted) tetrahedral fashion with similar
structural parameters of the inorganic core. The nucleophilic
character of the thione groups is not sufficiently high to re-
place the Te atoms within the inorganic core. Instead, they
point away from the cluster core and form a two-dimensional
hydrogen-bonding network parallel to the (100) plane.
Figure 5. Molecular structure of 6 (top) and 7 (bottom) without H atoms. El-
lipsoids are drawn at 50%. v=2Àx, Ày, Àz. Selected structural parameters
[
Š, 8]: 6: Sn1ÀTe1: 2.9141(6), Sn1ÀTe2 2.7668(6), Sn1ÀTe3 2.7697(6), Sn2ÀTe1
2
2
.9222(6), Sn2ÀTe2 2.7627(6), Sn2ÀTe4 2.7587(6), Sn3ÀTe1 2.9029(6), Sn3ÀTe3
.7580(6), Sn3ÀTe4 2.7551(6), Sn-Te-Sn 79.72(1)-86.70(2), Te-Sn-Te 92.64(2)-
1
19.28(2); 7: Sn1ÀTe1 2.7461(7), Sn1ÀTe2 2.7515(6), Sn1ÀTe3 2.7543(6), Sn2À
v
Te1 2.7567(6), Sn2ÀTe2 2.7509(7), Sn2ÀTe3 2.7524(7), Sn1-Te1-Sn2 82.50(2),
v
Sn1-Te2-Sn2 82.50(2), Sn1-Te3-Sn2 100.73(2), Te1-Sn1-Te2 97.61(2), Te1-Sn1-
v
Remarkable results were observed upon treatment of 2 with
the bifunctional carbohydrazide H N C(O)N H , which produced
Te3 108.64(2), Te2-Sn1-Te3 121.51(2), Te1-Sn2-Te2 97.38(2), Te1-Sn2-Te3
v
1
06.15(2), Te2-Sn2-Te3 123.10(2).
3
2
2
3
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Figure 7. Molecular structures of 10 (top) and 11 (bottom). Ellipsoids are
drawn at 50%. Organic substituents are denoted as sticks without H atoms.
Selected structural parameters [Š, 8]: 10: Sn1ÀTe1: 2.7346(12), Sn2ÀTe1:
2
.7290(12), Sn1-Te1-Sn2: 94.11(3); 11: Sn1ÀTe1: 2.768(1), Sn2ÀTe1: 2.750(1),
Sn1ÀCl1: 2.655(3), Sn2ÀCl1: 2.829(3), Sn1-Te1-Sn2: 92.48(3), Sn1-Cl1-Sn2:
3.17(8), Cl1-Sn1-Te1: 87.89(7), Cl1-Sn2-Te1: 84.88(7).
9
Figure 6. Molecular structures of 8 (top) and 9 (bottom) without H atoms
and disorder. Ellipsoids are drawn at 50%. [vi]=1Àx, Ày, 1Àz; [vii]=1Àx,
the coordination polyhedron around Sn2 are occupied by C7,
N2, N3, and Te1, and the apical position by Cl3. N2 is depro-
tonated, as rationalized by a short N2ÀSn1 bond (2.142(8) Š).
1
Ày, 1Àz. Selected structural parameters [Š, 8] for 8: Sn1ÀTe1: 2.7256(6),
v
i
v
i
Sn1ÀTe1 2.8510(7), Sn1ÀS1 2.469(1), C7ÀS1: 1.769(6), Sn1-Te1-Sn1 81.12(2),
vi
vi
Te1-Sn1-Te1 98.88(2), S1-Sn1-Te1 111.75(5), S1-Sn1-Te1 92.98(4); 9: Sn1ÀTe1
5
The deprotonation of the organic HR substituent at N2 indu-
2
2
.7446(5), Sn1ÀTe2 2.7567(5), Sn1ÀTe3 2.7546(5), Sn2ÀTe1 2.7391(5), Sn2ÀTe2
vii
.7464(5), Sn2ÀTe3 2.7629(5), C7ÀS1: 1.683(7), C20ÀS2: 1.663(9), Sn1-Te1-
ces the different coordination at Sn2, as is also shown below
for 12. The carbohydrazide unit activates self-complementary
NÀH···O hydrogen-bonding interactions through O1 and the
N4 (see the Supporting Information, Figure S22).
vii
Sn2 81.83(1), Sn1-Te2-Sn2 81.48(1), Sn1-Te3-Sn2 99.48(2), Te1-Sn1-Te2
9
8.15(2), Te1-Sn1-Te3 121.91(2), Te2-Sn1-Te3 108.55(2), Te1-Sn2-Te2 98.53(2),
vii
vii
Te1-Sn2-Te3 117.79(2), Te2-Sn2-Te3 110.98(2).
The central structural motif of the molecular structure of 11
(11·1.5CH Cl monoclinic space group C2/c, Z=8) is an asym-
compounds 10, 11, and 12, with so-far unprecedented struc-
tural motifs and stronger intramolecular interaction of inorgan-
ic and organic moieties. Compound 10 (10·CH Cl , monoclinic
2
2,
metric Sn-Te-Sn-Cl four-membered ring (see Figure 7, bottom).
All the tin atoms exhibit a distorted octahedral coordination,
which has been unprecedented in RSn/E cluster chemistry (E=
2
2
space group P2 /c, Z=4) consists of a central [Sn TeCl ] inor-
1
2
3
5
5
5
6
6
ganic unit with a pentadentate organic HR substituent (R =
CMe CH C(Me)NN} C(O), see Figure 7, top). The SnÀTe bond
S, Se, Te). The pentadentate HR
and HR
(R =
{
CMe CH C(Me)NNC(O)NNH ) ligands connect the Sn-Te-Sn-Cl
2
2
2
2
2
2
lengths are slightly longer and the Sn-Te-Sn angle is slightly
more acute than in 1. The pentacoordinate Sn atoms co-exist
in trigonal bipyramidal (Sn1) and square pyramidal (Sn2) coor-
dination environment. Both coordination geometries can be
continuously transferred into each other by a Berry-type
pseudo-rotation, as quantified by the t parameter (t=1 for an
ideal trigonal bipyramidal and t=0 for an ideal square pyrami-
four-membered ring with Sn3. The organic ligands are depro-
tonated at N4 and N8, causing short NÀSn bonds. Notably, the
6
HR organic ligand does not undergo condensation with the
1
keto group of an R ligand. Instead, the ligand realizes self-
complementary NÀH···Cl interactions. Within the Sn-Te-Sn-Cl
ring the SnÀTe bond lengths differ by only 0.018 Š, whereas
the SnÀCl bond lengths differ much more notably, by 0.174 Š.
The Sn-Te-Sn angle (92.48(3)8) is more acute than the Sn-Cl-Sn
[
25]
dal coordination). For Sn1 t is 0.82, with Cl1 and N1 in the
axial positions, whereas for Sn2 t is 0.02. The basal positions in
[
26]
(93.17(8)8) angle.
12383
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Compound 12 was obtained in two pseudo-polymorphic
crystalline modifications. Complex 12·5CH Cl (triclinic space
group P 1¯ , Z=4) crystallizes directly from a dichloromethane
Sn7 (t=0.16). At the inner side of the inorganic scaffold short
intermolecular Te···Te distances are observed (Te1···Te4:
3.500(1) Š, Te4···Te7: 3.542(1) Š). Intermolecular hydrogen
bonding leads to a dimerization through NÀH···O self-comple-
mentary interactions.
2
2
solution upon layering with n-hexane. Because of rapid decom-
position of the crystals, we only present a structural model of
the compound and do not discuss structural details. Complex
1
2·2CH Cl2 (triclinic space group P 1¯ , Z=2) formed through
2
NMR Spectroscopy
a crystal-to-crystal transformation from 12·5CH Cl upon loss
2
2
119
125
of three molecules of dichloromethane per cluster molecule in
the inert oil used for the crystallographic investigation within
one day. We observed cracks within the transformed crystal
under a light-microscope; however, the crystals of the second
pseudo-polymorph produce a homogeneous diffraction pat-
tern. During the transformation, the cell volume per formula
Sn and Te NMR experiments in CD Cl and CDCl give in-
2 2 3
sights to the integrity and potential dynamic behavior of the
clusters in solution. The signals are sharp for small complexes
1 and 2. The reduced solubility of the larger complexes as well
as dynamic processes in solution leads to broadening of the
signals under loss of the fine structure. For these reasons,
3
2
117
119
1
119
125
unit decreases by about 348 Š , which confirms to the loss of
J( Sn- Sn) and J( Sn- Te) coupling constants were only
1
117
125
three solvent molecules of dichloromethane. Suspending
determined for 1 and 2 ( J( Sn- Te) satellites were also ob-
1
13
1
2·2CH Cl in dichloromethane led to decomposition of the
served, but are not given here). H and C NMR spectra of the
compounds show the expected resonances of the organic li-
gands.
2
2
crystals, hence we were not able to check the reversibility of
the transformation.
In the relatively complicated cluster architecture in 12 (see
The successive generation of SnÀTe bonds leads to a signifi-
5
119
Figure 8), a [Sn Te Cl ] backbone is linked by two H R ligands
cant shift to higher fields in the Sn NMR spectroscopic ex-
7
8
4
2
5
5
and one HR ligand. The H R ligands connect Sn1 with Sn5
periments (1: d=À272, 2: d=À546, 3: d=À577 ppm). The
2
5
2
117
119
and Sn2 with Sn4. The HR ligand connects Sn6 with Sn7 (N7À variations in the coupling constants J( Sn– Sn) (1: 387, 2:
1
1
119
125
Sn7: 2.158(10) Š). Sn3 remains isolated and exhibits an R
156 Hz) and J( Sn– Te) (1: 4.72, 2: 2.64 kHz) reflect the dif-
ferent molecular geometry of each complex and are in agree-
ment with known organotin complexes with this structural
ligand. Intramolecular NÀH···O hydrogen-bonding interactions
generate a molecular capsule. The inorganic backbone com-
prises a sequence of an [Sn Te] moiety, two [Sn Te ] rings and
[
27]
119
125
motif. Contrariwise to the Sn NMR data, the Te NMR sig-
nals are shifted to the lower field (1: d=À287, 2: d=
212 ppm).
2
2
2
one Sn atom, which are connected by three m-Te atoms. Addi-
tional chlorine substituents are coordinated to Sn1, Sn2, and
Sn7. The tin atoms show different coordination numbers and
coordination environments. Sn4 and Sn5 exhibit a tetrahedral
environment. Sn1 (t=0.34), Sn2 (t=0.44), Sn3 (t=0.96), Sn6
The hydrazone complexes show further shift to higher field
119
125
in the Sn NMR spectra (5: d=À680 ppm). Within the Te
NMR spectra, the Te atoms within the alternating four-mem-
bered ring in 5 accord with a signal at d=483 ppm, whereas
the Te atoms between the rings produce a signal at d=
À660 ppm. In 6, the two signals at d=À844 and d=449 ppm
(
t=0.84) are coordinated in a distorted trigonal bipyramidal
5
fashion. Again, the deprotonation of the organic HR ligand
provokes a quadratic pyramidal coordination environment at
can be assigned to the m-Te atoms and the m -Te atom, respec-
3
tively, according to the expected significant upfield shift with
increasing coordination number.
Two signal sets are found in the NMR spectra of 8 with an
119
intensity of approximately 1:1. In the Sn NMR spectrum, two
narrow signals are found at d=À601 and À605 ppm. These
signals most probably arise from an equilibrium of two isomers
in solution with the crystallographically determined trans ar-
rangement and a (hypothetic) cis arrangement of the organic
substituents (see the Supporting Information, Figure S32), re-
spectively. DFT calculations confirm a shift of 4 ppm to higher
119
field in the Sn NMR spectrum, and a slightly higher energy
À1
of the cis isomer is observed (+5.2 kJmol ; for further details
see the Supporting Information).
DFT Calculations
The consecutively performed, stepwise reactions of A with
(
Me Si) Te was additionally studied by means of quantum
3 2
Figure 8. Molecular structure of 12 in 12·2CH
0%. Organic substituents are denoted as sticks without H atoms. Selected
structural parameters [Š, 8]: SnÀTe : 2.732(1)–2.882(1), Sn-Te-Sn: 81.19(3)-
00.38(3), Te-Sn-Te: 94.94(3)-121.57(3).
2 2
Cl . Ellipsoids are drawn at
chemical investigations employing density functional theory
DFT) methods. The condensation cascade that was subject to
the studies is outlined in Scheme 2.
5
(
1
Chem. Eur. J. 2015, 21, 12376 – 12388
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Full Paper
The common driving force for all of the condensation steps
is the generation of the extraordinary stable SiÀCl bond in
À1
Me SiCl, with an energy of about 468 kJmol , under cleavage
3
of the weak SiÀTe bond in (Me Si) Te, with an energy of about
3
2
À1 [28]
2
69 kJmol .
À1
The overall energy decreases by about 94 kJmol per con-
densation step (see Figure 9, top). This suggests that all of the
presented species should be predominant at a certain stage of
the condensation cascade. As pointed out above, we were not
able to isolate species I. Figure 9 (bottom) illustrates the in-
creasingly labile character of the obtained clusters. Whereas
the overall energy for the generation is negative, replacement
of SnÀCl bonds for SnÀTe bonds results in the shown course
of the cluster stabilities.
Scheme 2. Proposed reaction for the stepwise formation of the organotin
telluride cage compound 3 and basic concept of the quantum chemical
analysis.
Calculations of the natural charges through natural popula-
[
29]
tion analysis (NPA) of the DFT wave function give small posi-
IV
tive values of about +0.9 to +1.1 at the formal Sn atoms in
the organotin sesquitelluride clusters (see the Supporting In-
formation, Table S16), beside small negative values of À0.4 to
À0.5 at the Te atoms. The small charges accord with nearly
identical electronegativities of Sn and Te. Low polarity of the
inorganic cluster core in combination with the high steric
demand of the organic ligand obviously enabled the isolation
of discrete organotin telluride compounds.
Time-dependent DFT calculations (TD-DFT) of the singlet and
triplet excitation energies of 1, 2, I, and 3 underline the ob-
served bathochromic shift upon expansion of the inorganic
[
30]
core. The minimum singlet excitation energy drops signifi-
cantly from about 3.0 in 1 to 2.2 eV in 3 (see Figure 10). This
can be attributed to the increasing energy level of the highest
occupied molecular orbital (HOMO; with highest contribution
of Te 5p atomic orbitals (AOs)), which is excited into energeti-
cally low-lying antibonding orbitals involving RSn units that do
not differ as notably in energy as the HOMO level for the dif-
ferent (RSn)/E systems. The relatively low absorption energy,
situated within the visible-light range, is also in perfect agree-
ment with the observed light sensitivity of the compounds in
solution.
Figure 9. DFT analysis of the formation pathway. Relative energies for the
À1
formation of molecules 1, 2, I, and 3 are given in kJmol . Top: Total reac-
tion energies, as calculated by subtraction of the sum of the total energies
of the starting materials A and (Me
3
2
Si) Te from the sum of the total energies
of the respective species plus Me
3
SiCl as side product. The total energy de-
À1
creases by about 47 kJmol per newly created SnÀTe bond. Bottom: Reac-
tion energies disregarding the energy differences within the silyl reactants,
namely the energy differences between (formed) SiÀCl and (broken) SiÀTe
bonds in Me
3
SiCl and (Me
3
Si)
2
Te, respectively, which amounts to approxi-
À1
mately 199 kJmol per newly created SnÀTe bond. Details are provided in
Figure 10. Singlet excitation energies with increasing cluster core size, as
calculated by means of time-dependent DFT calculations.
the Supporting Information.
Chem. Eur. J. 2015, 21, 12376 – 12388
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ꢀ 2015 Wiley-VCH Verlag GmbH & Co. KGaA, Weinheim

Full Paper
1
13 29
2
13 125
29
5
.53 ppm (s, J( C- Si)=50.4 Hz, J( C- Te) =6.9 Hz); Si NMR
Conclusion
1
29
125
1
29
(
79 MHz, CDCl ): d=À4.94 ppm (s, J( Si- Te) =275 Hz, J( Si-
3
1
3
125
C)=50.4 Hz);
Te NMR (126 MHz, CDCl3): d=À853 ppm (s,
We have shown that discrete organotin telluride clusters can
be stabilized, and thus be isolated, by attachment of C,O- and
C,N-chelating ligands. These clusters can be obtained by step-
wise condensation reactions of the organotin trichloride
1
125
29
J( Te- Si)=275 Hz).
1
Compound 1: R SnCl (0.500 g, 1.54 mmol) was dissolved in tolu-
3
ene (10 mL). (Me Si) Te (0.106 g, 0.385 mmol) was added at room
3
2
temperature. It was then stirred for 24 h. The solution was layered
with n-pentane (10 mL). Yellow crystals of compound 1 formed
within one day, which were collected and dried in high vacuum.
Yield: 0.22 g (0.31 mmol, 81% calculated on the basis of
1
1
1
R SnCl and (Me Si) Te to yield [(R SnCl ) Te] (1), [(R SnCl) Te ]
3
3
2
2 2
2
2
1
(
2), and [(R Sn) Te ] (3). The treatment of 2 and 3 with different
4 6
substituted hydrazines yielded a large variety of corresponding
hydrazine derivatives, with or without rearrangement of the in-
organic cluster core (4–12).
We further envisage exploring the photophysical properties
and thermochemical processes of organotin telluride com-
pounds as materials with fine-tuneable physical and chemical
properties.
1
(Me Si )Te). M.p.: 1458C (decomposition). H NMR (300 MHz, CDCl ):
3
2
3
3
1
119
d=1.40 (s, J( H- Sn)=179 Hz, 12H, Me
), 2.40 (s, 6H, Me),
2
3
1
119
13
2
.98 ppm (s, J( H- Sn)=183 Hz, 4H, CH2); C NMR (75 MHz,
CDCl ): d=25.05 (Me ), 29.17 (Me), 44.73 (CSn), 54.72 (CH ),
3
2
2
119
2
14.41 ppm (CO); Sn NMR (149 MHz, CDCl ): d=À272 ppm (s,
3
1
119
125
2
119
117
125
J( Sn- Te) =4.72 kHz,
J( Sn- Sn)=387 Hz);
Te NMR
1
125
119
(
126 MHz, CDCl ): d=À287 ppm (s, J( Te- Sn)=4.72 kHz); IR:
3
u˜ =3344.2 (w), 3251.2 (w), 3143.3 (w), 2951.7 (m), 2854.1 (m),
2
830.1 (m), 1660.7 (s), 1499.7 (w), 1459.3 (m), 1389.8 (w), 1368.8
Experimental Section
(
m), 1332.4(m), 1259.1(w), 1239.4(w), 1187.2(m), 1139.3(w),
À1
1116.5(m), 1021.5(w), 965.6(w), 801.3(w), 624.5(s), 499.3 cm (m);
General
UV/Vis (onset): 2.6 eV; EDX: calcd Sn/Te/Cl=2.00:1.00:4.00; found:
All manipulations were performed under argon atmosphere and
strict exclusion of light. All solvents were dried and freshly distilled
Sn/Te/Cl=2.00:1.00:3.98.
1
Compound 2: R SnCl (0.500 g, 1.54 mmol) was dissolved in tolu-
3
1
[31]
prior to use. R SnCl3 was prepared according to reported meth-
ods, (Me Si) Te was prepared as described below. Other reagents
ene (10 mL). (Me Si) Te (0.423 g, 1.54 mmol) was added at 08C. It
3
2
3
2
was stirred for 30 min and warmed up to room temperature. The
resulting yellow precipitate was filtered and washed with toluene.
Orange crystals of compound 2 formed within one day upon dis-
solving the yellow precipitate in dichloromethane and layering
with n-pentane. Yield: 0.51 g (0.67 mmol, 86% calculated on the
1
13
31
119
were purchased from Sigma–Aldrich. H-, C-, Si-, Sn-, and
125
Te NMR spectroscopic measurements were carried out using
a Bruker DRX 250 MHz, DRX 300 MHz, DRX 400 MHz, and DRX
00 MHz spectrometer at 258C. The chemical shifts were quoted in
ppm relative to the residual protons of deuterated solvents in the
5
1
basis of (Me Si )Te). M.p.: 1348C (decomposition); H NMR
3
2
1
13
H NMR and C NMR spectra. Me Si, Me Sn, and Me Te were used
3
1
119
4
4
125
2
(
(
(
(
(
(
300 MHz, CDCl ): d=1.12 (s, J( H- Sn)=160 Hz, 12H, Me ), 2.28
s, 6H, Me), 2.59 (s, J( H- Sn)=148 Hz, 4H, CH ) ppm; C NMR
3
2
2
9
119
as external standard for Si, Sn, and Te NMR measurements.
MS (ESI) measurements were performed on a Thermo Fischer Sci-
entifics Finnigan LTQ-FT. IR spectroscopy was performed with
3
1
119
13
2
75 MHz, CDCl ): d=25.68 (Me ), 30.19 (Me), 46.78 (CSn), 54.55
3
2
119
CH ), 204.54 ppm (CO); Sn NMR (149 MHz, CDCl ): d=À546 ppm
2
3
À1
À1
a Bruker Tensor 37 between 4000 and 400 cm (Æ0.01 cm ) in at-
tenuated total reflection. Elemental analysis was performed on an
Elementar vario micro apparatus. Energy-dispersive X-ray spectros-
copy analysis, EDX, was performed using the EDX device Voyag-
er 4.0 of Noran Instruments coupled with the electron microscope
CamScan CS 4DV. Data acquisition was performed with an acceler-
ation voltage of 20 kV and 100 s accumulation time. UV/Vis spectra
were measured on a Varian Cary 5000 spectrometer in reflectance.
Thermogravimetric analysis (TGA) and differential scanning calorim-
etry (DSC) were performed simultaneously on a Netzsch STA 400 in
an aluminium oxide crucible in argon atmosphere with a heating
1
125
119
2
119
117
125
s,
J( Te- Sn)=2.64 kHz,
J( Sn- Sn)=165 Hz);
Te NMR
1
125
119
126 MHz, CDCl ): d=212 ppm (s, J( Te- Sn)=2.64 kHz); IR: u˜ =
3
3
1
135.0 (w), 3047.0 (w), 2927.3 (w), 2842.4 (m), 1687.7 (s), 1452.6(w),
408.0 (w), 1378.1 (w), 1358.5 (m), 1332.7 (w), 1234.9 (w), 1174.2
À1
(
s), 1111.6 (m), 1014.9 (w), 956.7 (w), 837.1 (w), 606.7 cm (m); UV/
Vis (onset): 2.1 eV; EDX: calcd Sn/Te/Cl=1.00:1.00:1.00; found: Sn/
Te/Cl=1.00:0.99:0.92; elemental analysis calcd (%) for
C H Cl O Sn Te : C 18.92, H 2.91; found: C 18.71, H 2.79.
12
22
2
2
2
2
1
Compound 3: R SnCl (0.100 g, 0.308 mmol) was dissolved in di-
3
chloromethane (10 mL). (Me Si) Te (0.126 g, 0.462 mmol) was
3
2
À1
added at room temperature. The solution was stirred for 5 h. The
intensive red solution was layered with n-pentane (10 mL). Red
crystals of compound 3 formed within one day, which were col-
lected and dried in high vacuum. Yield: 0.065 g (0.040 mmol, 52%
rate of 10 Kmin .
Syntheses
calcd on the basis of (Me Si )Te). M.p.: 1468C (decomposition);
(
Me Si) Te : Prepared by varying the reported method for the syn-
3
2
3
2
1
3
1
119
[32]
H NMR (300 MHz, CD Cl ): d=1.14 (s, J( H- Sn)=136 Hz, 24H,
thesis of (Me Si) Se reported by Schmidt and Ruf.
Ammonia
2 2
3
2
3
1
119
Me ), 2.21 (s, 12H, Me), 2.54 ppm (s, J( H- Sn)=124 Hz, 8H, CH2);
(
250 mL) was condensed onto sodium (5.90 g, 257 mmol) at
2
1
3
C NMR (75 MHz, CD Cl ): d=26.38 (Me ), 27.91 (Me), 30.50 (CSn),
À408C. Tellurium (16.5 g, 130 mmol) was added slowly in small
portions. The mixture was stirred for 4 h at À408C and slowly
warmed up to room temperature thereupon. Ammonia was al-
lowed to evaporate, and the resulting colorless powder (Na Te)
was dried in vacuum. It was subsequently suspended in THF
2
2
2
119
5
5.55 (CH ), 211.04 ppm (CO); Sn-NMR (112 MHz, CD Cl ): d=
2 2 2
125
À577 ppm; Te NMR (126 MHz, CD Cl ): no signal found; IR: u˜ =
2
2
2
840.7 (w), 1690.6 (s), 1451.0 (w), 1391.9 (w), 1354.6 (w), 1326.9
2
(
(
m), 1323.9 (m), 1173.9 (s), 1110.2 (s), 1012.0 (w), 958.6 (w), 835.8
À1
m), 716.7 (m), 607.5 cm (s); UV/Vis (onset): 1.9 eV; HRMS (ESI): m/
(
250 mL) and freshly distilled Me SiCl (32 mL, 252 mmol) was
3
+
+
z calcd for [C H O Sn Te ] ([MÀC H OSnTe ] ): m/z=1164.5688;
added. The solution was heated at reflux for 3 h and filtered. THF
was removed in vacuo. The product was obtained as colorless
liquid by fractional distillation under reduced pressure. Yield:
18 33
3
3
4
6
11
2
found: 1164.5714; EDX: calcd Sn/Te=0.67:1.00; found: Sn/Te=
.69:1.00.
Compound 4: Compound 2 (0.050 mg, 0.066 mmol) was dissolved
in dichloromethane (10 mL). hydrazine solution (0.35 mL,
0
1
2
2.8 g (83.2 mmol, 65%). H NMR (400 MHz, CDCl ): d=0.50 ppm
3
1
1
13
13
(s, J( H- C)=121.0 Hz, 18H); C NMR (101 MHz, CDCl3): d=
A
Chem. Eur. J. 2015, 21, 12376 – 12388
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ꢀ 2015 Wiley-VCH Verlag GmbH & Co. KGaA, Weinheim

Full Paper
À1
1
molL in THF) was added at room temperature. The resulting
Me), 2.45 (s, 9H, CH ), 3.60 (brs, 4H, NH), 6.80–7.30 ppm (m, 20H,
2
orange solution was stirred for 30 min and subsequently layered
Ph); EDX: calcd Sn/Te=0.67:1.00, found Sn/Te=0.65:1.00.
2
with n-hexane (10 mL). Red crystals of compound 4·4CH Cl2
Compound 8: Compound 2 (0.050 g, 0.066 mmol) and 4-phenyl-
thiosemicarbazide (0.022 g, 0.203 mmol) were dissolved in di-
chloromethane (10 mL). After 1 h, the solution was layered with n-
hexane (10 mL). Yellow crystals of compound 8 formed within one
formed within one day, which were collected and dried in high
vacuum. They were insoluble in all common organic solvents.
Yield: 0.010 g (2.3 mmol, 21% calculated on the basis of 2). IR: u˜ =
648.6 (w), 3334.0 (w), 3208.6 (w), 2980.5 (m), 2844.6 (m), 2286.6
w, br), 2148.6 (w), 2049.9 (w), 1980.3 (w), 1660.3 (m), 1608.5 (m),
584.8 (m), 1426.4 (m), 1382.1 (m), 1249.2 (m), 1203.8 (m), 1143.6
s), 1095.3 (s), 1003.4 (m), 956.2 (m), 845.0 (s), 800.5 (s), 732.0 (s),
57.8 (s), 585.8 (w), 510.8 (w), 493.2 (w), 469.4 (w), 434.5 cm (w);
3
(
1
week, which were collected and dried in high vacuum. Yield:
1
1
(
(
8 mg (0.018 mmol, 27% calculated on the basis of 2). H NMR
3
1
119
500 MHz, CD Cl ): d=1.13 (s, 6H, J( H- Sn)=150 Hz, Me ), 1.20
2
119
2
2
(
6
3
1
s, 6H, J( H- Sn)=147 Hz, Me ), 2.17 (s, 3H, CH ), 2.18 (s, 3H,
CH ), 2.32 (s, 3H, J( H- Sn)=152 Hz, Me), 2.37 (s, 3H, J( H-
Sn)=153 Hz, CH ), 6.74 (s, 1H, NH), 6.80 (s, 1H, NH), 7.02–7.06
2
2
À1
3
1
119
3
1
2
+
HRMS (ESI): m/z calcd for [C H N Sn Te ] : 1206.6494; found:
206.6515; EDX: calcd Sn/Te=1.00:1.00; found: Sn/Te=1.00:1.04
Cl was not considered because of dichloromethane solvent mole-
119
1
8
39
6
3
4
2
1
(
(
m, 2H, Ph), 7.28–7.33 (m, 4H, Ph), 7.56–7.61 ppm (m, 4H, Ph);
13
C NMR (125 MHz, CD Cl ): d=24.72 (Me ), 24.90 (Me ), 29.98 (Me),
2
2
2
2
cules).
3
0.10 (Me), 37.26 (CSn), 37.60 (CSn), 47.88 (CH ), 47.95 (CH ), 120.32
2 2
(
1
Ph), 120.37 (Ph), 123.37 (Ph), 129.44 (Ph), 139.74(Ph), 150.12 (CN),
Compound 5: Compound 2 (0.10 g, 0.13 mmol) was dissolved in
dichloromethane (10 mL). N H ·H O (0.03 mL, 50–60% N H ) was
added at room temperature. A red cloudy precipitate appeared
rapidly within the solution, but re-dissolved after 15 min. After
119
50.53 ppm (CN);
Sn NMR (187 MHz, CD Cl ): d=À601,
2
2
2
4
2
2
4
125
À605 ppm; Te NMR (158 MHz, CD Cl ): no signal found; IR: u˜ =
2
2
3
660.9 (w), 2840.1 (m), 2710.8 (w), 1690.7 (s), 1451.2 (w), 1359.8 (s),
1
172.1 (s), 1130.3 (s), 1013.2 (s), 959.6 (m), 876.8 (w), 796.5 (s), 744.5
3
0 min, the deep-red solution was layered with n-hexane (10 mL).
À1
(
m), 607.5 (m), 485.5 (w), 437.2 (w), 406.4 cm (w); HRMS (ESI): m/z
Red crystals of compound 5 formed within one day, which were
collected and dried in high vacuum. Yield: 40 mg (0.024 mmol,
+
calcd for C H N S Sn Te : 988.8502 ([M+H] ); found: 988.8511;
26 35
6
2
2
2
EDX: calcd S/Sn/Te=1.00 :1.00:1.00, found S/Sn/Te=0.98:1.00:0.96.
The doublet set of signals in the NMR spectra is presumably
caused by a trans/cis equilibrium in solution. For further details,
see the DFT part below.
5
5% calculated on the basis of 2). M.p.: 1508C (decomposition);
1
3 1 119
H NMR (300 MHz, CDCl ): d=1.08 (s, J( H- Sn)=135 Hz, 24H,
Me ), 1.84 (s, 12H, Me), 2.32 (s, J( H- Sn)=139 Hz, 8H, CH2),
5
2
3
3
1
119
2
1
3
.44 ppm (s, 8H, NH2); C NMR (75 MHz, CDCl ): d=17.20 (Me),
3
7.90 (Me ), 35.68 (CSn), 51.49 (CH ), 151.75 ppm (CN); Sn NMR
1
19
2
2
25
Compound 9: Compound 4 (0.050 g, 0.031 mmol) was dissolved in
dichloromethane (5 mL). 4-phenylthiosemicarbazide (0.021 g,
0.124 mmol), dissolved in methanol (5 mL), was added at room
temperature. After 1 h, the solution was layered with n-hexane
(10 mL). Red crystals of 9·2MeOH formed within one week, which
were collected and dried in high vacuum. Yield: A few single crys-
tals, which were insoluble in organic solvents. EDX: calcd S/Sn/Te=
0.33:0.67:1.00; found: S/Sn/Te=0.35:0.68:1.00.
1
(
4
187 MHz, CD Cl ): d=À680 ppm; Te NMR (158 MHz, CD Cl ): d=
2
2
2
2
83, À660 ppm; IR: u˜ =3339.2 (w), 3251.2 (w), 3143.5 (w), 3029.8
(
1
w), 2952.1 (w), 2928.6 (w), 2882.4 (m), 2829.4 (m), 1499.8 (w),
456.8 (w), 1407.4(w), 1359.8 (m), 1258.7 (w), 1240.1 (w), 1194.6
(
w), 1121.7(m), 1093.3 (s), 967.7 (m), 799.4 (m), 698.6 (w), 653.6 (w),
À1
5
05.5 cm (m); UV/Vis (onset):1.8 eV; HRMS (ESI): m/z calcd for
+
C H N Sn Te : 1206.6494 ([MÀC H N SnTe ] ); found: 1206.6494;
18
39
6
3
4
6
13
2
2
EDX: calcd Sn/Te=0.67:1.00; found: Sn/Te=0.68:1.00.
Isolation of compounds 10–12: Compound
2
(0.100 g,
Compound 6: Compound 2 (0.050 g, 0.066 mmol) was dissolved in
dichloromethane (10 mL). Phenylhydrazine (0.022 g, 0.203 mmol)
was added at room temperature. After 30 min, the solution was
layered with n-hexane (10 mL). Red crystals of compound 6
formed within one day, which were collected and dried in high
vacuum. Yield: 35 mg (0.021 mmol, 64% calculated on the basis of
0.131 mmol) was dissolved in dichloromethane (10 mL). Carbohy-
drazide (0.014 g, 0.155 mmol) was added at room temperature.
The solution was stirred for 30 min and subsequently layered with
n-hexane (10 mL). Colorless crystals of 10·CH
11·1.5CH Cl , and red crystals of 12·5CH Cl
week side by side. Single crystals of 12·5CH
under retention of the macroscopic morphology of the crystals
into 12·2CH Cl in inert oil within 24 h. The determination of the
Cl
formed within one
Cl were transformed
, yellow crystals of
2
2
2
2
2
2
2
2
1
3
1
119
2
). H NMR (300 MHz, CD Cl ): d=1.20 (s, J( H- Sn)=120 Hz),
2 2
3
1
119
1
3
8H, Me ), 1.92 (s, 9H, Me), 2.39 (s, J( H- Sn)=129 Hz, 6H, CH ),
.53 (brs, 3H, NH), 6.70–7.20 ppm (m, 15H, Ph);
2
2
2
2
1
19
Sn NMR
Te NMR
individual yields was not possible due to the mixture of com-
pounds. EDX of 10: calcd Sn/Te=1.00:0.50; found: Sn/Te=
1.00:0.53 (chlorine was not considered because of the dichloro-
methane solvent molecules). EDX of 11: calcd Sn/Te=1.00:0.33;
found Sn/Te=1.00:0.35 (chlorine was not considered because of
the dichloromethane solvent molecules). EDX of 12: calcd Sn/Te=
1.00:0.88, found Sn/Te=1.00:0.90 (chlorine was not considered be-
cause of the dichloromethane solvent molecules).
1
25
(
(
(
149 MHz, CD Cl ): d=48 (SnCl), À626 ppm (SnTe);
2
2
158 MHz, CD Cl ): d=449 (m -Te), À844 ppm (m-Te); IR: u˜ =3650.6
2
2
3
w), 3318.1 (w), 3206.3 (w), 2980.6 (m), 2883.1 (m), 2838.3 (m),
2
1
1
6
707.4 (w), 2371.0 (w), 1598.6 (s), 1493.8 (s), 1453.1 (m), 1363.1 (m),
333.1 (w), 1306.1, (w), 1250.0 (m), 1210.6 (s), 1170.1 (m), 1132.5 (s),
067.9 (m), 994.5 (w), 962.1 (w), 885.2 (w), 800.9 (w), 744.3 (s),
À1
90.4 (s), 655.7 (w), 584.1 (w), 504.1 (m), 450.6 cm (w); HRMS
+
(
ESI): m/z calcd for C H N Sn Te : 1434.7439 ([MÀSnCl ] ); found:
3
6
51
6
3
4
3
1
434.7449; EDX: calcd Sn/Te=1.00:1.00, found Sn/Te=0.97:1.00.
X-ray crystallography
Compound 7: A saturated solution of 6 in CD Cl was sealed in an
2
2
NMR test tube. After two weeks at room temperature, red crystals
Data collection was performed on STOE IPDS2 and IPDS2t diffrac-
tometers using graphite-monochromatized MoKa radiation (l=
0.71073 Š) at 100 K (4·4CH Cl was measured at 250 K). Structure
of compound 7·3CH Cl grew inside the tube, which were collect-
2
2
ed and dried in high vacuum. An alternative route for the directed
synthesis of 7 is as follows: Compound 4 (0.020 g, 0.012 mmol)
was dissolved in dichloromethane (5 mL). Phenylhydrazine (0.01 g,
2
2
solution and refinement by direct methods and full matrix least-
2
[33]
squares on F , respectively; SHELXTL software.
Details of the
0
.09 mmol) was added at room temperature. The solution was
stirred for one hour and subsequently layered with n-hexane
10 mL). Yield: 0.007 g (0.003 mmol, 25% calculated on the basis of
measurements, structure solutions and refinements as well as addi-
tional are provided in the Supporting Information. CCDC 1059622
((Me Si) Te), 1059623 (1), 1059624 (2), 1059625 (3), 1059626
(
6
3
2
1
). H NMR (300 MHz, CD Cl ): d=1.16 (s, 24H, Me ), 2.06 (s, 12H,
(4·4CH Cl ), 1059627 (5), 1059628 (6·C H ), 1059629 (7·3CH Cl ),
2 2 6 14 2 2
2
2
2
Chem. Eur. J. 2015, 21, 12376 – 12388
www.chemeurj.org
12387
ꢀ 2015 Wiley-VCH Verlag GmbH & Co. KGaA, Weinheim

Full Paper
1
059630 (8), 1059631 (9·2MeOH), 1059632 (10·CH Cl ), 1059633
Dehnen, Z. Anorg. Allg. Chem. 2012, 638, 1663–1666; c) J. P. Eußner, S.
Dehnen, Chem. Commun. 2014, 50, 11385–11388; d) J. P. Eußner, B. E.
Barth, U. Justus, N. W. Rosemann, S. Chatterjee, S. Dehnen, Inorg. Chem.
2
2
(11·1.5CH Cl ), 1059634 (12·5CH Cl ), and 1059635 (12·2CH Cl )
2 2 2 2 2 2
contain the supplementary crystallographic data for this paper.
These data are provided free of charge by The Cambridge Crystal-
lographic Data Centre.
2015, 54, 22–24.
[
[
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8
1
Keywords: cluster
calculations · tellurium · tin · X-ray diffraction
compounds
·
density
functional
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Chem. Eur. J. 2015, 21, 12376 – 12388
www.chemeurj.org
12388
ꢀ 2015 Wiley-VCH Verlag GmbH & Co. KGaA, Weinheim