Preparation and conformation of organo-bridged bis[tris(arylchalcogenolato) tin] compounds - An experimental and quantum chemical study

Article abstract of DOI:10.1002/zaac.200800263

Seven organo-bridged bis[tris(arylchalcogenolato)tin] compounds with the general formulae (R′E)₃Sn-R-Sn(ER′)₃ (R = -(CH₂)₄-, 1,4-bis(methyl)benzene, 4,4′-bis(methyl) biphenyl; R′ = Ph, 1-Np, 2-Np; E = S, Se) wer

Full text of DOI:10.1002/zaac.200800263

DOI: 10.1002/zaac.200800263
Preparation and Conformation of Organo-Bridged
Bis[tris(arylchalcogenolato)tin] Compounds ؊ An Experimental and Quantum
Chemical Study
Hari Pada Nayek, Heiko Niedermeyer, and Stefanie Dehnen*
Marburg, Philipps-Universität Marburg, Fachbereich Chemie, Wissenschaftliches Zentrum für Materialwissenschaften (WZMW)
Received June 23rd, 2008.
Dedicated to Dr. habil. Werner Hanke in Recognition and Gratitude for his Work done for this Journal over the
Last Decades
Abstract. Seven organo-bridged bis[tris(arylchalcogenolato)tin]
compounds with the general formulae (RЈE)3SnϪRϪSn(ERЈ)3
(R ϭ Ϫ(CH2)4Ϫ, 1,4-bis(methyl)benzene, 4,4Ј-bis(methyl)biphenyl;
RЈ ϭ Ph, 1-Np, 2-Np; E ϭ S, Se) were synthesized and charac-
terized by means of X-ray diffractometry as well as NMR spec-
troscopy. Three different conformations of the arylchalcogenolato
groups ERЈ with respect to the bridging group R were rationalized
and explained by means of quantum chemical investigations.
Keywords: Tin; Arylchalcogenolates; DFT calculations; NMR
spectroscopy; Tinorganyls; X-ray Diffractometry
Introduction
In this paper, we report the syntheses and crystal struc-
tures of a series of a novel type of arylchalcogenolato-
substitued tinorganyl compounds according to the general
Organotin and organochalcogenolatotin compounds have
been extensively studied during the last few decades due to
interesting catalytic or biological activities, as well as their
precursor function for the generation of tinchalcogenide
films for opto-electronic applications [1Ϫ11]. Stannoxanes,
for example, catalyze the formation of acetals or esters from
alcohols and ketones [12] or acids and alcohols [13], respec-
tively. [Ph3Sn(SR)] (HSR ϭ 2-mercaptobenzoxazole or 5-
chloro-2-mercaptobenzothiazole) exhibits lipoxygenase in-
hibitory activities [14]. Tetra(thiophenolato)tin was used for
the syntheses of thin films of SnS and SnS2 [15]. Addition-
ally, organotin chlorides were starting materials for the
synthesis of a number cyclic compounds R6Sn3S3 or
adamantine-type structures (RSn)4S6 (e.g. R ϭ C6F5,
C6H4F, Ph, C6H4Me, Me) by reactions with S(SiMe3)2 or
Na2S·9H2O [16]. The employment of tin thiolates
recently resulted in the formation of ternary
clusters like [Cu4Sn3(edt)6(μ3-O)(PPh3)4](ClO4)2 ·3CH2Cl2,
fromula (RЈE)3SnϪRϪSn(ERЈ)3, (R
ϭ
Ϫ(CH2)4Ϫ,
1,4-bis(methyl)benzene, 4,4Ј-bis(methyl)biphenyl; RЈ ϭ Ph,
1-Np, 2-Np; E ϭ S, Se). In spite of very similar compo-
sitions, the compounds show different conformations of the
groups surrounding the tin atoms. Quantum chemical inves-
tigation using density functional theory (DFT) [19] meth-
ods rationalized that the predominant conformer is the
thermodynamically preferred one. The title compounds are
currently explored with respect to their applicability as syn-
thons in the preparation of heterometallic, mixed coordi-
nation/organometallic polymers.
Results and Discussion
Syntheses
Compounds 1 and 2 were synthesized by reacting a meth-
anolic solution of 1, 4-bis(trichlorostannyl)butane [20]
(C40H38S6 Sn2 1) or 4, 4Ј-bis(trichlorotinmethyl)biphenyl
[21] (C50H42S6Sn2 2) with a methanolic solution of sodium
thiophenolate [22] (Scheme 1). Compounds 3, 4 and 5 were
synthesized by reacting 1,4-bis(trichlorostannyl)butane
(C40H38Se6Sn2 3, C64H50Se6Sn2 4) or 1,4-bis(trichlorostan-
nylmethyl)benzene [20] (C44H38Se6Sn2 5) with diphenyldise-
lenide [23] or di-1-naphtyldiselenide [24] in the presence of
tetrasodium tetrahydridoborate borohydride for reduction
of the SeϪSe bond and thus the in situ formation of the
corresponding arylchalcogenate salts in ethanol (Scheme 2).
Compounds 6 and 7 were synthesized by reacting a toluene
solution of 1, 4-bis(trichlorostannyl)butane (C64H50S6Sn2 6)
[(Ph3P)2Cu]2SnS(edt)2 ·2CH2Cl2 ·H2O,
[(Ph3P)2Cu]2-
SnS(edt)2 ·2DMF·H2O and [(Ph3P)Cu]2Sn(SPh)6 ·3H2O,
were synthesized by reactions of [Cu(PPh3)2(MeCN)2]ClO4
with Sn(edt)2 (edt ϭ ethane-1,2-dithiolate) [17], by reaction
of [(PPh3)3CuBr] with (Bu4N)2[Sn3S4(edt)3], or by reaction
of Sn(SPh)4 with CuCN and PPh3 [18].
* Prof. Dr. Stefanie Dehnen
Fachbereich Chemie der Philipps-Universität Marburg
Hans-Meerwein-Strasse
D-35032 Marburg, Germany
Fax: (ϩ49)6421/28-25653
E-mail: E-mail: dehnen@chemie.uni-marburg.de
Z. Anorg. Allg. Chem. 2008, 634, 2805Ϫ2810
© 2008 WILEY-VCH Verlag GmbH & Co. KGaA, Weinheim
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H. P. Nayek, H. Niedermeyer, S. Dehnen
Scheme 1 Syntheses of compounds 1 and 2.
Scheme 2 Syntheses of compounds 3, 4 and 5.
Scheme 3 Syntheses of compounds 6 and 7.
or 1,4-bis(trichlorostannylmethyl)benzene (C68H50S6Sn2 7)
with a toluene solution of thionaphthol in the presence of
triethylamine as a base (Scheme 3). Details of the synthesis
procedures are provided in the experimental section.
Crystal Structures
All compounds were structurally characterized by means of
single-crystal X-ray diffractometry [25, 26]. Figure 1 shows
the molecular structures and provides selected interatomic
distances and angles of 1Ϫ7. Table 1 summarizes details of
the data collection, structure solution and refinement. In
spite of different packing schemes, a common feature of all
comounds is their intramolecular inversion symmetry or
near inversion symmetry which is only frustrated to be ideal
by the conformation of the butyl group in 6. The tin atoms
in 1Ϫ7 all show a distorted tetrahedral environment,
formed by the chalcogen donor atoms of the three aryl-
chalcogenolato ligands and one carbon atom of the bridg-
Fig. 1 Structures of compounds 1-7.
˚
Selected distances /A and angles /° in 1 Ϫ 7: 1: SnϪC 2.150(3), SnϪS
2.4050(9)-2.4172(8), CϪS 1.784 (3)-1.785(3), CϪSnϪS 112.60(8)-117.93(10),
SϪSnϪS 95.89(4)-109.67(4); 2: SnϪC 2.176(3), SnϪS 2.4019(10)-2.4252(10),
CϪS 1.785(3)-1.792(4), CϪSnϪS 107.43(10)-113.76(11), SϪSnϪS 105.19(4)-
110.46(3); 3: SnϪC 2.149(3), SnϪSe 2.5248(10)-2.5413 (9), CϪSe 1.926(4)-
1.936(4), CϪSnϪSe 110.66(10)-112.17(11), SeϪSnϪSe 108.00(4)-113.15(3);
4: SnϪC 2.152(5), SnϪSe 2.5397(10)-2.5493(8), CϪSe 1.811(11)-1.971(8),
CϪSnϪSe 107.82(14)-116.21(14), SeϪSnϪSe 98.32(3)-111.38(4); 5: SnϪC
2.173(6), SnϪSe 2.5266(10)-2.5402(8), CϪSe 1.920(7)-1.932(6), CϪSnϪSe
107.46(15)-117.17(18), SeϪSnϪSe 103.26(3)-110.86(3); 6: SnϪC 2.170(12),
2.194(14) SnϪS 2.345(4)-2.466(5), CϪS 1.790(17)-1.795(12), CϪSnϪS
91.3(5)-126.6(7), SϪSnϪS 108.59(10)-109.15(10); 7: SnϪC 2.168 (3), SnϪS
2.4126(13)-2.4250(12), CϪS 1.782(4)-1.790 (3), CϪSnϪS 108.52(10)-
115.72(10), SϪSnϪS 99.42(3)-109.84(4).
˚
ing organyl group each (SnϪC 2.149(3)Ϫ2.194(14) A,
˚
SnϪS 2.345(5)Ϫ2.466(5) A (1, 2, 6, 7) SnϪSe
˚
2.5248(10)Ϫ2.5493(8) A (3, 4, 5)). The orientation of the
arylchalcogenalato groups around the tin atoms with re-
spect to the SnϪC bond including the organyl bridge, one
can distinguish three different conformer types that are
sketched in Figure 2: in Type I, all the organochalcogenol-
ato groups are oriented towards the bridging organyl
group, according to an all-cis conformation of the
C1ϪSnϪEϪCaryl connection (E ϭ S, Se; 1, 3, 4, 7). Type
II provides a mixture of cis and trans conformations (2, 5).
In Type III, all the organochalcogenolato groups are di-
rected away from the bridging organyl group to result in an
all-trans conformer (6). Dihedral angles C1ϪSnϪEϪC of
1Ϫ6 are provided in the caption.
DFT calculations
In order to shed light on the observation of a certain pre-
ferrence for one conformer rather than the other in the solid
state, and to explore whether this might be maintained in
solution, as well, density functional theory (DFT) [19] cal-
culations were performed employing the program system
Turbomole [27] (see experimental section). As an example,
we optimized both electronic and geometric structure of
three molecules of the type (RЈS)3SnϪ(CH2)4ϪSn(SRЈ)3
(RЈ ϭ Ph, 1-naphthyl or 2-naphthyl, according to 1, 6 and
the RЈS analogs of 3, 4 and 5 in all three different confor-
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Z. Anorg. Allg. Chem. 2008, 2805Ϫ2810

Organo-Bridged Bis[tris(arylchalcogenolato)tin] Compounds
Table 1 Crystal data and experimental details of the single-crystal X-ray analyses of compounds 1Ϫ7 [25, 26].
Compound
1
2
3
4
5
6
7
Empirical formula
Formula weight /g·molϪ1
Crystal system
C40H38S6Sn2
948.44
C50H42S6Sn2
1072.58
monoclinic
P 21/c
12.038(2)
16.771(3)
11.896(2)
C40H38Se6Sn2
1229.84
C64H50Se6Sn2
1530.18
C44H38Se6Sn2
1277.88
monoclinic
C2/c
17.605(4)
7.4957(15)
33.528(7)
C64H50S6Sn2
1248.78
C68H50S6Sn2
1296.82
monoclinic
P 21/n
13.257(5)
13.023(5)
16.256(7)
triclinic
triclinic
triclinic
trigonal
Space group
P1
P1
P1
R3a)
¯
¯
¯
˚
a /A
10.040(2)
10.190(2)
10.429(2)
111.47(3)
95.57(3)
90.24(3)
987.3(3)
1
1.595
1.610
4-60
12041
9.1186(18)
9.997(2)
13.042(3)
70.94(3)
71.55(3)
71.79(3)
1036.6(4)
1
1.970
6.499
5-52
6871
11.005(2)
12.026(2)
12.031(2)
100.09(3)
114.29(3)
96.93(3)
1395.4(5)
1
1.821
4.848
4-52
13701
13.5899(19)
13.5899(19)
24.876(5)
˚
b /A
˚
c /A
α /°
β /°
γ /°
106.73(3)
97.69(3)
91.02(3)
3
˚
V /A
2299.9(8)
2
1.549
1.392
4-52
16075
4476
0.0472
3479
4384.6(15)
4
1.936
6.150
5-52
7231
3874
0.0687
2737
235
3978.7(11)
3
1.564
1.220
4-58
12898
4790
0.0482
2686
2806.1(19)
2
1.535
1.156
4-52
38626
5459
0.1090
4372
Z
ρcalc /g·cmϪ3
μ(MoKα) /mmϪ1
2° range /°
Reflections measured
Independent reflections
R(int)
5499
0.0529
4627
3725
0.0498
3400
5020
0.0484
3327
Ind. reflections (I > 2σ(I))
Parameters
217
262
293
366
230
343
R1 (I > 2σ(I))
wR2 (all data)
GooF (all data)
Max. peak/hole /eϪ ·10Ϫ6pmϪ3
0.0255
0.0756
1.109
0.0322
0.0744
0.929
0.0305
0.0805
0.992
0.0342
0.0733
0.824
0.0362
0.0836
0.869
0.0556
0.1604
1.011
0.0340
0.0845
0.983
1.114/Ϫ0.609
0.702/Ϫ1.158
1.354/Ϫ1.224
1.537/Ϫ0.951
0.956/Ϫ0.730
1.566/Ϫ2.023
0.841/Ϫ0.989
a) refined as a partial racemic twin with a batch scale factor of 0.43(9); rotational disorder of the n-butyl group is not shown in figure 1 for clarity.
Table 2 Values of dihedral angles /° as resulting form DFT calcu-
lations of thiolato compounds (RЈS)3SnϪRϪSn(SRЈ)3 (RЈ/R ϭ Ph/
nBu, 1-Np/nBu, 2-Np/nBu) and selenolato compound
(PhSe)3SnϪXylylϪSn(SePh)3, according to three possible types of
conformations. Experimentally observed values for compounds
exhibiting the respective R/RЈ combination (3 and 4 containing
selenolato groups RЈSe instead of thiolato groups RЈS) are given
in parantheses.
RЈE/
PhS/nBu
1-NpS/nBu 2-NpS/nBu
PhSe/p-Xylyl
Type I
38.2Ϫ46.5
(1: 28.72Ϫ64.26) (4, Se:
(3, Se:
25.64Ϫ80.01)
37.3-46.2
28.7Ϫ50.1
2.8Ϫ82.8
Fig. 2 Different relative orientations of the organic or aryl chalco-
genolato groups aroud tin atoms, assigned to the conformer types,
I, II and III. Dihedral angles observed in compounds 1-7 /°:
1 (Type I, S) 28.72-64.26; 2 (Type II, S) 47.99, 134.45, 168.37; 3(Type I, Se)
25.64-81.01; 4 (Type I, Se) 5.57-78.00; 5 (Type II, Se) 40.73, 74.20, 157.70; 6
(Type III, S) 129.81-167.96; 7 (Type I, S) 11.43-68.67.
5.57Ϫ78.00)
Type II cis 17.2Ϫ84.2
21.6, 46.8
23.1, 40.5
37.0Ϫ45.3
(5: 40.73,
74.20)
trans 132.5Ϫ171.5
127.3Ϫ174.3 106.2Ϫ176.1
142.5Ϫ148.6 120.6Ϫ152.6
174.2, 179.9
(5: 157.73)
mations. Table 2 provides the resulting dihedral angles in
comparison with the experimentally observed ones.
Type III 145.7Ϫ147.9
144.6Ϫ149.7
(6: 129.81Ϫ167.96)
Intramolecular steric effects are well reproduced, as can
be seen by comparison of the structural parameters. Largest
deviations are found in those cases, where calculations con-
sider RЈS ligands at the tin atoms whereas the experimen-
tally obtained compound are ligated by RЈSe groups. Table
3 provides the relative energies of the resulting conformers.
For E ϭ S, all calculated species prefer the all-cis confor-
mation type I, which is indeed realized by most of the com-
pounds in the solid state. Although the stabilization is very
small, this is a clear hint for a thermodynamic support of
the observed conformation. For the calculated PhSe/p-Xylyl
combination, a slight preference for the cis-trans mixture
was reproduced as experimentally observed for respective
compound 5. The only case where the calculated structural
preference does not agree with the experimental finding is
the 2-NpS/nBu combination as observed in 6 Ϫ the only
compound obtained so far that features an all-trans con-
figuration type III: according to the calculations, type III is
disadvantaged by 2.5 kJ·molϪ1 with repsect to the mixed
type II, and it is by 16.5 kJ·molϪ1 less stable than the pre-
ferred all-cis conformation (type I). Since the calculations
represent gas phase conditions, we are in the position to
judge about the thermodynamic preferences of isolated
molecules that might be overcompensated by intermolecu-
lar interactions in the crystal lattice.
Z. Anorg. Allg. Chem. 2008, 2805Ϫ2810
© 2008 WILEY-VCH Verlag GmbH & Co. KGaA, Weinheim
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2807

H. P. Nayek, H. Niedermeyer, S. Dehnen
Table 3 Relative energies ΔE /kJ·molϪ1 of the three conformer
types I, II and III, modelled for thiolato compounds
(RЈS)3SnϪRϪSn(SRЈ)3 (RЈ/R ϭ Ph/nBu, 1-Np/nBu, 2-Np/nBu)
and selenolato compound (PhSe)3SnϪXylylϪSn(SePh)3 using
DFT methods. Most stable conformers are highlighted by grey
background, experimental conformers are indicated by an asteriks.
and Ϫ21.47, respectively. Beside similar changes in δ upon
variation of the organic groups (3 Ǟ 4, 4 Ǟ 5) as observed
for the thiolato compounds, the overall shift to again higher
field is due to the substitution of less electronegative seleno-
lato ligands for the thiolato groups, thus increasing the
shielding of the tin atoms.
RЈE/R
PhS/nBu
1-NpS/nBu
2-NpS/nBu
PhSe/p-Xylyl
Conclusion
Type I
Type II
Type III
Ϫ11.4 *
Ϫ5.4
0.0
Ϫ24.0 *
Ϫ20.3
0.0
Ϫ16.5
Ϫ2.5
0.0*
Ϫ1.5
Ϫ15.0 *
0.0
A series of organo-bridged bis[tris(arylchalcogenolato)tin]
compounds was prepared and characterized. The obser-
vation of three different types of conformers was investi-
gated by DFT calculations. In accordance to these investi-
gations, an all-cis orientation of arylchalcogenolato groups
is favored in the case of thiolato compounds, whereas selen-
olato groups can lead to the preferrence of a cis-trans mixed
conformation. The future aim is to study the reactivity of
such compounds towards transition metal complexes in or-
der to produce novel ternary clusters or ternary metal or-
ganic frameworks.
In 6, the all-trans situation allows for a highly symmetric
arrangement of the nearly linear molecules in the crystal
lattice, which would definitely be diminuated by different
orientation of the 2-naphthyl groups. This is not the case
for the two further compounds with naphtyl substituents: 4
carries 1-naphtyl ligands that cannot not be arranged in a
straight parallel manner and 7 is forced into an at least
more bent conformation of the SnϪRϪSn backbone due
to the rigid xylyl bridge. Figure 3 illustrates the highly sym-
metric and dense crystal packing in 6.
Experimental Section
General All synthetic work was performed under purified argon
atmosphere using double manifold Schlenk lines or dry N2 atmos-
phere within a glove box. The solvents were dried and degassed by
standard methods under an argon atmosphere. CDCl3 was distilled
under Argon. 13C and 119Sn NMR spectra were recorded on Bruker
Advance 300 and Bruker Advance DRX 400 spectrometers. Com-
mercially available reagents were used as received. Bis-(trichloro-
stannyl) alkyl or aryl compounds, Na(SPh), Ph2Se2, 1-Np2Se2, were
prepared according to literature procedures.
Synthesis of compounds 1 and 2
To a solution of 1.185 mmol of NaSPh in 5 mL of dry methanol,
a solution of bis(trichlorostannyl)organyl (0.1975 mmol) in 5 mL of
dry methanol was added slowly at 0 °C. A white powder occurred
immediately. The mixture was stirred for 24 hours, filtered, washed
with methanol and hexane and dried in vacuo. Crystals were ob-
tained from a DCM/hexane mixture within two days.
Figure 3 Fragment of the crystal packing in 6, veiwed along the
crystallographic c axis.
1, 4-Bis [tris(thiophenolato)stannyl]butane (1): Yield: 64 %. 13C
NMR (100 MHz, CDCl3, 25 °C): δ ϭ 21.18 (CH2), 28.60 (CH2),
127.40, 129.10, 130.40, 135.40, (Ar), 119Sn NMR (CDCl3):δ ϭ
89.44 (s)
NMR spectroscopy
All compounds were characterized by means of NMR spec-
troscopy (see experimental section). In the 119Sn NMR spec-
tra, each of these compounds shows a single signal indicat-
ing that both tin atoms are situated within the same chemi-
cal environment in solution. Thiolato compounds 1, 2, 6
and 7 show signals at δ ϭ 89.4, 59.78, δ ϭ 85.49, and δ ϭ
55.44, respectively. The shift in δ value toward higher field
is put down to the change of the thiophenolate by more
electron rich thionaphthylate groups (1 Ǟ 6), and by replac-
ing the bridging n-butyl group by the electron rich dimeth-
ylbiphenyl or dimethylxylyl moiety (6 Ǟ 2 or 7). Selenolato
compounds 3, 4 and 5 produce signals at δ ϭ Ϫ4.92, Ϫ6.2,
4, 4Ј-Bis [tris(thiophenolato)tinmethyl]biphenyl (2): Yield: 70 %. 13C
NMR (75.5 MHz, CDCl3, 25 °C): δ ϭ 27.9 (CH2), 126.0, 126.4,
127. 9,128.0, 129.2, 133.8, 134.4, 136.9 (Ar), 119Sn NMR (CDCl3):
δ ϭ 59.78 (s)
Synthesis of compounds 3, 4 and 5
RЈ2Se2 (0.5927 mmol) was dissolved in 5 mL of degassed absolute
ethanol. Six equivalents of Na[BH4] were added to this solution
in small portions until the solution became completely colourless.
0.1975 mmol of the respective bis(trichlorostannyl)-organyl com-
pound was dissolved in 5 mL of ethanol and added to the
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Z. Anorg. Allg. Chem. 2008, 2805Ϫ2810

Organo-Bridged Bis[tris(arylchalcogenolato)tin] Compounds
Na(SePh) solution slowly at 0 °C. The mixture was stirred for 24
hours, filtered, washed with ethanol and hexane and dried in vacuo.
The compounds crystallized from DCM/hexane mixture within
one week.
[2] R. C. Mehrotra, V. D. Gupta, D. Sukhani, J. Inorg. Nucl.
Chem. 1967, 29, 1577Ϫ1580.
[3] K. C. Kumara Swamy, R. O. Day, R. R. Holmes, J. Am. Chem.
Soc. 1988, 110, 7543Ϫ7544.
[4] Kalsoom, M. Mazhar, S. Ali, M. F. Mahon, K. C. Molloy, M.
I. Chaudry, Appl. Organomet. Chem. 1997, 11, 47Ϫ55.
[5] D. Dakternieks, K. Jurkschat, H. Wu, E. R. T. Tiekink,
Organometallics 1993, 12, 2788Ϫ2793.
[6] M. Gielen, K. Jurkschat, J. Organomet. Chem. 1984, 273,
303Ϫ312.
[7] D. Dakternieks, K. Jurkschat, D. Schollmeyer, H. Wu,
Organometallics 1994, 13, 4121Ϫ4123.
[8] Dakternieks, K. Jurkschat, D. Schollmeyer, H. Wu, J.
Organomet. Chem. 1995, 492, 145Ϫ250.
1,4-Bis[tris(selenophenolato)stannyl]butane (3): Yield: 60 %, 13C
NMR (100 MHz, CDCl3, 25 °C): δ ϭ 21.00(CH2), 28.10(CH2),
123.30, 126.60, 128.40, 135.80, (Ar), 119Sn NMR (CDCl3): δ ϭ
Ϫ4.92 (s)
1,4-Bis[tris(1-selenonaphthylato)stannyl]butane (4): Yield: 58 %. 13
C
NMR (100 MHz, CDCl3, 25 °C): δ ϭ 22.50 (CH2), 28.80 (CH2),
125.66, 126.30, 126.77, 127.98, 128.55, 128.98, 129.41, 129.83,
134.10, 136.90 (Ar),119Sn NMR (CDCl3): δ ϭϪ6.2 (s)
[9] Y. Azuma, M. Newcomb, Organometallics 1984, 3, 9Ϫ14.
[10] N. Belai, M. T. Pope, Polyhedron 2006, 25, 2015Ϫ2020.
[11] R. Hauser, K. Merzweiler, Z. Anorg. Allg. Chem. 2002, 628,
905Ϫ906.
1,4-Bis[tris(selenophenolato)stannylmethyl]benzene (5): Yield: 73 %.
13C NMR (100 MHz, CDCl3, 25 °C): δ ϭ 30.00 (CH2), 124.18,
28.05, 129.17, 137.09, (Ar), 119Sn NMR (CDCl3): δ ϭ Ϫ21.47 (s)
[12] J. Otera, T. Mizutani, H. Nozaki, Organometallics 1989, 8,
2063Ϫ2065.
[13] J. Otera, N. Dan-oh, H. Nozaki, J. Org. Chem. 1991, 56,
5307Ϫ5311.
[14] M. N. Xanthopoulou, S. K. Hadjikakou, N. Hadjiliadis, M.
Kubicki, S. Skoulika, T. Bakas, M. Baril, I. S. Bulter, Inorg.
Chem. 2007, 46, 1187Ϫ1195.
[15] a) G. Barone, T. G. Hibbert, M. F. Mahon, K. C. Molloy, L.
S. Price, I. P. Parkin, A. M. E. Hardy, M. N. Field, J. Mater.
Chem. 2001, 11, 464Ϫ468; b) G. Barone, T. Chaplin, T. G.
Hibbert, A. T. Kana, M. F. Mahon, K. C. Molloy, I. D. Worse-
ley, I. P. Parkin, L. S. Price, J. Chem. Soc., Dalton Trans.
2002, 1085Ϫ1092.
Synthesis of compounds 6 and 7
To a solution of 2-thionaphthal (1.2668 mmol) in 5 mL of toluene,
Et3N (1.2668 mmol) was added and stirred for ten minutes. A solu-
tion of the respective bis(trichlorostannyl)organyl compound
(0.2113 mmol) in 5 mL of toluene was then added dropwise. The
mixture was stirred for 12 hours, toluene was removed under re-
duced pressure, and 10 mL of methanol were added to the obtained
solid The mixture was filtered and the solid was washed with meth-
anol, hexane and dried in vacuo. The compounds are crystallized
from DCH/Hexane mixture within one week.
1,4-Bis[tris(thionaphthylato)stannyl]butane (6): Yield: 55 %. 13C
NMR (100 MHz, CDCl3, 25 °C): δ ϭ 21.80 (CH2), 28.80 (CH2),
125.56, 126.32, 126.59, 127.26, 127.67, 128.43, 132.27, 132.52,
133.60, 134.36 (Ar), 119Sn NMR (CDCl3): δ ϭ 85.49 (s)
[16] a) H. Berwe, A. Haas, Chem. Ber. 1987, 120, 1175Ϫ1182; b)
B. Menzebach, P. Bleckmann, J. Organomet. Chem. 1975, 91,
291Ϫ294.
[17] X. Wang, T. Sheng, R. Fu, S. Hu, S. Xiang, L. Wang, X. Wu,
Inorg. Chem. 2006, 45, 5236Ϫ5238.
[18] L. Wang, T. Sheng, X. Wang, D. Chen, S. Hu, R. Fu, S. Xiang,
X. Wu, Inorg. Chem. 2008, 47, 4054Ϫ4059.
[19] a) R. G. Parr, W. Yang, Density Functional Theory of Atoms
and Molecules, Oxford University Press, New York 1988; b) T.
Ziegler, Chem. Rev. 1991, 91, 651Ϫ667.
1,4-Bis[tris(thionaphthylato)stannylmethyl]benzene (7): Yield: 67 %.
13C NMR (100 MHz, CDCl3, 25 °C): δ ϭ 31.0 (CH2), 125.54,
126.687, 126.754, 127.20, 127.75, 127.86, 128.17, 128.66, 131.6,
133.6 (Ar), 119Sn NMR (CDCl3): δ ϭ 55.44 (s)
[20] a) B. Zobel, A. Duthie, D. Dakternieks, Organometallics 2001,
20, 2820Ϫ2826; b) B. Jousseaume, H. Riague, T. Toupance,
Organometallics 2002, 21, 4590Ϫ4594.
Methods of the quantumchemical investigations
The DFT calculations [19] were performed using the Ridft program
[27] within the program system Turbmole [28], employing the
BP86-functional [29]. Basis sets were of def2-SV(P) quality
(SV(P) ϭ split valence plus polarization except for H atoms) [30].
For Sn, the basis included an effective core potential (ECP-28) in
all calculations [31]. The calculations were undertaken without
symmetry restriction (C1). Convergence into local minima was ra-
tionalized by analytical calculation of the second derivatives using
the program Aoforce [32].
[21] B. Jousseaume, H. Riague, T. Toupance, H. Allouchi, Or-
ganometallics 2007, 26, 3908Ϫ3917.
[22] S. Oae, T. Takata, Y. H. Kim, Tetrahedron 1980, 37, 37Ϫ44.
[23] H. J. Reich, J. M. Renga, I. L. Reich, J. Am. Chem. Soc. 1975,
97, 5434Ϫ5447.
[24] G. Mugesh, A. Panda, H. B. Singh, N. S. Punekar, R. J.
Butcher, J. Am. Chem. Soc. 2001, 123, 839Ϫ850.
[25] Details on the measurement and X-ray structural refinement
of 1-7: All single crystal measurements have been performed
at a Stoe IPDS-II diffractometer at 100 K (1-3, 5-7) or at an
Stoe IPDS diffractometer at 193 K (4), using MoKα radiation
Acknowledgements. This work was financially supported by the
Deutsche Forschungsgemeinschaft (DFG).
˚
(λMoKα ϭ 0.71073 A) and a graphite monochromator. The
structure solution was performed by direct methods, followed
by full-matrix-least-squares refinement against F2, using
Shelxs-97 and Shelxl-97 software [26]. Table 1 summarizes
the data of the X-ray diffractometry. CCDC 692583Ϫ692589
contains the supplementary crystallographic data for this
paper. These data can be obtained free of charge from The
References
[1] R. Kumar, H. E. Mabrouk, D. G. Tuck, J. Chem. Soc. Dalton
Trans. 1988, 1445-1446.
Z. Anorg. Allg. Chem. 2008, 2805Ϫ2810
© 2008 WILEY-VCH Verlag GmbH & Co. KGaA, Weinheim
www.zaac.wiley-vch.de
2809

H. P. Nayek, H. Niedermeyer, S. Dehnen
Cambridge Crystallographic Data Centre via www.ccdc.cam.-
ac.uk/data_request/cif.
[26] G. W. Sheldrick, Shelxtl 5.1, Bruker AXS Inc., 6300 Enterprise
Lane, Madison, WI 53719Ϫ1173, USA, 1997.
[27] a) K. Eichkorn, O. Treutler, H. Öhm, M. Häser, R. Ahlrichs,
Chem. Phys. Lett. 1995, 242, 652Ϫ660; b) K. Eichkorn, F. Wei-
gend, O. Treutler, R. Ahlrichs, Theor. Chem. Acc. 1997, 97,
119Ϫ124.
[28] a) R. Ahlrichs, M. Bär, M. Häser, H. Horn, C. Kölmel, Chem.
Phys. Lett. 1989, 162, 165Ϫ169; b) O. Treutler, R. Ahlrichs, J.
Chem. Phys. 1995, 102, 346Ϫ355; c) M. von Arnim, R.
Ahlrichs, J. Chem. Phys. 1999, 111, 9183Ϫ9190.
[29] a) A. D. Becke, Phys. Rev. A 1988, 38, 3098Ϫ3109; b) S. H.
Vosko, L. Wilk, M. Nusair, Can. J. Phys. 1980, 58, 1200Ϫ1205;
c) J. B. Perdew, Phys. Rev. B 1986, 33, 8822Ϫ8837.
[30] F. Weigend, R. Ahlrichs, Phys. Chem. Chem. Phys. 2005, 7,
3297-3305.
[31] B. Metz, H. Stoll, M. Dolg, J. Chem. Phys. 2000, 113,
2563Ϫ2569.
[32] a) P. Deglmann, K. May, F. Furche, R. Ahlrichs, Chem.
Phys. Lett. 2004, 384, 103Ϫ107; b) P. Deglmann, F. Furche,
R. Ahlrichs, Chem. Phys. Lett. 2002, 362, 511Ϫ518;
c) P. Deglmann, F. Furche, J. Chem. Phys. 2002, 117,
9535Ϫ9538.
2810
www.zaac.wiley-vch.de
© 2008 WILEY-VCH Verlag GmbH & Co. KGaA, Weinheim
Z. Anorg. Allg. Chem. 2008, 2805Ϫ2810