1-D-Tin(II) Phenylchalcogenolato complexes ∞ 1[Sn(EPh)2] (E = S, Se, Te) - Synthesis, structures, quantum chemical studies and thermal behaviour

Article abstract of DOI:10.1002/ejic.200900940

A series of three 1-D-tin(II) phenylchalcogenolato complexes _∞¹[Sn(EPh)₂] (E = S, Se, Te) were synthesized in yields > 80% by reaction of SnCl₂ with two equivalents of PhESiMe₃ in organic solvents. In

Full text of DOI:10.1002/ejic.200900940

FULL PAPER
DOI: 10.1002/ejic.200900940
1
1
-D-Tin(II) Phenylchalcogenolato Complexes [Sn(EPh) ] (E = S, Se, Te) –
ϱ
2
Synthesis, Structures, Quantum Chemical Studies and Thermal Behaviour
[
a]
[a,b]
[c]
[a]
[a]
Andreas Eichhöfer,* Ji-Jun Jiang,
Heino Sommer, Florian Weigend, Olaf Fuhr,
Dieter Fenske,[ Cheng-Yong Su, and Gernot Buth
a,c]
[b]
[d]
Keywords: Tin / Chalcogens / Complexes / X-ray diffraction / TGA / Density functional calculations
A series of three 1-D-tin(II) phenylchalcogenolato complexes
either selenium or tellurium atoms. The bond situation is dis-
cussed on the basis of density functional calculations. Ther-
mal treatment mostly leads to the formation of the corre-
sponding phase pure tin(II) chalcogenides however sublima-
tion plays an increasing role ongoing from the tellurolato to
the thiolato complex especially for the use of vacuum condi-
tions. The investigation of the volatile cleavage products re-
veals the occurence of more complex reactions in the gas
1
ϱ
[Sn(EPh)
by reaction of SnCl
organic solvents. In the crystal the molecules form two dif-
2
] (E = S, Se, Te) were synthesized in yields Ͼ 80%
2
with two equivalents of PhESiMe in
3
1
ϱ 2
ferent types of one-dimensional chains. In [Sn(SPh) ] the tin
atoms are distorted trigonal pyramidal coordinated by sulfur
atoms (two bonds within a monomer and one longer bond
1
between neighbored monomers), while in
ϱ
[Sn(EPh)
2
] (E =
Se, Te) the tin atoms show contacts to two neighbored mono-
mers leading to a fourfold coordination of the tin atoms by
phase than the formal stoichiometric cleavage of EPh
S, Se, Te) with formation of SnE.
2
(E =
[
13–16]
[17]
Introduction
(SPh)
2
as well as Sn(SePh)
2
have been synthesized
before while no report could be found for the tellurium ana-
logue. However the structures of only a few compounds of
this type are reported including monomeric [Sn(S-2,4,6-
tC H C H ) ],
Sn(2-SeNC H ) ] ,
Metal chalcogenolato complexes have attracted interest
[
1–3]
due to their rich structural chemistry,
their potential use
and their relevance as
as precursors for M/Se materials[
4,5]
[
18]
[12]
dimeric [Sn{TeSi(SiMe ) } ]
and
4
9
6
2 2
3 3 2 2
models for active sites of chalcogen containing metalloprot-
[
11]
[
trimeric [Sn(S-2,6-(iC H ) C H ) ]
eins.[6,7]
5 4 2 2
3
7 2
6
3 2 3
1
[19]
1
as well as polymeric
SnC H ) ]. The build up of the structures is mostly de-
[Sn(StC H ) ]
and ϱ[Sn-
Tin(IV)chalcogenolato complexes like Sn(SPh)4,[8]
ϱ
4
9 2
[20]
(
[
9,10]
[11]
4
9 2
Sn(SePh)4
and Sn(Se-2-NC H )
as well as related
5
4 4
termined by the stereochemical effect of the “inert” electron
pair and the interplay of the steric demand of the organic
ligands vs. the tendency of tin(II) to realize higher coordi-
nation modes than two together with a minor influence of
the kind of chalcogen element.
tin(II) compounds like [Sn{ESi(SiMe ) } ] (E = S, Se,
3
3 2 2
Te)[ and [Sn(2-SeNC H ) ]
12]
[11]
have been studied in view
5
4 2 2
of their use as precursor compounds for MOCVD of SnE
and SnE (E = S, Se) while the corresponding tin(II) com-
2
pounds also attracted interest due to the synthesis of “car-
bene analogues” and the realisation of low coordination
modes. Synthetic procedures for compounds with the gene-
ral formula Sn(ER) (E = S, Se, Te; R = organic group)
are especially for thiolato complexes well established. With
respect to the compounds under investigation Sn-
Reported here are the synthesis of three 1-D-Tin(II)
phenylchalcogenolato complexes 1 [Sn(EPh) ] (E = S, Se,
ϱ
2
Te) by reaction of SnCl with two equivalents of PhESiMe3
in organic solvents along with their structural characteriza-
tion and an investigation of their thermal behaviour.
2
2
[
a] Institut für Nanotechnologie, Forschungszentrum Karlsruhe,
Postfach 3640, 76021 Karlsruhe, Germany
Fax: +49-7247-82-6368
E-mail: eichhoefer@int.fzk.de
Results and Discussion
[
b] MOE Laboratory of Bioinorganic and Synthetic Chemistry and
State Key Laboratory of Optoelectronic Materials and Technol-
ogies, School of Chemistry and Chemical Engineering, Sun Yat-
Sen University,
Synthesis and Structure
Guangzhou 510275, P. R. China
[
[
c] Institut für Anorganische Chemie der Universität,
Engesserstrasse, Geb. 30.45, 76128 Karlsruhe, Germany
d] Institut für Synchrotronstrahlung (ISS), Forschungszentrum
Karlsruhe GmbH,
The tin(II) chalcogenolato complexes 1 [Sn(SPh) ] (1),
ϱ
2
1
] (2) and 1
[Sn(SePh)
[Sn(TePh) ] (3) were prepared by re-
ϱ
2
ϱ
2
action of anhydrous SnCl2 with two equivalents of
Postfach 3640, 76021 Karlsruhe, Germany
PhESiMe (E = S, Se, Te) in dme for 1 and 2 or thf for 3
Supporting information for this article is available on the
WWW under http://dx.doi.org/10.1002/ejic.200900940.
3
in accordance to Scheme 1.
410
© 2010 Wiley-VCH Verlag GmbH & Co. KGaA, Weinheim
Eur. J. Inorg. Chem. 2010, 410–418

1
-D-Tin(II) Phenylchalcogenolato Complexes 1
[Sn(EPh) ] (E = S, Se, Te)
ϱ 2
bridged in one dimension by both phenylselenolato ligands
Se(1), Se(2) and Se(3), Se(4)] to form infinite chains along
b (Figure 2). Two of the Sn–Se distances [Sn(1)–Se(1):
66.87(8), Sn(1)–Se(2): 267.57(7), Sn(2)–Se(3): 268.32(7),
Sn(2)–Se(4): 267.37(8) pm] are distinctly smaller than the
secondary” Sn–Se contacts [Sn(1)–Se(3) 291.45(7), Sn(2)–
Se(2) 298.02(7), Sn(1)Ј–Se(4) 321.80(7), Sn(2)–Se(1)Ј
[
2
“
3
10.73(7) pm]. The shorter Sn–Se distances are similar to
Scheme 1.
[21]
those found in AsPh [Sn(SePh) ] (264.9–267.0 pm)
and
Therefore the
4
3
[
22]
[Yb(C H O) ][Sn(SePh) ] (262.9–268.5).
4
8
6
3 2
1
crystallizes in the orthorhombic space group Pca21
crystal structure of 2 consists of Sn(SePh) units [Se–Sn–Se
2
(Table 3). In the crystal structure the Sn(SPh) units of 1
2
angles: Se(1)–Sn(1)–Se(2) 88.15(3), Se(4)–Sn(2)–Se(3)
82.37(3)] which are linked by four additional weaker sele-
nium to tin donor-acceptor bonds in order to form one di-
mensional chains. The polymeric structure is thus compar-
are µ -bridged in one dimension by one of the phenylthiol-
2
ato ligands (S(2)) to form infinite chains along a (Figure 1)
while the other SPh group coordinates the tin atom as a
terminal ligand. Two of the three Sn–S distances Sn(1)–S(1)
–
1
[19]
1
able to those found for [Sn(StC H ) ]
and ϱ[Sn-
ϱ
4
9 2
[
251.8(2) pm] and Sn(1)–S(2) [257.7(2) pm] are distinctly
smaller than the contact between Sn(1) and S(2)Ј with
73.1(2) pm. Although these shorter distances are slightly
longer than the Sn–S bond [243.5(1) pm] found in mono-
[20]
(SnC H ) ].
4 9 2
2
[18]
meric [Sn(S-2,4,6-tC H C H ) ] one can therefore better
4
9
6
2 2
describe the structure as consisting of monomeric Sn-
SPh) units which are linked by two additional weaker sul-
(
2
fur to tin donor-acceptor bonds to form the polymeric
chains (see chapter Quantum Chemical Considerations).
This leads in summary to a distorted trigonal pyramidal
coordination around the tin atom [S–Sn(1)–S angles: S(1)–
Sn(1)–S(2) 77.16(6), S(1)–Sn(1)–S(2)Ј 92.68(6), S(2)–Sn(1)–
S(2)Ј 87.58(5)°]. The polymeric structure thus differs from
1
[19]
1
[20]
those found for [Sn(StC H ) ]
and [Sn(SnC H ) ]
ϱ
4
9 2
ϱ
4 9 2
where the tin atoms were found to be fourfold coordinated
by the thiolato ligands. A similar trigonal pyramidal coordi-
nation was observed for two of the tin atoms in trimeric
Figure 2. Section of the crystal structure of 1
[Sn(SePh) ] (2) viewed
ϱ 2
down a (50% ellipsoids, H atoms omitted for clarity). Symmetry
transformation for generation of equivalent atoms: Ј –x + 1/2, y –
1/2, –z + 1/2. Selected bond length [pm]: Sn(1)–Se(1) 266.87(8),
Sn(1)–Se(2) 267.57(7), Sn(2)–Se(3) 268.32(7), Sn(2)–Se(4)
[18]
[
Sn(S-2,6-(iC H ) C H ) ] .
3 7 2 6 3 2 3
2
67.37(8), Sn(1)···Se(3) 291.45(7), Sn(2)···Se(2) 298.02(7), Sn(1)Ј···
Se(4) 321.8(1), Sn(2)···Se(1)Ј 310.7(1). Selected bond angles (°):
Se(1)–Sn(1)–Se(2) 88.15(3), Se(1)–Sn(1)–Se(3) 83.85(1), Se(2)–
Sn(1)–Se(3) 86.37(1), Se(4)–Sn(2)–Se(3) 82.37(3), Se(4)–Sn(2)–Se(2)
8
3.00(1), Se(3)–Sn(2)–Se(2) 84.92(1), Sn(1)–Se(2)–Sn(2) 92.88(1),
Sn(2)–Se(3)–Sn(1) 94.21(1).
3
crystallises also in the monoclinic space group P2 /n
1
with two formula units in the asymmetric unit (Table 3).
Similar to 2 the Sn(TePh) units of 3 are in the crystal µ -
2
2
bridged in one dimension by both of the phenyltellurolato
ligands [Te(1), Te(2) and Te(3), Te(4)] to form infinite
chains along b (Figure 3). Different bond lengths and
angles as well as different orientations of the phenyl rings
lead to another crystal packing for the Sn(TePh) units in 3
in comparison to 2 expressed by different lattice constants.
Figure 1. Section of the crystal structure of 1
down b (50% ellipsoids, H atoms omitted for clarity). Symmetry
2
ϱ
2
[Sn(SPh) ] (1) viewed
transformation for generation of equivalent atoms: Ј x + 1/2, –y However the bonding situation is similar to 2 with SnTePh
2
+
2
2, z. Selected bond length [pm]: Sn(1)–S(1) 251.8(2), Sn(1)–S(2)
57.7(2), Sn(1)–S(2)Ј 273.1(2). Selected bond angles (°): S(1)–
Sn(1)–S(2) 77.16(6), S(1)–Sn(1)–S(2)Ј 92.68(6), S(2)–Sn(1)–S(2)Ј
7.58(5), Sn(1)–S(2)Ј–Sn(1)Ј 97.03(5).
units [Sn(1)–Te(2) 287.2(1), Sn(1)–Te(1) 289.5(1), Sn(2)–
Te(4) 287.9(1), Sn(2)–Te(3) 288.4(1) pm]; [Te(2)–Sn(1)–
Te(1) 87.28(3), Te(4)–Sn(2)–Te(3) 91.31(3)] which are linked
by weaker tellurium to tin donor acceptor bonds [Sn(1)–
8
2
crystallises in the monoclinic space group P2 /n with Te(4) 327.4(1), Sn(2)–Te(1) 312.8(1), Sn(1)–Te(3) 316.8(1),
1
two formula units in the asymmetric unit (Table 3). In con- Sn(2)Ј–Te(2) 334.5(1) pm] to form the one dimensional
trast to 1 the Sn(SePh) units of 2 are in the solid state µ - chains. Two different Sn–Te bond length [280.0(1) and
2
2
Eur. J. Inorg. Chem. 2010, 410–418
© 2010 Wiley-VCH Verlag GmbH & Co. KGaA, Weinheim
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411

A. Eichhöfer et al.
FULL PAPER
2
95.6(1) pm] were also found in dimeric [Sn{TeSi-
[
12]
(SiMe ) } ]
where the tin atoms adopt a distorted trigo-
3
3 2 2
nal pyramidal coordination in the crystal.
Figure 3. Section of the crystal structure of 1
[Sn(TePh) ] (3) viewed
ϱ 2
down a (50% ellipsoids, H atoms omitted for clarity). Symmetry
transformations for generation of equivalent atoms: Ј –x + 3/2, y –
1
/2, –z + 1/2. Selected bond length [pm]: Sn(1)–Te(2) 287.2(1),
Sn(1)–Te(1) 289.5(1), Sn(2)–Te(4) 287.9(1), Sn(2)–Te(3) 288.4(1),
Sn(1)···Te(4) 327.4(1), Sn(2)···Te(1) 312.8(1), Sn(1)···Te(3)Ј 316.8(1),
Sn(2)Ј···Te(2) 334.5(1). Selected bond angles (°): Te(2)–Sn(1)–Te(1)
8
7.28(3), Te(2)–Sn(1)–Te(3) 91.12(1), Te(1)–Sn(1)–Te(3) 78.06(1)
Te(4)–Sn(2)–Te(3) 91.31(3), Te(4)–Sn(2)–Te(1) 89.20(2), Te(3)–
Sn(2)–Te(1) 80.36(1), Sn(1)–Te(1)–Sn(2) 93.69(1), Sn(2)Ј–Te(3)–
Sn(1) 92.28(1).
A comparison of the measured and calculated X-ray
powder diffraction patterns for 1, 2 and 3 reveal their crys-
talline purity with respect to the formation of other crystal-
1
] (1), 1
Figure 4. UV/Vis spectra of
ϱ
[Sn(SPh)
2
ϱ 2
[Sn(SePh) ] (2) and
1
ϱ
[Sn(TePh) ] (3) a) in solid state (powder in mineral oil between
2
line compounds (Figure S1). Slightly increasing differences quartz plates) and b) in thf.
in the position of the peaks with increasing detection angle
arise from the temperature difference of the detection of the
single crystal data and the powder patterns.
UV/Vis spectra in thf display two nearly similar curves
for 1 and 2 with maxima at 257 nm and 265 nm respectively
most probably dominated by strong π-π* transitions of the
chalcogenolato ligands (Figure 8). 3 although not com-
Optical Properties
Dried crystalline powders of 1, 2 and 3 appear light-yel- pletely soluble and slowly decomposing shows an onset of
low, yellow and golden-yellow, respectively. The UV/Vis a weak and broad absorption already at 560 nm which
spectra in the solid state display a small shift in the absorp- might be assigned to ligand to metal charge transfer transi-
tion onset on going from 1 (440 nm) to 2 (470 nm) and a tions followed by two shoulders at 280 nm and 232 nm. Cal-
significant red shift for 3 (690 nm) (Figure 4). All spectra culation of the electronic triplet excitation spectrum of the
show only weakly pronounced features.
mononuclear compounds Sn(EPh) (E = S, Se, Te) with
2
Upon going from 1 to 3 the solubility decreases signifi- time-dependent density functional theory (for technical de-
cantly presumably due to the change in the structures as tails see next section) reveals that the lowest excitations
well as a stronger bonding of the large and soft base telluro- show a similar energetic shift from the sulfur to the tel-
lato ligands to the large and soft acid tin atoms compared lurium species as observed in the measurements. However
to the thiolato and selenolato ligands. While 1 is well solu- the strong red-shift which was especially observed in the
ble in thf similar amounts of 2 need mixtures of more solid state spectra of 3 compared to that of 2 is not repro-
strongly coordinating solvents like CH CN and dmf. Al- duced in the calculations; calculated lowest excitations are
3
though 3 shows some solubility in thf or CH CN it is only at 1.8 eV(Te), 2.2 eV (Se) and 2.4 eV (S), see Figure S2 of
3
well soluble in dmso. However all solutions of 3 show upon the supplementary material. This discrepancy is not too
standing decomposition indicated by the formation of black surprising, as intermolecular interactions in the one-dimen-
precipitates of SnTe as already observed for ether solutions sional chains are not considered in the calculations. The
of the related silylated compound [Sn{TeSi(SiMe ) } ] by lowest excitation mainly is a transition from the HOMO,
3
3 2 2
[4]
addition of Lewis bases like CH CN.
located at the chalcogen atoms, to the LUMO, located
3
412
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© 2010 Wiley-VCH Verlag GmbH & Co. KGaA, Weinheim
Eur. J. Inorg. Chem. 2010, 410–418

1
-D-Tin(II) Phenylchalcogenolato Complexes 1
[Sn(EPh) ] (E = S, Se, Te)
ϱ 2
mainly at the Sn atom (Figure 5). Similar is true for the two LMOs are obtained from CMOs by unitary transformation
excitations following in energy, so the lowest excitations are with the requirement that they have to be localized at as
[
30]
p-p ligand to metal charge transfer transitions.
few as possible atoms (Pipek-Mezey localization ). In this
way one loses the information of orbital energies, but gains
objects that are suited for intuitive interpretation (bonds,
lone pairs). We note that this transformation is not unique,
i.e. different localization procedures will lead to slightly dif-
ferent LMOs. In Figure 6 (left hand side) we show the rel-
evant LMOs located at tellurium and tin for the monomer:
the Te–Sn and the Te–C bond (LMO1, LMO2), s-type lone
pairs at tin and tellurium (LMO3, LMO4) and a p-type
lone-pair at tellurium (LMO5). For the bonds also the con-
tributions from the bond partners (from a Mulliken popula-
[
31]
tion analysis ) are shown. As expected, the Te–Sn-bond is
significantly polarized towards the tellurium atom, the C–
Te bond is slightly polarized towards the carbon atom.
6 5 2
Figure 5. Molecular frontier orbitals of monomeric Sn(TeC H ) .
Contours are drawn at 0.05 a.u., orbital energies (right) are given
in eV.
Quantum Chemical Considerations
The bond situation within a monomeric Sn(EPh) (E =
2
S, Se, Te) unit may be described by two-electron-two-centre
E–Sn and E–C bonds. The remaining electrons form two
lone pairs at each of the chalcogen atoms and one at the
tin atom. For a better understanding and in order to ratio-
nalize the polymerization, density functional calculations
[
23]
(
program system TURBOMOLE,
BP-86 func-
[
24,25]
[26]
tional,
def2-SV(P) bases
plus RI-J auxiliary
bases, effective core potentials for tin and tellurium
[
27]
[28,29]
)
were carried out. The frontier molecular orbitals for the
monomer in C2v symmetry with E = Te are shown in Fig-
ure 5; the shape is very similar for E = S, Se. The highest
occupied molecular orbital (HOMO) is the antisymmetric
combination of the p-orbitals of the tellurium atoms per-
Figure 6. Selected localized molecular orbitals (Pipek-Mezey local-
ization) of Sn(TeC H ) (left) and [Sn(TeC H ) ] (right). Contours
6 5 2 6 5 2 2
are drawn at 0.05 a.u. The numbers indicating the contributions
from bond partners are calculated by a Mulliken population analy-
pendicular to the molecular plane, p (Te). The HOMO-2
z
mainly consists of their symmetric combination plus small
contributions from p (Sn). HOMO-1 and HOMO-3 are in sis.
z
the molecular plane; HOMO-1 consists of p (Sn) plus s(Sn)
x
together with symmetry-matching combinations of p (Te)
Formation of polymers is studied for E = Te in detail,
x
and p (Te); HOMO-3 involves p (Sn) and similar combina- differences for E = S are given in the end. Polymerization
y
y
tions from the tellurium atoms. The ratio of atomic contri- is driven mainly by electron transfer from the p orbitals
z
butions to the MOs and even their energetic sequence de- from the E atoms (electron donor, Lewis base) of one
pend on spatial extension and energy difference of s- and monomer to the empty p orbitals of the Sn atom (electron
z
p-orbitals of E (for E = Se HOMO-3 and HOMO-2 are acceptor, Lewis acid) of a second monomer. This can be
interchanged, for E = S additionally HOMO-1 and seen from the changes of some of the LMOs from the
HOMO). The lowest unoccupied orbital (LUMO) is the monomer to the dimer, right hand side of Figure 6. One
p (Sn) plus small contributions of p (Te). Agreement with observes significant electron transfer to the empty p orbital
z
z
z
the simple description given in the beginning of this section (LMO5) of the tin atom of the second monomer; the contri-
can be achieved by the consideration of localized molecular bution of this atom to this LMO amounts to 0.41 electrons
orbitals (LMOs); this is also helpful for understanding the (from a Mulliken population analysis for this LMO). Fur-
mechanism of polymerization. LMOs are linear combina- ther the polar character of the intramolecular Sn–Te-bond
tions of the occupied canonical MOs (CMOs), i.e. those (LMO1) is enhanced; it is very similar to that of the inter-
resulting Hartree–Fock or DFT calculations (Figure 5); molecular Sn–Te bond. In the same way electrons are trans-
Eur. J. Inorg. Chem. 2010, 410–418
© 2010 Wiley-VCH Verlag GmbH & Co. KGaA, Weinheim
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413

A. Eichhöfer et al.
FULL PAPER
ferred from p (Te) of the second unit to p (Sn) of the first
z
z
unit. For each dimer the two remaining p (Te), which are
z
not involved in this bond, are used to bind to the next dimer
by the same mechanism. This on the other hand means that
in each dimer the tin atoms act as acceptors for electrons
from two further tellurium atoms (additional to that of the
monomer).
For E = Se matters are very similar, but for E = S each
tin atom is connected only to one further sulfur atom. This
may have steric reasons, but also the lower energy of the
p(S) orbitals compared to the p(Te) might be considered.
This will lead to less pronounced electron transfer from sul-
fur to tin and thus to a preference for accepting electrons
from only one additional sulfur atom. For clarity we finally
note that the d-orbitals of Sn do not play a role in these
considerations. This is confirmed by values for their occu-
pation from natural population analyses (NPA),[ which
in all cases amount to less than 0.01 electrons.
32]
1
] (1), 1
ϱ
[Sn-
Figure 7. Thermogravimetric analysis of
ϱ
[Sn(SPh)
2
1
(
SePh)
2
ϱ 2
] (2) and [Sn(TePh) ] (3) under a) He gas flow and b) in
vacuo (see also Table 1).
Thermal Behaviour
Table 1. Experimental and theoretical mass loss (due to Scheme 2)
1
ϱ 2
Upon heating 1 starts to melt around 198 °C to give a for the thermal gravimetric analyses (Figure 7) of [Sn(SPh) ] (1),
1
1
ϱ
[Sn(SePh)
2
ϱ 2
] (2) and [Sn(TePh) ] (3).
brownish-yellow liquid and decomposes around 280 °C
while 2 and 3 start to visibly decompose with formation of
black powders already at 180 °C and 108 °C, respectively.
In order to investigate the thermal properties of 1–3 in more
detail we first performed thermogravimetric analysis under
helium gas flow and under vacuum conditions. In addition
thermolysis experiments were then carried out in Schlenk
tubes to further investigate the cleavage products.
Compound Experimental mass loss [%]
He gas flow vacuum
Theoretical mass loss [%]
1
2
3
62.4
58.1
53.1
90.8
76.9
63.3
55.3
54.1
53.4
Thermogravimetric analyses under helium gas flow dis-
play clearly one step mass losses for 2 and 3 while 1 displays
a minor gradual mass loss starting around 125 °C before
the main decomposition step which occurs between 265 °C
Scheme 2.
and 348 °C (Figure 7a, Table 1). The selenolato complex 2 While for 3 the difference is about 10% for the thermal
decomposes between 200 °C and 310 °C while 3 is, as al- treatment of 2 the experimental mass loss of even more dif-
ready indicated by its instability in solution, much more fers from its theoretical value compared to the TGA under
unstable than 1 and 2 and decomposes between 126 °C and helium atmosphere. For 1 the residue is only 9.2% in mass
206 °C. The X-ray powder patterns of the residues reveal of the precursor complex and is characterised by powder
the formation of pure binary SnE (E = S, Se, Te) XRD to be solely elemental tin suggesting not only subli-
[
33–35]
phases
(Figure S3) comparable with the pyrolysis mation but also a different thermal reaction than observed
VI
products of the Sn precursor molecules (Ph Sn) E (E = under atmospheric pressure.
S, Se, Te) which start to decompose around 330 °C. Car-
3
2
[
36]
In order to further investigate the cleavage products,
bon and hydrogen contents were found to be less than 1%. thermolysis experiments were carried out in preparative
While the experimental total mass loss for 3 is in good scale (ca. 200 mg) under N atmosphere (up to 350 °C) and
2
agreement with the calculated value for the formal cleavage in vacuo (up to 300 °C) in Schlenk tubes located inside a
of one equivalent of TePh from Sn(TePh) to yield SnTe tube furnace (for details see experimental part and Table 2).
2
2
according to Scheme 2, it differs for 1 and 2 (see Table 1).
The cleavage products of the thermolysis of 1 under N2
Thermogravimetric analyses in vacuo in principle also atmosphere could by careful condensation be almost com-
display one step mass losses for 1–3 with two weak shoul- pletely separated in a yellow crystalline powder and a pale
ders indicated for 3 (Figure 7b). Again, the tellurolate com- yellow liquid. However apart from the identification of the
[
37,38]
plex 3 decomposes much earlier, already between 50 °C and liquid main product SPh by NMR
it was not possible
2
145 °C, than 1 and 2. The X-ray powder patterns of the to clearly identify the other compounds (see experimental
residues of 2 and 3 indicate formation of pure orthorhom- section). In contrast, for the thermolysis of 1 under vacuum
bic SnSe and SnTe, respectively (C, H Ͻ 1%). Now for all conditions only the formation of a light yellow solid pre-
compounds the experimental mass change is not in line cipitate on the walls of the glass tube outside the furnace is
with the calculated one according to Scheme 2 and Table 1. observed which is identified by powder XRD to consist
414
www.eurjic.org
© 2010 Wiley-VCH Verlag GmbH & Co. KGaA, Weinheim
Eur. J. Inorg. Chem. 2010, 410–418

1
-D-Tin(II) Phenylchalcogenolato Complexes 1
[Sn(EPh) ] (E = S, Se, Te)
ϱ 2
Table 2. Thermolysis data of 1
Compound Final temperature [°C] Residue[a] Residual mass [%] (th.)[b] Identified cleavage products[c] Visible mp/decomp. [°C]
Thermolysis under N
[Sn(SPh)
] (1), 1
[Sn(SePh)
] (2) and 1
[Sn(TePh) ] (3).
ϱ
2
ϱ
2
ϱ 2
2
1
2
3
350
350
350
SnS
SnSe
SnTe
36.7 (44.7)
41.0 (45.9)
46.0 (46.6)
S(Ph)
Se(Ph)
Te(Ph)
2
198/280
–/180
–/108
2
2
Thermolysis under vacuum (2ϫ10–6 mbar)
1
2
3
300
300
300
Sn
SnSe
SnTe
8.2 (–)
21.9 (45.9)
36.0 (46.6)
Sn(SPh)
2
, Sn(SPh)
4
198/–
–/180
–/110
[
a] Identified by powder-XRD (C, H Ͻ 1%). [b] Calculated mass% of the residue due to the formal cleavage of one equivalent of
E(Ph) (E = S, Se, Te) (Scheme 2) with the exception of the vacuum thermolysis of Sn(SPh) where 100% sublimation was assumed. [c]
Identified by H-, C-NMR or powder XRD.
2
2
1
13
mainly of 1 (Figure 8). However the sublimation is ac- ment but decomposes at the hot walls of the tube before
companied by a partial decomposition reaction of 1 to give being able to leave the hot reaction zone.
a 8.2% (TGA: 9.2%) mass percent residue of elemental tin
Decomposition of 3 under N2 atmosphere yields an
and in the sublimate appropriate amounts of the oxidation orange oil as the cleavage product which was identified by
1
13
[42,43]
product Sn(SPh) as proven by the corresponding powder
H- and C-NMR to consist of TePh2
with small
4
[
39,8]
diffraction patterns
(26% decomposition product).
amounts of unidentifiable side products. This is in agree-
ment with the proposed reaction mechanism according to
Scheme 2 and the results of the investigations of the ther-
molysis of [Sn{TeSi(SiMe ) } ] which was reported to de-
3
3 2 2
compose cleanly at 250 °C to yield SnTe and Te{Si-
[
12]
1
13
(
SiMe ) } . In contrast H and C NMR spectra of the
3 3 2
cleavage products from the thermolysis experiment of 3 un-
der vacuum in a Schlenk tube (a red powder and a yellow
liquid) show several signals for aromatic C and H atoms
and do not clearly reveal the formation of TePh which
2
again indicates a more complex decomposition reaction
then expected according to Scheme 2.
These findings are partially in agreement with observa-
tions on the thermal reactions of [Sn{ESi(SiMe ) } ] (E =
3
3 2 2
S, Se) where the cleavage products were contaminated with
unidentifiable SiMe -containing species. However for these
3
compounds the formed binary chalcogenides SnE (E = S,
Se) also proved to be extremely rich in elemental tin which
was in our case only observed for the vacuum thermolysis
[
12]
of 1.
Conclusions
Figure 8. Powder XRD pattern of the cleavage products of the ther-
molysis of 1
with the calculated one of Sn(SPh)
–6
ϱ
2
[Sn(SPh) ] (1) under vacuum (2ϫ10 mbar) compared
[8]
Reaction of SnCl with two equivalents of PhESiMe (E
2
3
4
and 1.
=
S, Se, Te) yielded the 1-D-tin(II) phenylchalcogenolato
1
The yellow cleavage product of the thermal treatment of complexes [Sn(EPh) ] in high yields. The closely related
ϱ
2
1
13
2
under nitrogen clearly display in the H- and C-NMR 1D chain structure of the selenolato and tellurolato com-
[
40,41]
spectra peaks of the main product SePh2
together with plex in the solid state differ from the thiolato analogue with
not yet identifiable additional peaks. Thermolysis of 2 un- respect to the coordination modes of the tin atoms which
der vacuum resulted also in the formation of a yellow liquid is found to be larger in the case of the heavier chalcogen
which condenses outside the furnace but in addition a black elements. DFT calculations reveal that the structures should
metallic mirror is formed on the walls of the glass tube in- be described as consisting of monomeric “Sn(EPh) ” units
2
1
13
side the furnace. Due to the H and C NMR spectra the which are linked by additional weaker chalcogen to tin do-
liquid cleavage products contain several not identifiable nor acceptor bonds to form polymeric chains. With respect
compounds while the black precipitate on the glass walls to the optical and thermal behaviour [Sn(TePh) ] shows a
1
ϱ
2
was characterized to be orthorhombic SnSe like the residue significant red shift of the absorption onset and a distinctly
in the quartz boat. In line with the mass loss this suggests reduced thermal stability compared to the other two homo-
that 2 distinctly sublimes under the conditions of the experi- logues. While thermal treatment of the tellurolate complex
Eur. J. Inorg. Chem. 2010, 410–418
© 2010 Wiley-VCH Verlag GmbH & Co. KGaA, Weinheim
www.eurjic.org
415

A. Eichhöfer et al.
FULL PAPER
leads under comparable mild conditions (200 °C, N ) to the 156.96 SeC
6
H
) ].
5
–); m/zexp 586.78, rel. int. 100 [m/zcalc 586.77
2
3
–
Sn(SeC
6
H
5
almost stoichiometric formation of SnTe and TePh2 the
other reactions are ongoing from the tellurolato to the thi-
olato complex and by the use of vacuum conditions increas-
[
1
Sn(TePh)
2
] (3): To a solution of SnCl [0.38 g (1.983 mmol)] in
2
60 mL of thf PhTeSiMe [0.96 mL (4.17 mmol)] is added at
3
ingly dominated by sublimation. In addition investigations –70 °C. Soon the reaction solution turns orange and a voluminous
of the volatile reaction products suggest more complex re- precipitate forms. The reaction solution is warmed up to 4 °C over-
actions in the gas phase than the formal stoichiometric night without stirring and then kept at this temperature in a refrig-
erator. Tiny yellow needles of 3 form in a deep dark yellow solution
which are filtered cool and quickly washed with a 1:1 mixture of
thf/dme (cooled to –5 °C) to give a total yield of 82% (0.862 g). 3
is slightly soluble in thf and well soluble in dmso. However all solu-
tions show upon standing decomposition with formation of SnTe.
12 2
C H10SnTe (528.09): calcd. C 27.3, H 1.9; found C 27.2, H 2.0.
cleavage of EPh (E = S, Se, Te) with formation of SnE.
However the investigations suggest that more easily sublim-
2
able compounds [Sn(ER) ] (E = S, Se; R = alkyl group)
2
could have a potential for the use as single source precursor
compounds for the synthesis of SnE in CVD processes.
IR (KBr): ν˜ = 3035 (m), 3025 (w), 2973 (w), 1940 (w, br), 1865 (w,
br), 1800 (vw, br), 1566 (s), 1498 (vw), 1467 (s), 1428 (m), 1384 (s),
1
1
322 (m), 1294 (m), 1262 (w), 1173 (w), 1157 (w), 1059 (vw, br),
013 (m), 996 (w), 900 (w), 836 (w), 802 (w), 727 (vs), 689 (vs), 649
Experimental Section
–
1
4
Synthesis: Standard Schlenk techniques were employed throughout
(m), 450 (s) cm . UV/Vis (thf) λmax = 402 nm (br); ε = 0.0988ϫ10
l mol cm , λ = 278 nm (sh); ε = 0.7888ϫ10 l mol cm , λmax
= 233 nm (sh); ε = 1.172ϫ10 l mol cm . H NMR [300 MHz,
(CD SO]: δ = 7.0 (t, 2 H, meta-CH), 7.11 (1 H, para-CH), 7.68
(d, 2 H, ortho-CH) ppm. C{ H} NMR [75 MHz, (CD ) SO]: δ =
3 2
114 (s, CTeSn), 125.7 (s, para-CH), 129 (s, meta-CH), 139.3 (s, or-
tho-CH) ppm. ESI-TOF-MS: m/zexp 206.95, rel. int. 100, (m/zcalc
2
–
3
–1
–1
4
–1
–1
the syntheses using a double manifold vacuum line (10 mbar)
with high purity nitrogen (99.99990%). The solvents thf (tetrahydo-
furan), dme (1,2-dimethoxyethan) and ethyl ether were dried with
4
–1
–1 1
3 2
)
1
3
1
sodium-benzophenone, and distilled under nitrogen. PhSSiMe
3
and
and PhTe-
were prepared according to literature procedures.
[44]
SnCl
SiMe
2
were purchased from Aldrich. PhSeSiMe
3
[
45]
3
–
06.95 TeC
6
H
5
); m/zexp 324.85, rel. int. 25, (m/zcalc 324.85
[
Sn(SPh)
2
] (1): SnCl
2
[0.162 g (0.85 mmol)] is dissolved in 10 mL of
–
TeSnC
6 5
H ); m/zexp 734.74, rel. int. 50 [m/zcalc 734.74 Sn-
dme to give a clear solution. Upon addition of PhSSiMe [0.34 mL
1.79 mmol)] tiny yellow needles soon start to crystallize from the
3
3–
(
TeC H ) ].
6 5
(
solution. Filtration and washing with ethyl ether after two days
resulted in 0.20 g of 1. Evaporation of the pure filtrate to dryness,
redissolution of the solid residue in 10mL of thf and layering with
ethyl ether yielded further 0.03g of 1 to give a total yield of 81%.
Thermolysis: Thermolysis experiments were carried out using a
Linn High Term FRHT-70/500/1100 programmable tube furnace,
70 cm long and 4 cm in diameter equipped with a ca. 50ϫ3 cm
borosilicate Schlenk tube. For experiments under vacuum the tube
was directly connected with a cool trap to a turbo molecular pump
setup from Edwards (vacuum 10 mbar) while for thermolysis un-
der nitrogen the tube with the cool trap were connected via a Viton
tubing to a mercury bubbler of a Schlenk line. The samples to be
pyrolysed were placed in either quartz or porcelain boats in the
center of the furnace (ca. 200 mg). For all samples the oven was
1
is soluble in thf, slightly soluble in dme and not soluble in ethyl
ether. C12 Sn (337.01): calcd. C 42.8, H 3.0, S 19.0; found C
2.8, H 3.0, S 19.5. M.p. 198 °C. IR (KBr): ν˜ = 3053 (m, sh), 3049
m), 3010 (w), 1938 (w, br), 1859 (w, br), 1796 (w, br), 1732 (w, br),
572 (m), 1472 (m), 1460 (m, sh), 1433 (s), 1384 (s), 1328 (w), 1298
m), 1263 (m), 1181 (w), 1158 (w, br), 1081 (m), 1066 (m), 1021
–
6
H
10
S
2
4
(
1
(
–1
(
m), 895 (w), 835 (w), 732 (vs), 687 (vs), 475 (s) cm . UV/Vis (thf) programmed to ramp at a rate of 2 °C/min to 350 °C under a static
4
–1
–1 1
–6
λmax=257 nm;ε=3.4ϫ10 lmol cm . HNMR[300 MHz,(CD
3
)
2
-
2
pressure of N and to 300 °C under vacuum (2ϫ10 mbar) and
SO]: δ = 7.29 (t, 1 H, para-CH), 7.38 (t, 2 H, meta-CH) , 7.52 (d,
hold at this temperature for 1h before allowing the oven to cool to
SO]: δ = room temperature. The solid residues in the porcelain or quartz
27.6 (s, para-CH), 128.0 (s, ortho-CH), 129.9 (s, meta-CH), 136.2 boats were weighed and characterized by powder X-ray analyses
13
1
2
1
H, ortho-CH) ppm. C{ H} NMR [75 MHz, (CD
3
)
2
(
1
s, CSSn) ppm. ESI-TOF-MS: m/zexp 109.01, rel. int. 100, (m/zcalc
while the volatile cleavage products which deposit in the part of the
tube outside the furnace and in the cool trap were collected with
thf (liquid products) for NMR and ESI-TOF analysis or investi-
gated by powder XRD in the case of solids.
–
6 5
09.01 SC H ); m/zexp 446.94, rel. int. 100 [m/zcalc 446.94
3
–
Sn(SC
6
H
5
) ].
[Sn(SePh)
2
] (2): SnCl [0.154 g (0.81 mmol)] is dissolved in 25 mL
2
of thf to give a clear solution. Upon addition of PhSeSiMe
0.34 mL (1.79 mmol)] the mixture immediately turns yellow and a
voluminous precipitate forms. Standing overnight yields thin yellow
needles of 2 which are filtered and washed with dme to give a total
yield of 86% (0.30 g). 2 is sparingly soluble in thf and well soluble
3
Details of the Thermolysis of 1: The cleavage products of 1 could
by careful condensation be almost completely separated in a yellow
powder and a pale yellow liquid. The liquid contains beside the
[
[46,47]
main product SPh
2
other products with aromatic C and H
atoms which could not be identified by NMR spectroscopy. The
XRD powder pattern of the yellow powder reveals the existence of
crystalline material however it does not match that of 1. ESI-TOF
in dmf and dmso. C12
2
H10Se Sn (430.81): calcd. C 33.5, H 2.3;
found C 34.2, H 2.6. IR (KBr): ν˜ = 3052 (m), 3015 (w), 2980 (w),
–
1
1
1
8
936 (w, br), 1865 (w, br), 1793 (w, br), 1732 (vw, br), 1631 (w),
570 (s), 1470 (s), 1432 (m), 1384 (s), 1323 (m), 1296 (m), 1264 (w), (m/zcalc 109.01, m/zexp 108.99, rel. int. 44) but do not display the
mass spectra of solutions of this powder in thf show SPh ions
–
178 (w), 1158 (w, br), 1097 (vw, br), 1066 (m), 1017 (m), 997 (w),
3
characteristic fragment [Sn(SPh) ] (m/zcalc 446.94, m/zexp 446.94)
–1
–
94 (w), 840 (w), 726 (vs), 686 (vs), 666 (s), 460 (s) cm . UV/Vis
which was found as the major component beside SPh in solutions
–1
–1
1
(
thf) λmax = 266 nm; ε = 3.6ϫ104 l mol cm . H NMR of 1. Instead other fragments which contain tin atoms and a higher
–
[
300 MHz, (CD
3
)
2
SO]: δ = 7.32 (m, 3 H, meta-CH, para-CH), 7.62
S:C/H ratio were found like SnS
3
C
6
H
7
(m/zcalc 294.87, m/zexp
13
1
–
(
d, 2 H, ortho-CH) ppm. C{ H} NMR [75 MHz, (CD
28.3 (s, para-CH), 130 (s, meta-CH), 130.5 (s, CSeSn), 131.3 (s,
ortho-CH) ppm. ESI-TOF-MS: m/zexp 156.96, rel. int. 100, (m/zcalc
3
)
2
SO]: δ =
294.84 rel. int. 11), SnS
int. 100), SnS 13 (m/zcalc 508.86, m/zexp 508.86 rel. int. 40) and
SnS 17 (m/zcalc 616.87, m/zexp 616.86 rel. int. 4). Suggestions
3 12 9
C H (m/zcalc 368.89, m/zexp 368.88 rel.
1
5 18
C H
6 24
C H
416
www.eurjic.org
© 2010 Wiley-VCH Verlag GmbH & Co. KGaA, Weinheim
Eur. J. Inorg. Chem. 2010, 410–418

1
-D-Tin(II) Phenylchalcogenolato Complexes 1
[Sn(EPh) ] (E = S, Se, Te)
ϱ 2
for the structures of these fragments are difficult to make because
no other S, C, H containing ligands could be identified in the mass
spectra.
single-crystal X-ray analysis by using the program package STOE
WinXPOW.[
51]
Physical Measurements: C, H, S elemental analyses were performed
on an “Elementar vario Micro cube” instrument.
Crystallography: Crystals suitable for single-crystal X-ray diffrac-
tion were taken directly from the reaction solution of the com-
pound and then selected in perfluoroalkylether oil. Single-crystal
X-ray diffraction data of 1 and 2 were collected using graphite-
monochromatised Mo-K radiation (λ = 0.71073 Å) on a STOE
α
IPDS II (Imaging Plate Diffraction System). Single-crystal X-ray
UV/Vis absorption spectra of 1–3 in solution were measured on a
Varian Cary 500 spectrophotometer in quartz cuvettes. Solid state
absorption spectra were measured as micron sized crystalline pow-
ders between quartz plates with a Labsphere integrating sphere.
1H-NMR and 13C-NMR spectra were recorded on a Bruker DPX
Avance 300.
diffraction data of 3 were collected using synchrotron radiation (λ
=
0.80 Å) on a STOE IPDS II (Imaging Plate Diffraction System)
at the ANKA synchrotron source in Karlsruhe. Raw intensity data
were collected and treated with the STOE X-Area software Version
IR spectra were measured on a Perkin–Elmer Spectrum GX as KBr
pellets in a region from 4000 to 350 cm .
–1
1.39. Data for all compounds were corrected for Lorentz and pola-
2 3
Thermogravimetric analyses were run in Al O crucibles on a
risation effects. Based on a crystal description numerical absorption
–
6
corrections were applied for 1 and 3 (Table 3).[
48]
thermobalance STA 409 from Netzsch in vacuo (7ϫ10 mbar) or
with a dynamic helium gas flow (25 mL/ min) at a heating rate of
2 °C/min. The crucibles were filled (20–35 mg) inside an argon
glove box, transferred in Schlenk tubes and mounted under a
stream of argon to the balance. However trace contamination of
The structures
were solved with the direct methods program SHELXS of the
SHELXTL PC suite programs,[49] and were refined with the use of
the full-matrix least-squares program SHELXL. Molecular dia-
grams were prepared using Diamond.[
50]
2
oxygen indicated by the formation of SnO and SnO could not be
Table 3. Crystallographic data for 1
and 1
[Sn(TePh) ] (3).
[Sn(SPh)
] (1), 1
[Sn(SePh)
] (2)
totally avoided in this way in all cases. Caution should be taken
with respect to the toxic and bad smelling volatile products formed
in the thermolysis.
ϱ
2
ϱ
2
ϱ
2
1
2
3
Mass spectra were taken on a Time of Flight (TOF) mass spec-
trometer (Bruker Daltonics, MicroTOF-QII) equipped with an
electrospray ion source (off axis sprayer). The solutions were
sprayed at typical flow rates of about 180 µL/h and nebulized using
dry nitrogen. The desolvation glass capillary was heated to 180 °C.
For all ion signals observed the charge state was immediately evi-
dent from their isotopomere splitting and assignment to an ionic
species was unequivocally confirmed by comparison to the com-
puted isotopic distribution. All m/z values given in the text corre-
spond to the most abundant peak of the respective distributions.
fw [g/mol]
Crystal system
Space group
Cell
a [Å]
b [Å]
337.01
orthorhombic
430.81
monoclinic monoclinic
P2 /n P2 /n
528.09
Pca2
1
1
1
7.141(1)
6.110(1)
26.740(5)
11.708(2)
11.893(2)
18.427(4)
93.32(3)
2561.3(9)
8
12.389(3)
11.833(2)
18.504(4)
101.89(3)
2654.5(9)
8
c [Å]
β [°] 3
V [Å ]
Z
1166.8(4)
4
190
T [K]
150
130
λ [Å]
MoK
α
MoK
α
0.8000
2.643
8.651
1888
56
–3
d
c
[g cm ]
1.919
2.509
656
2.234
7.644
1600
52
–1
Acknowledgments
µ(λ) [mm]
F(000)
2θmax [°]
49
This work was supported by the National Science Foundation of
China (Grant 20525310, 20773167) the Deutsche Forschungsge-
meinschaft (center for functional nanostructures CFN) and the Re-
search Center of Karlsruhe. The authors are grateful to E. Tröster
and N. Metz for their valuable assistance in the practical work.
Measured reflns.
Unique reflns.
3512
1851
0.0516
17192
4805
0.0350
4172
351
0.0242
0.0565
12661
4379
0.0535
3930
351
0.0272
0.0688
R
int
Reflns. with IϾ2σ(I) 1755
Refined params.
137
0.0373
0.0996
[
a]
R1[IϾ2σ(I)]
[b]
wR2(all data)
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= {Σ[w(F 2 2)2]/Σ[w(F ) ]}1/2.
2 2
[
a] R = Σ||F | – |F ||/Σ|F |. [b] wR – F
1
o
c
o
2 o c o
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[Sn(SPh)
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1
ϱ
[Sn(SePh)
2
ϱ 2
] (2) and [Sn(TePh) ] (3) were measured on a STOE
6
STADI P diffractometer (Cu-Kα1 radiation, Germanium mono-
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3
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Eur. J. Inorg. Chem. 2010, 410–418
© 2010 Wiley-VCH Verlag GmbH & Co. KGaA, Weinheim
www.eurjic.org
417

A. Eichhöfer et al.
FULL PAPER
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