Preparation of 17 sulfur-rich chain-like thiaalkanes R-S x-R′-Sy-R and R-Sx-R′-S y-R′-Sz-R (x, y, z > 2) from titanocene thiolate complexes

Article abstract of DOI:10.1002/ejic.200300591

Two novel Cp₂Ti(Cl)S₃R'S₃Tr complexes have been prepared by reaction of the six-membered metallacycles Cp ₂TiS₄R' (Cp = η⁵-C₅H ₅, R' = CMe₂, 1,1-C₆H₁₀) with the sulfenyl chloride TrSCl (Tr = CPh₃) at 20 °C. These complexes were treated with: (a) sulfenyl chlorides (RSCl or RSSCl) to obtain 11 new thiaalkanes of the type R-S_x-R'-S_y-R (R = Tr, 4-ClC ₆H₄, 2-C₁₀H₇; x = 3, y > 2), or (b) with SO₂Cl₂, SCl₂ or S₂Cl ₂ to prepare six sulfur-rich species of the type Tr-S _x-R'-S_y-R'-S_z-Tr (x, z = 3, y > 3), as well as Cp₂TiCl₂. The thiaalkanes decompose upon heating to give mixtures of various linear and cyclic polysulfanes R₂S _n and R'S_m. Wiley-VCH Verlag GmbH & Co. KGaA, 69451 Weinheim, Germany, 2004.

Full text of DOI:10.1002/ejic.200300591

FULL PAPER
Preparation of 17 Sulfur-Rich Chain-Like Thiaalkanes R؊Sx؊RЈ؊Sy؊R and
R؊Sx؊RЈ؊Sy؊RЈ؊Sz؊R (x, y, z Ͼ 2) from Titanocene Thiolate Complexes[‡]
Vera Münchow[a] and Ralf Steudel*[b]
Keywords: Alkanes / Ligand effects / Sandwich compounds / Sulfur / Titanium
Two novel Cp2Ti(Cl)S3RЈS3Tr complexes have been prepared
by reaction of the six-membered metallacycles Cp2TiS4RЈ
(Cp = η5-C5H5, RЈ = CMe2, 1,1-C6H10) with the sulfenyl chlor-
ide TrSCl (Tr = CPh3) at 20 °C. These complexes were treated
with: (a) sulfenyl chlorides (RSCl or RSSCl) to obtain 11 new
thiaalkanes of the type R−Sx−RЈ−Sy−R (R = Tr, 4-ClC6H4, 2-
to prepare six sulfur-rich species of the type
Tr−Sx−RЈ−Sy−RЈ−Sz−Tr (x, z = 3, y Ͼ 3), as well as Cp2TiCl2.
The thiaalkanes decompose upon heating to give mixtures of
various linear and cyclic polysulfanes R2Sn and RЈSm.
( Wiley-VCH Verlag GmbH & Co. KGaA, 69451 Weinheim,
Germany, 2004)
C10H7; x = 3, y Ͼ 2), or (b) with SO2Cl2, SCl2 or S2Cl2
Introduction
fanes R2Sn (n Ͼ 2) by reaction with organic or inorganic
SϪCl compounds.[1,6] These reactions take place at 25 °C
or below and often proceed quantitatively. A good example
is the synthesis of the homocycles S6 and S12 from titano-
cene pentasulfide Cp2TiS5 (1; Cp ϭ η5-C5H5) and sulfur
dichloride[7] shown in Scheme 1.
Thiaalkanes are derivatives of alkanes (including cycloal-
kanes) in which some of the CH2 groups have been replaced
by sulfur atoms. Numerous compounds of this type are
known, both chain-like and cyclic and mainly with a single
sulfane unit ϪSxϪ (x ϭ 1, 2,...) between two organic resi-
dues R.[1] In a narrower sense, thiaalkanes are compounds
with two or more sulfane units separated by organic groups,
for example RϪSxϪRЈϪSyϪRЈЈ. In the following we re-
strict our discussion to chain-like species of this type. While
thiaalkanes with single sulfur atoms or disulfane groups
have been prepared in large numbers by the classical meth-
ods of organosulfur chemistry,[2] and are widely used as
chemically resistant polymers,[3] almost no such species with
either tri-, tetra-, penta- or hexasulfane units are known.[4]
This is most surprising and unsatisfactory in the light of the
biological activity of many thiaalkanes, in particular cyclic
species, which makes them interesting to the pharmaceut-
ical industry as well as for applications in agroscience.[1,5]
In this work we report on the synthesis of chain-like sulfur-
rich thiaalkanes with two and three polysulfane units from
suitable titanocene thiolate complexes by ligand-transfer re-
actions.
Scheme 1
The nucleophilic attack of the chlorine atoms of SCl2 on
the titanium atom opens the metallacycle producing an in-
termediate that either reacts intramolecularly by route (a)
to give S6 and Cp2TiCl2, or intermolecularly with another
molecule of 1 to give a second linear intermediate which
then reacts with SCl2 to form S12 [route (b)]. While the reac-
tive intermediates shown in Scheme 1 are hypothetical, the
related dinuclear complex (Cp2TiCl)2S3 has been isolated
and characterized by X-ray crystallography.[8] Mononuclear
complexes of the type Cp2TiX(SxR) with sulfanido ligands
containing more than one sulfur atom have also been iso-
lated (e.g., X ϭ Cl or SR with aryl or alkyl groups R; x ϭ
2, 3[9]).
In recent years a number of mono- and dinuclear titano-
cene thiolate complexes have been used to synthesize sulfur-
rich homocycles, heterocycles and linear organic polysul-
[‡]
Sulfur Compounds, 236. Parts 229Ϫ235: R. Steudel et al., Top.
Curr. Chem. 2003, vols. 230 and 231.
[a]
Viale Regina Margherita 52/E, 36078 Valdagno (VI), Italy
E-mail: vera.anto@libero.it
[b]
Institut für Chemie, Sekr. C2, Technische Universität Berlin,
In this work we show how titanocene complexes with
thiaalkane ligands can be used to prepare the title com-
pounds containing up to 12 sulfur atoms. Most useful in
10623 Berlin, Germany
Fax: (internat.) ϩ49-30-3142-6519
E-mail: steudel@schwefel.chem.tu-berlin.de
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DOI: 10.1002/ejic.200300591
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Sulfur-Rich Chain-like Thiaalkanes
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this context were the two metallacycles Cp2TiS4CMe2 (2a) cyclopentadienyl (δ ϭ 6.36 ppm) and methyl protons (δ ϭ
and Cp2TiS4C6H10 (2b) first prepared by Giolando and 1.69 ppm) besides the multiplet of the phenyl hydrogens
Rauchfuss[10] from Cp2TiS5 and acetone or cyclohexanone, near δ ϭ 7.32 ppm. The violet color of the novel complexes
respectively (Scheme 2).
in solution is caused by an absorption peaking at 560 Ϯ
4 nm (in MeOH).
In the solid state complexes 3a and 3b are stable at 4 °C
for several weeks but they decompose in solution at 20 °C,
especially in the presence of air, with formation of Cp2TiCl2
and an ochre precipitate. Chlorinated solvents also initiate
a slow decomposition. Therefore, the samples always con-
tained a few percent of Cp2TiCl2 (probably with formation
of mixed crystals) which also originates from the side reac-
tion of TrSCl with 3a or 3b, respectively. However, for pre-
parative purposes the purity was sufficient (see below). The
Scheme 2
These air-stable compounds are soluble in organic sol-
vents. Both complexes have been used before to synthesize
heterocyclic sulfur compounds by reaction with dichloro-
sulfanes SnCl2.[11,12]
1
content of Cp2TiCl2 can be determined by H NMR spec-
troscopy (singlet at δ ϭ 6.57 ppm). Complexes 3a and 3b
are well soluble in benzene and carbon disulfide, but less so
in n-hexane and methanol.
Attempts to isolate the corresponding complexes using
other sulfenyl chlorides such as TrSSCl, 4-ClC6H4SCl and
2-C10H7SCl failed due to rapid decomposition of the ring-
opened complexes and their consecutive reactions with the
sulfenyl chlorides.
Results and Discussion
Ring-Opening Reaction with Ph3CSCl
One aim of this work was to isolate the chain-like inter-
mediates of the type shown in Scheme 1. To stabilize these
reactive species we have chosen a particularly bulky sub-
stituent R on the sulfenyl chloride. Reaction of complexes
2a or 2b with triphenylmethylsulfenyl chloride Ph3CSCl
(tritylsulfenyl chloride, TrSCl) in a molar ratio of 1:1 at 20
Synthesis of Thiaalkanes
Treatment of complexes 3a or 3b with one equivalent of
°C in benzene produced the violet complexes 3a and 3b as ClC6H4SCl in CS2 at 20 °C expectedly yields the asym-
shown in Scheme 3.
metrical hexathiaalkanes 4a and 4b shown in Scheme 5.
These reactions are rapid, as indicated by the immediate
color change from violet to orange-red on addition of the
sulfenyl chloride to the complexes 3a and 3b, respectively.
The reactions are also very clean: only one peak was ob-
served in the HPLC analysis of the isolated products 4a and
4b (besides the solvent peak).
Scheme 3
These reactions could easily be followed by HPLC analy-
sis of the reaction mixtures since the retention times of 3a
and 3b are higher than those of all other components in
the mixture. Therefore, the corresponding peaks were well
separated. Single crystals of 3a and 3b could not be ob-
tained due to their instability in solution but the spectro-
scopic results (1H and 13C NMR, IR, Raman, UV/Vis) as
well as their reactivity towards SCl compounds support the
connectivities shown in Scheme 4 (see Exp. Sect.). In the 1H
NMR spectrum of 3a there appears one singlet each for the
Scheme 5
Both bis-trisulfanes 4a and 4b could be isolated in high
purity as grayish-white powders in yields of 42% and 41%,
respectively.
When we tried to synthesize the symmetrical bis-trisul-
fanes TrϪS3ϪRЈϪS3ϪTr by reaction of complexes 2a and
2b with two equivalents of TrSCl, according to Scheme 6,
rather complex reaction mixtures were obtained regardless
of whether the reaction was carried out in CS2, CH2Cl2 or
benzene at 20 °C.
Scheme 4
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V. M ünchow, R. Steudel
FULL PAPER
were obtained analogously in 67% and 26% yields, respec-
tively.
The
two
particularly
sulfur-rich
thiaalkanes
TrϪS3ϪRЈϪS4ϪRЈϪS3ϪTr (7a,b), mentioned above, were
obtained as pure materials by oxidation of complexes 3a
and 3b, respectively, with sulfuryl chloride in CS2 solution
at 20 °C (see Scheme 9; yields: 41% 7a, 45% 7b).
Scheme 6
The reaction times of more than 15 hours for complete,
or nearly complete, disappearance of the starting materials
evidently favor side reactions, for example a sulfur transfer
between the intermediate sulfanido complexes as shown in
Scheme 7.
Scheme 7
Scheme 9
As a consequence, three major thiaalkane products were
detected by HPLC analysis, namely the expected (TrS3)2RЈ,
the asymmetrical TrS3RЈS4Tr and the sulfur-rich
(TrS3RЈ)2S4. The latter product most probably arises from
the autoxidation of the intermediate Cp2TiCl(S2RЈS3Tr)
(see below). In addition, several minor products of similar
retention time were detected but not identified. The identifi-
cation of members of a homologous series is sometimes
possible by inter- and extrapolation of the retention indices
as they are linear functions of the sulfur content.[1,13] In
other cases the independent preparation of the suspected
species is necessary, and will be described below. Because
of the complex composition of the reaction mixture no
workup has been attempted since, even under an inert at-
mosphere, too many side-products were formed. Treatment
of complexes 2a and 2b with TrCl also did not give the
desired product (TrS2)2RЈ since the reaction rate at 20 °C
was very low, allowing parallel decomposition reactions.
More successful were the reactions of complexes 2a and
2b with the sulfur-rich derivatives TrSxCl with x ϭ 2 and 3
resulting in the bis-tetra- and -pentasulfanes 5a,b and 6a,b
(Scheme 8).
Alternatively, 7a could be obtained from 3a by autoxid-
ation with air in organic solvents at 20 °C (Scheme 10; yield
15%). Insoluble titanium-containing side products were ob-
served as an ochre precipitate.
Scheme 10
Even more sulfur-rich derivatives were obtained by cleav-
age of complexes 3a and 3b with SCl2 or S2Cl2 (Scheme 11),
resulting in the corresponding penta- and hexasulfanes 8a,b
and 9a,b (undecathia- and dodecathiaalkanes; yields:
19Ϫ36%).
Scheme 8
The starting materials TrSxCl were prepared according
to published procedures[14] and the reaction took place in
benzene at 20 °C. The reactivity of TrSxCl (x ϭ 0Ϫ3)
towards titanocene polysulfido complexes evidently in-
creases with increasing x. TrϪS4ϪCMe2ϪS4ϪTr (5a) was
Scheme 11
These grayish-white or yellowish powder-like substances
isolated in 7% yield as a champagne-colored powder of m.p. are soluble in methyl tert-butyl (MTB) ether.
55 °C while the cyclohexylidene derivative Finally, we observed that various sulfenyl chlorides
TrϪS4ϪC6H10ϪS4ϪTr (5b) melts at 60 °C (yield 34%). The (RSCl) and disulfane chlorides (RSSCl) react with the com-
corresponding bis-pentasulfanes TrϪS5ϪRЈϪS5ϪTr (6a,b) plexes 3a and 3b to give the corresponding thiaalkanes. For
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Sulfur-Rich Chain-like Thiaalkanes
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example, TrSSCl and 3b produced the heptathiaalkane termine RS values the sulfur homocycles Sx (x ϭ 6, 8, 9, 10)
TrϪS3ϪC6H10ϪS4ϪTr 10 (Scheme 12).
are used as reference substances and their retention times tR
are measured under the same conditions. Then, their ca-
pacity factors kЈ ϭ (tR Ϫ t0)/t0 are calculated (t0: dead
time), the logarithms of which depend linearly on the num-
ber of sulfur atoms (nS) as follows: ln kЈ ϭ a ϩ b ϫ nS. The
latter relationship can be used to calculate a formal nS value
for any other substance by substituting its kЈ value into this
equation. The formal nS value obtained in this way defines
the retention index of the novel substance as follows: RS ϭ
100 ϫ nS. From the RS values of three members of the
series TrϪSxϪCMe2ϪSxϪTr (x ϭ 3, 4, 5) the following lin-
ear regression has been derived: RS ϭ 568 ϩ 128 ϫ x (r ϭ
0.998). For the analogous cyclohexylidene species Tr-Sx-
C6H10-Sx-Tr we obtained: RS ϭ 662 ϩ 134 ϫ x (r ϭ 0.997).
These relationships can be used to estimate the retention
times of other members of these series by inter- and extra-
polation. Pure methanol was used as the eluent in both
cases.
Scheme 12
The easily accessible aromatic sulfenyl chlorides
ClC6H4SCl and C10H7SCl produced the symmetrical bis-
trisulfanes 11a,b and 12a,b in 6Ϫ28% yield on reaction with
complexes 2a and 2b (Scheme 13).
Considerably longer homologous series have been ob-
served for the species (TrS3CMe2)2Sx (x ϭ 4Ϫ11) and
(TrS3C6H10)2Sx (x ϭ 4Ϫ12). In these cases the linear re-
gressions are: RS ϭ 965 ϩ 60 ϫ x (r ϭ 0.9997) and RS ϭ
1147 ϩ 61 ϫ x (r ϭ 0.99986). The slopes of these functions
are practically identical. The higher members of these series
were prepared by reaction of complexes 3a and 3b with
solutions of chlorosulfanes SnCl2 (n Ͼ 2) obtained by
chlorination of elemental sulfur.[16]
Scheme 13
The NMR and vibrational spectra of the novel thiaalk-
anes mainly show the presence of the corresponding organic
General Properties of the Novel Thiaalkanes
The thiaalkanes prepared in this work can be stored for groups R and RЈ with little, if any, dependence on the num-
several weeks at 4 °C without decomposition. They are re- ber of sulfur atoms. Even the Raman spectra contain little
adily soluble in carbon disulfide, benzene and MTB ether, information about the SS bonds, the stretching vibrations
but less so in n-hexane, n-pentane and methanol. As with of which usually show up as strong lines in the 400Ϫ520
other polysulfanes,[1] heating initiates decomposition reac- cmϪ1 region. However, compared to the strongest lines of
tions. This can best be seen from the mass spectra of com- the organic substituents (e.g. Tr: 1002 cmϪ1, C10H7: 1380
pounds 11a,b and 12a,b, which are of the type cmϪ1), the SS stretching vibrations often gave rise to only
RϪS3ϪRЈϪS3ϪR. The temperatures required to evaporate relatively weak signals in the indicated region. Therefore,
these large molecules in a high vacuum (150Ϫ200 °C) result the Raman spectra have not been listed in the Exp. Sect.[17]
in complete decomposition, and no molecular ions were ob-
served. However, all major peaks in the EI mass spectra
could be assigned to cations of the following degradation
and interconversion products: R2Sn (n ϭ 0Ϫ4), RЈSm (m ϭ
1Ϫ5), RS3RЈ, RS2, RS, and related smaller fragments. Some
Summary
We have synthesized two new titanocene polysulfido
of these polysulfanes are known as pure compounds.[1] Evi- complexes Cp2TiCl(S2RЈS3Tr) and 17 novel chain-like
dently, the SϪS bonds break homolytically on heating and thiaalkanes by reaction of TiϪS bonds with SϪCl com-
the fragments recombine to form chain-like species R2Sn pounds (sulfenyl chlorides, sulfuryl chloride and sulfurchlo-
and cyclic polysulfanes RЈSm. The observation of R2, how- rides). The thiaalkanes are of types RϪSxϪRЈϪSyϪR (x,
ever, indicates that CϪS bonds are also broken on elec- y Ͼ 2) and R-SxϪRЈϪSyϪRЈϪSzϪR (x, z ϭ 3, y Ͼ 3) and
tron impact.
have been isolated in moderate to low yields as colorless,
During the HPLC analyses of the reaction mixtures it grayish-white or grayish-yellow powder-like substances
was once more observed that the retention time of the mem- (R ϭ CPh3, 4-ClC6H4; RЈ ϭ CMe2, 1,1-C6H10). To the best
bers of a homologous series, differing only in the number of our knowledge, these are the most sulfur-rich acyclic
of sulfur atoms, systematically depends on the number of thiaalkanes of these types ever prepared. It has previously
sulfur atoms. This can best be shown if the retention index been shown that polysulfido ligands coordinated to a ti-
(RS) is used which is independent of the chromatographic tanium atom can be utilized for ligand-transfer reactions
system and is therefore a characteristic property of these with SϪCl compounds and other metals can also function
compounds (similar to the NMR chemical shift).[15] To de- as coordination centers (e.g. Zn[18]). Since a large number
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Synthesis of 1-(4-Chlorophenyl)-3-{1-methyl-1-[(triphenylmethyl)-
trisulfanyl]ethyl}trisulfane (4a): A mixture of 4-ClC6H4SCl (1 mL)
and CS2 (49 mL) was used to titrate a solution of 3a (0.45 g,
0.68 mmol) in 50 mL of CS2 dropwise until the violet color had
changed to orange-red. After filtration the solution was shaken
with ca. 0.5 g of silica gel for a few minutes to remove residual
Cp2TiCl2 (color change to yellow).The gel was filtered off and
washed with CS2 (50 mL). Removal of the solvent produced an oil
which was dissolved in a mixture of MTB ether (5 mL) and n-
pentane (10 mL). The solvent was partly evaporated until a tur-
bidity appeared, whereupon the solution was cooled to Ϫ78 °C.
After decantation from the precipitated oil the solution was evapo-
rated in vacuo and the residue dissolved in MTB ether (5 mL) and
n-pentane (5 mL). Stepwise cooling of this solution to Ϫ50 °C pro-
duced a champagne-colored powder which was isolated and
washed with n-pentane (35 mL). Yield: 0.17 g (42%). M.p. 90Ϫ95
°C. C28H25ClS6 (589.4): calcd. C 57.06, H 4.28, S 32.65; found C
57.09, H 4.37, S 31.93. UV/Vis (methanol): λmax (%) ϭ 207 nm
(100), 238 (44), 277 (12), 316 (6). 1H NMR (CD2Cl2): δ ϭ 7.55
(dm, 2 H), 7.33 (m, 17 H), 1.69 (s, 6 H) ppm. 13C NMR (CD2Cl2):
δ ϭ 28.3, 64.9, 73.4, 127.3, 128.0, 129.3, 130.3, 131.9, 134.5, 135.6,
143.3 ppm. RS: 908.
of thiolate complexes of main group and transition metals
are known[19] the ligand-transfer method bears a tremen-
dous potential for further research in synthetic sulfur chem-
istry.
Experimental Section
General:[17] The reactions were carried out with exclusion of
moisture using carefully dried solvents. The chromatographic sys-
tem has been described previously (HPLC with UV absorbance
detector).[12] Octadecylsilane (C18) was used as the stationary
phase throughout and pure methanol as the eluent. The following
spectrometers were used: mass spectrometer AMD Intectra (based
on Varian MAT 311A equipment) with 70 eV electron energy;
NMR spectrometer WH 270 and ARX 200 by Bruker. FT-IR spec-
trometer Magna System 750 by Nicolet; Raman spectrometer
Ramanor U 1000 by Jobin Yvon, equipped with krypton ion laser
(647 nm), and FT-Raman spectrometer RFS 100 by Bruker with
Nd-YAG laser (1064 nm). UV/Vis diode array spectrometer 990 by
Waters (190Ϫ800 nm; on-line connected to the chromatographic
system). With one exception (12b) NMR spectra were recorded at
200 MHz. 13C NMR spectra are 1H broad-band decoupled.
Elemental analyses were performed using a HewlettϪPackard
CHN analyzer 185 as well as a PerkinϪElmer Series II CHNS ana-
lyzer 2400.
Synthesis
of
1-(4-Chlorophenyl)-3-{1-[(triphenylmethyltri)sul-
fanyl]cyclohexyl}trisulfane (4b): In analogy to the preparation of
4a, complex 3b (0.27 g, 0.39 mmol) was titrated. After removal of
the silica gel the solvent was evaporated in vacuo producing an oil
which was dissolved in a small amount of MTB ether followed by
partial evaporation of the solvent until a sticky foam had formed.
Upon addition of MTB ether (5 mL) this turned into a beige pow-
der. After addition of n-pentane (25 mL) and cooling to Ϫ50 °C
for 2 h a crystalline product was obtained which was filtered off
and washed with n-pentane. Yield: 0.10 g (41%). M.p. 162 °C.
C31H29ClS6 (629.4): calcd. C 59.16, H 4.64, S 30.57; found C 59.32,
H 4.86, S 29.25. UV/Vis (methanol): λmax (%) ϭ 207 nm (100), 238
(39), 278 (13), 315 (6). 1H NMR (CD2Cl2): δ ϭ 7.52 (dm, 2 H),
7.33 (m, 17 H), 1.2Ϫ2.2 (multiplets, 10 H) ppm. 13C NMR
(CD2Cl2): δ ϭ 23.0, 25.0, 35.4, 70.8, 75.3, 127.3, 128.1, 129.3,
130.4, 131.9, 134.4, 135.9, 143.3 ppm. RS: 1080.
Synthesis of Chloro(3,3-dimethyl-7,7,7-triphenyl-1,2,4,5,6-pentathia-
heptyl)titanocene (3a): TrSCl (1.75 g, 5.63 mmol) and 2a (1.57 g,
4.51 mmol) were stirred in benzene at 30Ϫ40 °C for 150 min. After
removal of the solvent in vacuo the residue was dissolved in CS2
(30 mL), n-pentane (70 mL) was added and the solution was cooled
to Ϫ26 °C whereupon a mixture of 3a and Cp2TiCl2 (ca. 10%)
crystallized out, which was isolated, washed with n-pentane
(30 mL) and dried in air (red-blue powder). Yield: 2.4 g (2.16 g of
pure 3a, 73%). The Cp2TiCl2 can be removed by stirring the solu-
tion with silica gel but the yield is then dramatically lower. M.p.
(dec.): 133 °C. C32H31ClS5Ti (659.3): calcd. C 57.29, H 4.72, S
21.89 (Cp2TiCl2 content taken into account); found C 55.33, H
4.72, S 22.21. The low carbon value is explained by titanium car-
bide formation on combustion in the CHN analyzer. UV/Vis
(methanol): λmax (%) ϭ 223 nm (100), 241 (87), 295 (23), 382 (7),
556 (9). 1H NMR (CD2Cl2): δ ϭ 7.32 (m, 15 H), 6.36 (s, 10 H),
1.69 (s, 6 H) ppm. Retention index (RS): 570.
Synthesis of 1-{1-Methyl-1-[(triphenylmethyl)tetrasulfanyl]ethyl}-3-
(triphenylmethyl)tetrasulfane (5a): Solid TrSSCl (1.50 g, 4.37 mmol)
was added in portions and with stirring to a solution of 2a (0.76 g,
2.18 mmol) in benzene (100 mL). Stirring for 30 min resulted in a
color change to red. After evaporation of the solvent the residue
was dissolved in CH2Cl2 (50 mL) and shaken with some silica gel
(5 min). After filtration and evaporation of the solvent the residue
was recrystallized from a CS2/n-pentane mixture (5:25). Yield:
0.12 g (7%). M.p.: 55 °C. C41H36S8 (785.3): calcd. C 62.71, H 4.62,
S 32.67; found C 62.95, H 4.85, S 33.03. UV/Vis (methanol): λmax
(%) ϭ 231 nm (100), 301 (22). 1H NMR (CDCl3): δ ϭ 7.30 (m),
1.58 (s) ppm. 13C NMR (CDCl3): δ ϭ 29.0, 64.3, 73.7, 127.3, 128.0,
130.3, 143.0 ppm. RS: 1071.
Synthesis of Chloro(3-cyclohexylidene-7,7,7-triphenyl-1,2,4,5,6-
pentathiaheptyl)titanocene (3b): TrSCl (1.00 g, 3.22 mmol) and 2b
(1.00 g, 2.57 mmol) were stirred in benzene at 30Ϫ40 °C for
180 min. After removal of the solvent in vacuo the residue was
dissolved in CS2 (20 mL), n-pentane (60 mL) was added and the
solution was cooled to Ϫ26 °C for 15 h, whereupon a mixture of
3a and Cp2TiCl2 (ca. 10%) crystallized out, which was isolated,
washed with n-pentane (40 mL) and dried in air (red-blue powder).
Yield: 0.77 g (0.69 g of pure 3b, 39%). The Cp2TiCl2 can be re-
moved by stirring the solution with silica gel but the yield is then
dramatically lower. M.p. (dec.): 95Ϫ100 °C. C35H35ClS5Ti (699.3):
calcd. C 58.92, H 4.94, S 20.64 (Cp2TiCl2 content taken into ac-
Synthesis
of
1-(Triphenylmethyl)-3-{1-[(triphenylmethyl)tetra-
sulfanyl]cyclohexyl}tetrasulfane (5b): Preparation in analogy to the
synthesis of 5a from complex 2b (0.25 g, 0.64 mmol), TrSSCl
(0.44 g, 1.29 mmol) in benzene (30 mL) and using less CH2Cl2
(20 mL). Yield: 0.18 g (34%). M.p.: 60 °C. C44H40S8 (825.3): calcd.
count); found C 58.42, H 4.64, S 18.72. UV/Vis (methanol): λmax C 64.03, H 4.89, S 31.08; found C 64.03, H 4.95, S 30.25. UV/Vis
(%) ϭ 209 nm (100), 240 (49), 288 (15), 383 (4), 564 (7). H NMR (methanol): λmax (%) ϭ 217 nm (100), 261 (22), 305 (13). 1H NMR
1
(CD2Cl2): δ ϭ 7.32 (m, 15 H), 6.37 (s, 10 H), 1.2Ϫ2.2 (multiplets,
(CDCl3): δ ϭ 7.34 (m), 1.2Ϫ2.3 (multiplets) ppm. 13C NMR
10 H) ppm. 13C NMR (CD2Cl2): δ ϭ 23.0, 24.9, 35.4, 71.5, 73.3, (CDCl3): δ ϭ 22.7, 24.8, 26.9, 35.6, 70.4, 73.6, 127.2, 128.0, 130.2,
115.9, 127.2, 128.0, 130.4, 143.5 ppm. RS: 686.
722
143.0 ppm. RS: 1186.
 2004 Wiley-VCH Verlag GmbH & Co. KGaA, Weinheim
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Eur. J. Inorg. Chem. 2004, 718Ϫ725

Sulfur-Rich Chain-like Thiaalkanes
Synthesis of 1-{1-Methyl-1-[(triphenylmethyl)pentasulfanyl]ethyl}-3- evaporation of the solvent a champagne-colored powder was ob-
FULL PAPER
(triphenylmethyl)pentasulfane (6a): Solid 2a (0.18 g, 0.52 mmol) was
tained. Yield: 0.24 g (45%). M.p.: 60 °C. C50H50S10 (971.6): calcd.
added in small portions with stirring to TrSSSCl (0.40 g,
1.07 mmol) in benzene (25 mL). After 10 min the solvent was eva- (%) ϭ 208 nm (100), 297 (7). H NMR (CD2Cl2): δ ϭ 7.31 (m, 30
C 61.81, H 5.19; found C 59.93, H 5.47. UV/Vis (methanol): λmax
1
porated, the residue was dissolved in CH2Cl2 (20 mL) and shaken
with ca. 0.1 g of silica gel for a few minutes to remove Cp2TiCl2.
After filtration and partial evaporation of the solvent excess n-pen-
tane was added followed by complete evaporation of the solvent.
The grayish-white residue was recrystallized from n-pentane. Yield:
0.30 g (67%). M.p.: 50 °C. C41H36S10 (849.4): calcd. C 57.98, H
4.27; found C 58.51, H 3.75. UV/Vis (methanol): λmax (%) ϭ
240 nm (100), 294 (41). 1H NMR (CD2Cl2): δ ϭ 7.33 (m, 30 H),
1.71 (s, 6 H) ppm. 13C NMR (CDCl3): δ ϭ 28.9, 64.8, 73.9, 127.3,
128.0, 130.3, 142.9 ppm. RS: 1212.
H), 1.2Ϫ2.2 (multiplets, 20 H) ppm. 13C NMR (CD2Cl2): δ ϭ 23.0,
25.0, 35.7, 70.8, 73.3, 127.3, 128.1, 130.4, 143.3 ppm. RS: 1397.
Synthesis of Bis{1-methyl-1-[(triphenylmethyl)trisulfanyl]ethyl}-
pentasulfane (8a): A solution of SCl2 (1 mL) in CS2 (50 mL) was
added dropwise and with stirring to a solution of 3a (0.90 g,
1.37 mmol) in CS2 (80 mL) until the color had changed from blue
to red-orange. After filtration some silica gel was added with stir-
ring. The solid was filtered off and washed with CS2 (20 mL). The
solvent of the combined solutions was evaporated and the oily resi-
due dissolved in MTB ether (25 mL). Cooling yielded a precipitate
which was isolated and dissolved again in MTB ether. Removal of
the solvent produced a beige powder. Yield: 0.20 g (32%). M.p.: 52
°C. C44H42S11 (923.5): calcd. C 57.22, H 4.58, S 38.19; found C
57.42, H 4.88, S 37.31. UV/Vis (methanol): λmax (%) ϭ 212 nm
Synthesis of 1-(Triphenylmethyl)-3-{1-[(triphenylmethyl)pentasul-
fanyl]cyclohexyl}pentasulfane (6b): TrSSSCl (0.48 g, 1.28 mmol)
was added in small portions with stirring to complex 2b (0.25 g,
0.64 mmol) in benzene (30 mL). After 10 min the solvent was re-
moved in vacuo, the residue dissolved in CH2Cl2 (20 mL) and
shaken with some silica gel until the color had changed to yellow.
After filtration and evaporation of the solvent the crude product
was recrystallized twice from a CS2/n-pentane mixture (5:25 mL)
by cooling to Ϫ78 °C. Yield: 0.15 g (26%). M.p.: 60 °C. C44H40S10
(889.5): calcd. C 59.42, H 4.53, S 36.05; found C 60.14, H 4.60, S
34.26. UV/Vis (methanol): λmax (%) ϭ 209 nm (100), 263 (19), 298
1
(100), 297 (9). H NMR (CD2Cl2): δ ϭ 7.34 (m, 30 H), 1.74 s, 12
H) ppm. 13C NMR (CD2Cl2): δ ϭ 28.6, 65.0, 73.6, 127.3, 128.1,
130.0, 143.3 ppm. RS: 1252.
Synthesis of Bis{1-[(triphenylmethyl)trisulfanyl]cyclohexyl}penta-
sulfane (8b): Preparation in analogy to 8a from complex 3b (0.83 g,
1.19 mmol). Yield: 0.14 g (23%). M.p.: 58 °C. C50H50S11 (1003.67):
calcd. C 59.84, H 5.02, S 35.14; found C 59.30, H 4.75, S 33.94.
UV/Vis (methanol): λmax (%) ϭ 208 nm (100), 297 (8). 1H NMR
1
(11). H NMR (CDCl3): δ ϭ 7.28 (m), 1.2Ϫ2.1 (multiplets) ppm.
13C NMR (CDCl3): δ ϭ 22.8, 24.8, 35.4, 70.9, 73.8, 127.3, 128.0,
(CD2Cl2): δ ϭ 7.32 (m, 30 H), 1.2Ϫ2.3 (multiplets, 20 H) ppm. 13
C
130.3, 143.0 ppm. RS: 1338.
NMR (CD2Cl2): δ ϭ 23.0, 25.0, 35.6, 70.9, 75.3, 127.3, 128.1,
Synthesis of Bis{1-methyl-1-[(triphenylmethyl)trisulfanyl]ethyl}-
tetrasulfane (7a). Method A: A solution of 0.61 mL of SO2Cl2 in
9.4 mL of benzene was added rapidly but dropwise to complex 3a
(0.90 g, 1.37 mmol) in CS2 (80 mL) until the color had changed
from purple to orange-red. After filtration the solution was shaken
with some silica gel to remove residual Cp2TiCl2. Filtration and
evaporation of the solvent yielded a yellow oil which was dissolved
in MTB ether (30 mL). Cooling to Ϫ78 °C gave an oily residue
which was dissolved again in MTB ether and the solvent evapo-
rated again. Yield: 0.25 g (41%).
Method B: Complex 3a (0.41 g, 0.59 mmol) was dissolved in a mix-
ture of benzene (150 mL), CS2 (75 mL) and CH2Cl2 (25 mL) and
stirred for 3 days resulting in a red-brown solution and an ochre
precipitate. The filtered solution was stirred with little silica gel for
5 min. and this was then filtered off and washed with CS2 (25 mL).
Evaporation of the solvent gave an oily residue which was dissolved
in a mixture of CH2Cl2 (3 mL), n-pentane (6 mL) and ethanol
(15 mL). On cooling to Ϫ78 °C the product precipitated as a beige
powder. Yield: 0.04 g (15%).%). M.p.: 54 °C. C44H42S10 (891.5):
calcd. C 59.28, H 4.75, S 35.97; found C 58.91, H 4.97, S 36.41.
UV/Vis (methanol): λmax (%) ϭ 213 nm (100), 297 (9). 1H NMR
(CD2Cl2): δ ϭ 7.31 (m, 30 H), 1.71 (s, 12 H) ppm. 13C NMR
(CD2Cl2): δ ϭ 28.6, 64.8, 73.1, 127.3, 128.0, 130.3, 143.3 ppm.
RS: 1217.
130.3, 143.3 ppm. RS: 1451.
Synthesis of Bis{1-methyl-1-[(triphenylmethyl)trisulfanyl]ethyl}-
hexasulfane (9a): A solution of S2Cl2 (1 mL) in CS2 (50 mL) was
added dropwise and with stirring to a solution of 3a (0.81 g,
1.23 mmol) in CS2 (80 mL) until the color had changed from violet
to orange-red. After stirring for 5 min the precipitated Cp2TiCl2
was filtered off and the filtrate was shaken with a small amount of
silica gel for 5 min. The solids were filtered off and washed with
CS2 (50 mL); the combined filtrates were evaporated and the re-
sulting oil was dissolved in a mixture of MTB ether and CS2
(40:5 mL). Evaporation of the solvent gave a foam-like product
which was pulverized, dissolved in CS2/ethanol/MTB ether
(10:10:5 mL) and cooled to Ϫ78 °C. Most of the solvents (CS2
and ether) were removed on a rotary evaporator and the ethanolic
solution was decanted off from the oily product. The latter was
mixed with CH2Cl2/n-hexane/ethanol (7:20:20) and cooled to Ϫ78
°C whereupon a sticky precipitate was obtained. This was isolated,
dissolved in a CH2Cl2/n-hexane/ethanol (7:20:10) mixture and this
was cooled to Ϫ78 °C, resulting in a solid precipitate. Yield: 0.11 g
(19%). M.p.: 55 °C. C44H42S12 (955.6): calcd. C 55.30, H 4.43, S
40.27; found C 54.78, H 4.71, S 41.29. UV/Vis (methanol): λmax
(%) ϭ 216 nm (100), 297 (12). 1H NMR (CD2Cl2): δ ϭ 7.32 (m,
30 H), 1.73 (s, 12 H) ppm. 13C NMR (CD2Cl2): δ ϭ 28.6, 65.0,
73.4, 127.3, 128.0, 130.3, 143.3 ppm. RS: 1334.
Synthesis of Bis{1-methyl-1-[(triphenylmethyl)trisulfanyl]cyclo-
hexyl}tetrasulfane (7b): Preparation in analogy to 7a (method A)
Synthesis
of
Bis{1-[(triphenylmethyl)trisulfanyl]cyclohexyl}-
from 3b (0.77 g, 1.10 mmol) in 80 mL of benzene. After the color hexasulfane (9b): Preparation in analogy to 9a from complex 3b
change from purple to orange-red the solvent was evaporated, the
residue dissolved in 50 mL CS2 and stirred with some silica gel.
The solution was filtered and the residue washed with 20 mL of
CH2Cl2. Evaporation of the solvent resulted in an oil which was
(0.72 g, 1.03 mmol) in 100 mL of CS2 by titration with sulfur di-
chloride. Cp2TiCl2 was filtered off and the solution stirred with
some silica gel which was then filtered off and the residue washed
with 20 mL of CS2. The solvent was evaporated and the remaining
dissolved in a mixture of 10 mL of CH2Cl2 and 50 mL of MTB oil dissolved in a mixture of 5 mL of CS2 and 20 mL of MTB ether.
ether. At Ϫ78 °C an oil precipitated which was isolated by decan- The solvents were evaporated until a turbidity appeared. Cooling
tation and dissolved in 50 mL of MTB ether. After complete to Ϫ78 °C resulted in a precipitate which was dissolved in 20 mL
Eur. J. Inorg. Chem. 2004, 718Ϫ725
www.eurjic.org
 2004 Wiley-VCH Verlag GmbH & Co. KGaA, Weinheim
723

V. M ünchow, R. Steudel
FULL PAPER
of MTB ether. Complete evaporation of the ether yielded a white
tration some silica gel was added to remove dissolved Cp2TiCl2
powder. Yield: 0.19 g (36%). M.p.: 55 °C. C50H50S12 (1035.7): calcd. and this was then filtered off and washed with CS2 (10 mL). The
C 57.98, H 4.87, S 37.15; found C 57.30, H 5.23, S 37.65. UV/Vis
combined solutions were evaporated and the oily residue was dis-
solved in MTB ether in an ultrasound bath. Cooling of the solution
to Ϫ50 °C gave a white powder which was isolated and dried in
(methanol): λmax (%) ϭ 208 nm (100), 297 (10). 1H NMR
(CD2Cl2): δ ϭ 7.33 (m, 30 H), 1.3Ϫ2.3 (multiplets, 20 H) ppm. 13
C
NMR (CD2Cl2): δ ϭ 23.0, 25.0, 35.5, 71.0, 73.3, 127.3, 128.1, air. Yield: 0.04 g (13%). M.p.: 55Ϫ57 °C. C23H20S6 (488.8): calcd.
130.3, 143.3 ppm. RS: 1540.
C 56.52, H 4.12, S 39.36; found C 55.98, H 4.61, S 38.20. UV/Vis
(methanol): λmax (%) ϭ 216 nm (85), 237 (100), 278 (28), 311 (15).
MS (200 °C): m/z (%) ϭ 382 (4), 350 (67), 318 (38), 286 (35), 265
(6), 254 (23), 234 (26), 202 (45), 191 (88), 170 (66), 159 (68), 138
(37), 128 (19), 115 (100), 106 (46). 1H NMR (400 MHz, CDCl3):
Synthesis of 1-(Triphenylmethyl)-3-{1-[(triphenylmethyl)trisulfanyl]-
cyclohexyl}tetrasulfane (10): TrSSCl (0.22 g, 0.64 mmol) was added
in portions to a solution of 3b (0.45 g, 0.64 mmol) in benzene
(60 mL) until the color had changed from violet to orange-red.
After evaporation of the solvent the residue was dissolved in CS2
(50 mL) and stirred with some silica gel for 5 min. After filtration
and washing the solid with CS2 (10 mL) the combined solutions
were partly evaporated. Some MTB ether and ethanol were added
until a turbidity appeared, whereupon the mixture was cooled to
Ϫ50 °C. The precipitated oil was isolated by decantation and dis-
solved in a small amount of CS2 and excess MTB ether. The sol-
vents were evaporated on a rotary evaporator until a foam ap-
peared which was dried in vacuo (beige powder). Yield: 0.04 g (8%).
M.p.: 60 °C. C44H40S7 (793.3): calcd. C 66.62, H 5.08, S 28.30;
found C 66.43, H 5.33, S 27.62. UV/Vis (methanol): λmax (%) ϭ
δ ϭ 8.05 (d, Jmeta ϭ 1.9 Hz, 2 H), 7.84 (m, 6 H), 7.67 (dd, Jortho
ϭ
8.6 Hz, Jmeta ϭ 1.9 Hz, 2 H), 7.52 (m, 4 H), 1.78 (s, 6 H) ppm.
RS: 952.
Synthesis
of
1-(2-Naphthyl)-3-{1-[(2-naphthyl)trisulfanyl]-
cyclohexyl}trisulfane (12b): Preparation in analogy to 12a from 3b
(0.35 g, 0.90 mmol) and C10H7SCl (0.35 g, 1.80 mmol). After dis-
solution in MTB ether a little ethanol and n-pentane were added
and the volume was reduced in vacuo until a turbidity appeared.
Stepwise cooling to Ϫ50 °C for precipitation and recrystallization
from an MTB ether/n-hexane mixture with addition of a little etha-
nol to initiate the precipitation. Grayish-white powder. Yield: 0.09 g
(19%). M.p.: 55Ϫ60 °C. C26H24S6 (528.9): calcd. C 59.05, H 4.57,
S 36.38; found C 58.26, H 4.18, S 35.66. UV/Vis (methanol): λmax
(%) ϭ 216 nm (83), 238 (199), 277 (28), 309 (16). MS (160 °C):
m/z (%) ϭ 382 (3), 368 (10), 350 (58), 336 (48), 318 (21), 286 (26),
1
207 nm (100), 267 (10), 298 (5). H NMR (CDCl3): δ ϭ 7.30 (m,
30 H), 1.2Ϫ2.1 (multiplets, 10 H) ppm. 13C NMR (CDCl3): δ ϭ
22.78, 24.87, 35.28, 70.33, 73.15, 73.63, 127.16, 127.24, 127.97,
128.02, 130.33, 130.37, 143.12, 143.30 ppm. RS: 1125.
1
272 (21), 254 (9), 242 (15), 210 (34), 191 (100), 178 (19). H NMR
Synthesis of 3-(4-Chlorophenyl)-1-{1-methyl-1-[(4-chlorophenyl)tri-
sulfanyl]ethyl}trisulfane (11a): Under nitrogen,
(CD2Cl2): δ ϭ 8.06 (d, Jmeta ϭ 1.9 Hz, 2 H), 7.84 (m, 6 H), 7.69
(dd, Jortho ϭ 8.6 Hz, Jmeta ϭ 1.9 Hz, 2 H), 7.53 (m, 4 H), multiplets:
2.08Ϫ2.13 (4 H), 1.54Ϫ1.65 (4 H), 1.31Ϫ1.40 (2 H) ppm. 13C NMR
(CD2Cl2): δ ϭ 22.93, 24.78, 35.47, 71.04, 126.80, 126.90, 127.68,
127.72, 127.78, 129.08, 129.54, 132.92, 133.36, 134.21 ppm. RS:
1070.
a solution of
ClC6H4SCl (0.50 g, 2.79 mmol) in CS2 (10 mL) was added dropwise
to complex 3a (0.49 g, 1.41 mmol) in CS2 (40 mL). Cp2TiCl2 was
removed by filtration and stirring with a small amount of silica gel.
The resulting clear solution was reduced to 5 mL, mixed with a
little n-pentane and cooled to Ϫ78 °C. The precipitated beige pow-
der was isolated and washed with n-pentane. Yield: 0.18 g (28%).
M.p.: 49Ϫ54 °C. C15H14Cl2S6 (457.6): calcd. C 39.37, H 3.08, S Acknowledgments
42.05; found C 39.15, H 2.89, S 41.87. UV/Vis (methanol): λmax
We are grateful to Dr. Yana Steudel for assistance with the graphics
and the nomenclature. This work has been supported by the
Deutsche Forschungsgemeinschaft.
(%) ϭ 214 nm (86), 241 (100), 275 (36), 306 (23). MS (150 °C): m/
z (%) ϭ 350 (1), 318 (17), 286 (73), 249 (21), 222 (9), 175 (45), 143
(100). 1H NMR (CDCl3): δ ϭ 7.53 (dm, 4 H), 7.34 (dm, 4 H), 1.78
(s, 6 H) ppm. 13C NMR (CDCl3): δ ϭ 28.5, 65.1, 129.3, 131.8,
134.7, 135.3 ppm. RS: 805.
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Synthesis of 1-(4-Chlorophenyl)-3-{1-[(4-chlorophenyl)trisulfanyl]-
cyclohexyl}trisulfane (11b): Under an atmosphere of nitrogen, a
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°C. C18H18Cl2S6 (497.6): calcd. C 43.44, H 3.65, S 38.66; found C
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(100), 241 (82), 277 (27), 304 (19). MS (180 °C): m/z (%) ϭ 350 (2),
318 (20), 289 (43), 286 (34), 254 (4), 222 (6), 210 (19), 178 (13), 175
(64), 145 (82), 143 (78), 114 (63), 108 (47), 81 (100). 1H NMR
(CDCl3): δ ϭ 7.53 (dm, 4 H), 7.33 (dm, 4 H), 1.3Ϫ2.2 (multiplets,
10 H) ppm. RS: 956.
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to 3a (0.20 g, 0.57 mmol) in CS2 (50 mL) with stirring. After fil-
724
 2004 Wiley-VCH Verlag GmbH & Co. KGaA, Weinheim
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Eur. J. Inorg. Chem. 2004, 718Ϫ725

Sulfur-Rich Chain-like Thiaalkanes
FULL PAPER
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Received August 22, 2003
Early View Article
Published Online December 12, 2003
Eur. J. Inorg. Chem. 2004, 718Ϫ725
www.eurjic.org
 2004 Wiley-VCH Verlag GmbH & Co. KGaA, Weinheim
725