Reactions of 1,2,4-Trithiolane and its 4-S-Oxide with diphosphane Pt 0 complexes

Article abstract of DOI:10.1002/ejic.200901229

Reactions of 1,2,4-trithiolanes with Pt⁰ complexes often proceed via an oxidative addition of the Pt⁰ complex fragment into the S-S bond and subsequent extrusion of a thioketone molecule by ring contraction. The six-membered intermediate 5a, formed in the course of the reaction of the parent 1,2,4-trithiolane (1a) and Pt0 complex 4, was detected by means of low-temperature NMR spectroscopy. Stable derivatives of this type (compounds 9, 11 and 12) were isolated either by using (dppe)Pt⁰ complex 8 or 1,2,4-trithiolane 4-Soxide (10). The molecular structures of platinum complexes 9, 11 and 12, as well as their unexpected stability, are discussed.

Full text of DOI:10.1002/ejic.200901229

FULL PAPER
DOI: 10.1002/ejic.200901229
Reactions of 1,2,4-Trithiolane and Its 4-S-Oxide with Diphosphane Pt0
Complexes
Holm Petzold,*[a,b] Thomas Weisheit,[a] Silvio Bräutigam,[a] Helmar Görls,[a]
Grzegorz Mloston,*[c] and Wolfgang Weigand*[a]
Dedicated to Professor Rolf Huisgen on the occasion of his 90th birthday
Keywords: 1,2,4-Trithiolanes / S ligands / Oxidative addition / Metallacycles / Reactive intermediates
Reactions of 1,2,4-trithiolanes with Pt0 complexes often pro-
ceed via an oxidative addition of the Pt0 complex fragment
into the S–S bond and subsequent extrusion of a thioketone
molecule by ring contraction. The six-membered intermedi-
ate 5a, formed in the course of the reaction of the parent
1,2,4-trithiolane (1a) and Pt0 complex 4, was detected by
means of low-temperature NMR spectroscopy. Stable deriva-
tives of this type (compounds 9, 11 and 12) were isolated
either by using (dppe)Pt0 complex 8 or 1,2,4-trithiolane 4-S-
oxide (10). The molecular structures of platinum complexes
9, 11 and 12, as well as their unexpected stability, are dis-
cussed.
In a recent paper, generation of parent thiosulfine 3a
from 1,2,4-trithiolane (1a) in the gas phase was reported.[2a]
The highly reactive intermediate 3a was frozen in an argon
matrix at 10 K and studied by means of spectroscopic meth-
ods (IR and UV/Vis spectroscopy). In addition, 3a was
transformed reversibly into the parent dithiirane H2C-
(-S-S-) by selective irradiation with UV light.[2a] Extension
of this method to 3,3,5,5-tetramethyl-1,2,4-trithiolane (1b)
revealed a smooth 1,4-H-shift in thiosulfine 3b containing
H-atoms at the β-position.[3] In another case, the gas-phase
thermolysis of a 1,2,4-trithiolane bearing two spiro-cyclo-
butanone rings at C(3) and C(5) yielded the ring-enlarged
isomeric dithiolactone after the rearrangement of the ini-
tially formed dithiirane.[4] These results are in good agree-
ment with the initially postulated course of thiosulfine re-
arrangement,[5] subsequently confirmed by calculations.[1a]
In addition to 1,2,4-trithiolane (1a), its regioisomers 1-S-
oxide and 4-S-oxide were also studied in the gas phase. In
both cases, thioformaldehyde S-oxide was found amongst
the major products.[2b]
Introduction
1,2,4-Trithiolanes with the general structure 1 belong to
the class of sulfur-rich heterocycles that are widely used as
convenient precursors for the generation of the elusive
thiosulfines (thiocarbonyl S-sulfides) 3.[1] Along with other
intermediates of this type (thiocarbonyl ylides, thiocarbonyl
S-oxides, thiocarbonyl S-imides, etc.) derived from thio-
ketones 2, they are considered to be so-called “sulfur-
centred” 1,3-dipoles.[1a] Huisgen and co-workers found that
3,3,5,5-tetraphenyl-1,2,4-trithiolane (1c) easily undergoes
thermal [3+2]-cycloreversion (refluxing CHCl3) to yield
thiobenzophenone (2c) and diphenylthiosulfine (3c)
(Scheme 1).[1b]
Scheme 1. Thermal [3+2]-cycloreversion of 1,2,4-trithiolanes 1a–c.
In a series of papers, we have shown that 3,3,5,5-tetra-
phenyl-1,2,4-trithiolane (1c) reacts with [Pt(PPh3)2(η2-
[a] Institut für Anorganische und Analytische Chemie, Friedrich- C2H4)] (4a) to yield a 1:1 mixture of thiobenzophenone
complex 6c and dithiolato complex 7c.[6] The mechanism of
Schiller-Universität Jena,
August-Bebel-Str. 2, 07743 Jena, Germany
this reaction is not fully understood yet, but it seems likely
that the conversion is initiated by the oxidative addition of
the [Pt0(PPh3)2] fragment into the sulfur–sulfur bond to
form an unstable six-membered platinacycle 5c.[6–8] Com-
pound 5c subsequently splits into 7c and thiobenzophenone
(2c), which then captures an additional equivalent of 4a to
afford complex 6c (Scheme 2). The course of the reaction
Fax: +49-3641-948102
E-mail: wolfgang.weigand@uni-jena.de
[b] Institut für Chemie, TU-Chemnitz,
Strasse der Nationen 62, 09111 Chemnitz, Germany
[c] Department of Organic and Applied Chemistry, University of
Lodz,
Tamka 12, 91-403 Lodz, Poland
Supporting information for this article is available on the
WWW under http://dx.doi.org/10.1002/ejic.200901229.
3636
© 2010 Wiley-VCH Verlag GmbH & Co. KGaA, Weinheim
Eur. J. Inorg. Chem. 2010, 3636–3641

Reactions of 1,2,4-Trithiolane and Its 4-S-Oxide with Pt0 Diphosphanes
4
1
depends on the phosphanes used for the preparation of 43.4 Hz and J(P,H) = 1.7 Hz], at δ = 5.54 ppm in the H
complexes of type 4. In the case of complexes containing a NMR spectrum. The AB spin system points to formation
diphosphane unit exhibiting a small P–Pt–P angle, the reac- of thioformaldehyde complex 6a, and the observed cou-
tion proceeds via [3+2]-cycloreversion of 1c as the slowest, pling constant fits well with other thiocarbonyl complexes
1
rate-determining step.[9] In general, the oxidative addition of this type.[6,8,9,12] The H NMR spectrum shows a singlet
2
of Pt0 complex fragments into the S–S bond of sulfur-rich at δ = 3.44 ppm with J(Pt,H) = 46.0 Hz.
heterocycles is attracting increasing interest with respect to
In order to gain more information on the structure of
the synthesis of thiolato, sulfenato and sulfinato com- the transient complex, related to the singlet localized at δ =
plexes.[7–10] In a recent paper, we showed that the reaction 22.7 ppm, Pt0 complex 8 was treated with 1a. After one
of [Pt(PPh3)2(η2-nb)] (4b) (nb = norbornene) with 3,5-(bis- hour at room temperature, the formation of a new product
spiro)cyclohexyl-1,2,4-trithiolane and its 1-S-oxide and 4-S- was detected by means of TLC. The 31P NMR spectrum
oxide regioisomers gives equimolar mixtures of dithiolato/ exhibits an A2 system localized at δ = 48.1 ppm with char-
thioketone, thiolato-sulfenato/thioketone and dithiolato/ acteristic 195Pt satellites [1J(Pt,P) = 2757 Hz]. Interestingly,
sulfine complexes, respectively.[8]
in the 1H NMR spectrum a doublet at δ = 4.35 ppm
[4J(P,H) = 8.4 Hz, 3J(Pt,H) = 54 Hz, 4 H], attributed to two
equivalent CH2 units, was also found. Elemental analysis
and single-crystal X-ray diffraction confirmed the structure
of complex 9 (Tables 1 and 2, Scheme 3). Unfortunately,
complex 9 is disordered around S(2) in the solid state, and
therefore bond lengths in that part of the molecule could
not be determined precisely (Figure 1).
Table 1. Selected bond lengths [Å] and bond angles [°] for com-
plexes 9, 11 and 12.
Complex
9[a]
11
12
Scheme 2. Reaction of 1,2,4-trithiolanes with [Pt(PPh3)2(η2-olefin)]
(olefin = C2H4 or nb) (4a,b).
Pt–P(1)
Pt–P(2)
Pt–S(1)
Pt–S(3)
S(1)–C(1)
C(1)–S(2)
S(2)–C(2)
C(2)–S(3)
2.2475(14)
2.2458(14)
2.3365(15)
2.3474(16)
2.2961(15)
2.2897(14)
2.3279(15)
2.3537(15)
1.830(7)
1.798(7)
1.824(7)
1.783(7)
1.493(5)
97.25(5)
90.82(5)
175.78(6)
174.58(5)
88.14(5)
83.85(5)
107.7(2)
112.1(4)
97.4(3)
2.2546(18)
2.2476(19)
2.3380(19)
2.347(2)
1.812(8)
1.796(8)
1.832(8)
1.772(9)
1.481(6)
86.02(7)
92.92(7)
175.66(8)
174.51(7)
89.49(7)
91.77(7)
105.9(3)
110.9(4)
99.0(4)
The aim of the present work was the synthesis and char-
acterization of platinacycles of type 5 derived from the par-
ent 1,2,4-trithiolane (1a) and its 4-S-oxide 10, which are
postulated to appear as initial intermediates in the reaction
pathway.
S(2)–O(1)
––
P(1)–Pt–P(2)
S(1)–Pt–S(3)
P(1)–Pt–S(3)
P(2)–Pt–S(1)
P(1)–Pt–S(1)
P(2)–Pt–S(3)
Pt–S(1)–C(1)
S(1)–C(1)–S(2)
C(1)–S(2)–C(2)
S(2)–C(2)–S(3)
C(2)–S(3)–Pt
86.49(5)
93.71(6)
175.57(5)
172.56(5)
89.85(5)
90.26(6)
Results and Discussion
Pt0 complexes, [PtL2(η2-C2H4)] (4a), [PtL2(η2-nb)] (4b)
(L
=
PPh3) and [PtL2(olefin)] (8) (L
=
1/2
Ph2PCH2CH2PPh2, olefin = C2H4) were treated with 1,2,4-
trithiolane (1a) or its 4-S-oxide 10.
Reaction of the parent 1,2,4-trithiolane (1a) with Pt0
complex 4b was performed in [D8]toluene at low tempera-
ture in an NMR tube. Shortly after 1a and 4b were mixed
at –50 °C, the recorded spectra showed only signals of the
starting compounds. After a few minutes, and warming to
–10 °C, a new, weak signal appeared in the 31P NMR spec-
trum at δ = 22.7 ppm. Further warming of the solution to
22 °C resulted in a higher intensity of this signal and the
appearance of the characteristic 195Pt satellites [1J(P,Pt) =
2825 Hz]. Other new signals corresponding to an AB spin
system [δ = 24.9/27.9 ppm, 1J(P,Pt) = 3311/4348 Hz, 2J(P,P)
120.6(4)
104.4(3)
121.5(5)
105.3(3)
[a] C(1), S(2) and C(2) are disordered.
Scheme 3. Ring enlargement of 1,2,4-trithiolane (1a) after treat-
ment with [Pt(dppe)(η2-C2H4)] (8).
1
= 17 Hz] as well as an A2 system [δ = 21.5 ppm, J(P,Pt) =
2890 Hz] were observed at 25 °C. The intensity of the signal
Complex 9 is stable at room temperature and does not
localized at δ = 22.7 ppm decreased further after one day at extrude thioformaldehyde. On the basis of 31P NMR spec-
25 °C, and the two new spin systems became more intense. troscopic data, we assumed that in the reaction of 1a with
The signal at δ = 21.5 ppm was assigned to the known 4b the corresponding platinacycle 5a [δ = 22.7 ppm, 1J(P,Pt)
dithiolato complex 7a.[11] In addition, this complex shows = 2825 Hz] would be formed analogously, but it spontane-
a characteristic triplet, with 195Pt satellites [3J(Pt,H) = ously eliminated thioformaldehyde to yield complexes 6a
Eur. J. Inorg. Chem. 2010, 3636–3641
© 2010 Wiley-VCH Verlag GmbH & Co. KGaA, Weinheim
www.eurjic.org
3637

H. Petzold, T. Weisheit, S. Bräutigam, H. Görls, G. Mloston, W. Weigand
FULL PAPER
Both complexes are distorted square planar (Figures 2
and 3). The P–Pt–P angles of 97.3(5)° in 11 and 86.02(7)°
in 12 differ significantly. The bond lengths for Pt–S and
Pt–P around the platinum atom correspond to the range
expected for dithiolato PtII complexes.[9–10]
Figure 1. ORTEP drawing (with 50% probability ellipsoids) of the
molecular structure of complex 9. S2 and the adjacent carbon
atoms are disordered. Therefore, the bond lengths and bond angles
between C2, S2 and C1 are not reliable. Hydrogen atoms are omit-
ted for clarity.
Figure 2. ORTEP drawing (with 50% probability ellipsoids) of the
molecular structure of complex 11. Hydrogen atoms are omitted
for clarity.
and 7a with an additional equivalent of 4b. According to
literature data, NiII and PdII complexes analogous to 9 have
been obtained by treatment of the corresponding dichlorido
complexes [M(dppe)Cl2] (M = Ni, Pd) with 1,3-dimercapto-
2-thiapropane S(CH2SH)2.[13] Moreover, the reaction of
Fe2(CO)9 with spiro-cycloaliphatic substituted 1,2,4-tri-
thiolanes of type 1 led to similar metallacycles containing
even more crowded substituents, for example, the ada-
mantane skeleton.[14]
In contrast to 1a, reaction of the “symmetrical” S-oxide
10 with complexes 4a and 8 yielded a single product in each
case (Scheme 4). The 31P NMR spectra of both products
are very similar, exhibiting a singlet (δ = 26.3 ppm and
49.5 ppm, respectively) with 195Pt satellites [1J(P,Pt) = 2908
1
and 2790 Hz, respectively]. The H NMR spectra show a
characteristic AB system at δ = 3.91/4.19 ppm [2J(H,H) =
12.6 Hz] and δ = 4.01/4.25 ppm [2J(H,H) = 12.6 Hz],
respectively. Finally, the FTIR spectra have intense absorp-
tion bands at 1032 and 1027 cm–1, characteristic of sulfox-
ides (R2SO). From these data, the complex structures were
postulated as platinacycle 11 and 12, respectively. Diffusion
of pentane vapours into solutions of 11 in thf and 12 in
chloroform yielded yellow crystals for both complexes, suit-
able for single-crystal X-ray diffraction analysis (Tables 1
and 2).
Figure 3. ORTEP drawing (with 50% probability ellipsoids) of the
molecular structure of complex 12. Hydrogen atoms are omitted
for clarity.
The six-membered platinacycle adopts a distorted chair
conformation. In contrast to starting compound 10, the
oxygen atom is located in the equatorial position in both
11 and 12. The determined S–O bond length in 12
[1.481(6) Å] is similar to that found in 10 [1.496(2) Å][15]
.
The appearance of only one AB spin system for the CH2
1
groups in the H NMR spectra of 11 and 12 indicates a
high flexibility for the ring system in solution.
It is still an open question why 5a decomposes spontane-
ously to yield 6a and 7a whereas metallacycle 9 is stable at
room temperature and can be isolated. A possible explana-
tion is based on the assumption that there is a significant
decrease in the intramolecular repulsion between the thiol-
ato ligands and the phosphane ligands after replacement of
Scheme 4. Reactions of Pt0 complexes 4a and 8 with 1,2,4-trithiol-
ane 4-S-oxide (10).
3638
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Eur. J. Inorg. Chem. 2010, 3636–3641

Reactions of 1,2,4-Trithiolane and Its 4-S-Oxide with Pt0 Diphosphanes
the two PPh3 ligands by dppe (Scheme 5). Fragmentation lease of the intramolecular ligand repulsion. Moreover,
of 5a to thioformaldehyde (2a) and 7a results in a smaller complexes 11 and 12 display an enhanced stability resulting
S–Pt–S angle in 7a and therefore leads to a decrease in the from oxidation of the thioether function.
repulsion between the sulfur and phosphorus atoms located
around the platinum atom. This hypothesis finds additional
Experimental Section
support in the significantly larger intramolecular S···P dis-
tances S(1)···P(1) and S(3)···P(2) (3.238 Å and 3.256 Å,
respectively) in 9. Both distances are significantly longer
than those found for 11 (3.216 Å and 3.103 Å, respectively).
All reactions were performed under an argon atmosphere by using
the standard “Schlenk technique”. 1,2,4-Trithiolane (1a)[17], its 4-
S-oxide 10[15], as well as [Pt(PPh3)2(η2-C2H4)] (4a),[18] [Pt(PPh3)2-
(η2-nb)] (4b)[9a] and [Pt(dppe)(η2-C2H4)] (8),[19] were prepared ac-
cording to known protocols. The NMR spectra were recorded with
Bruker DPX 400 and DPX 200 instruments. Chemical shifts refer
to signals of the solvent or 85% H3PO4 (external standard) for
31P NMR spectra. The IR spectra were recorded with a PERKIN-
ELMER system 2000 FTIR instrument. Elemental analyses were
performed with a Vario EL III CHNS (Elementaranalysen GmbH
Hanau) instrument.
Scheme 5. Schematic presentation of the intramolecular repulsion
between the phosphane and thiolato ligands around the platinum
centres in 5a and 9.
31P{1H} NMR In Situ Monitoring of the Reaction of 1a with 4b:
Compound 1a (4 mg, 0.0032 mmol) dissolved in [D8]toluene
(0.3 mL) was added dropwise to a cooled (–50 °C) solution of 4b
(26 mg, 0.032 mmol) in [D8]toluene (0.6 mL) in a NMR tube. The
NMR tube was immediately transferred into the NMR spectrome-
ter, and the reaction was monitored from –50 °C to 25 °C. Selected
spectra are presented in the Supporting Information.
Alternatively, dissociation of one of the two phosphanes
might form a free coordination site for the fragmentation
reaction to form a thioformaldehyde dithiolato complex.
Therefore, dissociation of one PPh3 could be the key step
for the fragmentation. In addition, the increased steric re-
pulsion, as well as the chelate effect, would favour dissoci-
ation of one PPh3 in 5a and 11, To gain more information
on possible phosphane dissociation, we treated complex 11
with free dppe. Release of the intramolecular repulsion en-
ergy and the chelate effect should form 12 and free PPh3 in
the course of this reaction. Indeed, complex 12 was detected
as the main product in this reaction. Formation of some
unidentified products hampered the precise determination
of the rate constant. However, the decay of 11 depends on
the concentration of dppe in the solution, making a dissoci-
ative mechanism unlikely. The increased stability of 11 rela-
tive to 5a might be explained by a different activation en-
ergy in one of the involved intermediates. It is not trivial to
estimate the role of the oxidation of the sulfur atom on
several intermediate steps during the fragmentation of 5a.
In general, it can be assumed that sulfenato ligands are
weaker sigma donors than thiolato ligands. This is sup-
ported by the elongation of the Pt–S bond upon oxidation
of the thiolato ligand.[8,10c,10d,10g,10h] On the other hand, the
sulfenato ligands showed a larger trans influence, indicating
that they are stronger sigma donors. Moreover, it was found
that oxidation of thiolato ligands to the sulfenato and
sulfinato ligands can cause shortening of the metal–sulfur
bond.[16] More detailed investigation would be necessary to
explain convincingly the enhanced stability of 11.
X-ray Analysis: The intensity data were collected with a Nonius
KappaCCD diffractometer, by using graphite-monochromated
Mo-Kα radiation (λ = 0.71069 Å) at –90 °C. Data were corrected
for Lorentz and polarization effects and for absorption effects.[12–22]
The structures were solved by direct methods (SHELXS)[23] and
refined by full-matrix least-squares techniques against |Fo|2
(SHELXL-97)[24]. All hydrogen atoms of the structures were in-
cluded at calculated positions with fixed thermal parameters (1.2–
1.5 times that of the related non-hydrogen atom). All non-disor-
dered, non-hydrogen atoms were refined anisotropically.[24] Com-
plex 9 is disordered around S(2); this disorder could not be re-
solved. Therefore, bond lengths and bond angles in this part of the
molecule are not discussed. ORTEP-3 for Windows[25] was used for
structure representations. More information on structure refine-
ment is given in Table 2 and ref.[26]
[Pt(dppe){(SCH2)2S}] (9): A solution of 8 (150 mg, 0.2 mmol) in
toluene (20 mL) was added to 1a (35 mg, 0.28 mmol) dissolved in
thf (10 mL). The mixture was stirred for an additional 2 h. After
that time, the volume of the solvent was reduced to ca. 3 mL. Ad-
dition of pentane (10 mL) resulted in the precipitation of the crude
product as a yellow powder. The product was filtered off and
washed with a small portion of pentane. Crystallization from thf/
pentane yielded 9 as yellow plates (120 mg, 0.16 mmol, 82%). M.
1
p. 130 °C (dec.); H NMR (200 MHz, CDCl3): δ = 7.76 (m, 8 H),
3
4
7.46 (m, 12 H), 4.35 [d, J(H,Pt) = 54 Hz, J(H,P) = 8.4 Hz, 4 H,
-(S-CH2)2-S], 2.28 [d, J(H,Pt) = 25 Hz, 2J(H,P) = 18 Hz, 4 H, P-
CH2CH2-P] ppm. 31P{1H} NMR (81 MHz, CDCl3): δ = 48.6 [s,
1J(P,Pt) = 2757 Hz] ppm. IR (CsI): ν = 3050, 2905, 1968, 1894,
˜
1818, 1727, 1484, 1104, 821, 747, 715, 704, 690, 531, 485 (PC3)
cm–1. C28H28OP2PtS3 (717.74): calcd. C 46.86, H 3.93, S 13.40;
found C 46.65, H 3.94, S 13.70.
Conclusions
In summary, stable derivatives of six-membered plati-
nacycles of type 5 were synthesized, isolated and charac-
terized. The fragmentation of 5a into thioformaldehyde
complex 6a and dithiolato complex 7a was confirmed by
means of in situ NMR spectroscopy. The stability of the
[Pt(PPh3)2{(SCH2)2S=O}] (11): Compound 4a (145.0 mg,
0.20 mmol), dissolved in toluene (6 mL), was added to a stirred
solution of 10 (13.6 mg, 0.10 mmol) in toluene (4 mL) at room tem-
perature over a period of 30 min. The reaction mixture turned yel-
low, and a white precipitate was formed. The reaction mixture was
platinacycle 9 with respect to 5a might be explained by re- stirred overnight, and the solid formed thereafter was filtered off.
Eur. J. Inorg. Chem. 2010, 3636–3641
© 2010 Wiley-VCH Verlag GmbH & Co. KGaA, Weinheim
www.eurjic.org
3639

H. Petzold, T. Weisheit, S. Bräutigam, H. Görls, G. Mloston, W. Weigand
Table 2. Data of single-crystal X-ray analyses of complexes 9, 11 and 12.
FULL PAPER
9
11
12
Empirical formula
Formula weight [gmol–1]
T [°C]
Crystal system
Space group
a [Å]
b [Å]
c [Å]
α [°]
C28H28P2PtS3
717.71
–90(2)
Monoclinic
P21/n
8.8320(2)
23.1538(4)
13.3482(2)
90
C38H34OP2 PtS3
859.86
–90(2)
Orthorhombic
P212121
11.0546(3)
14.7560(4)
21.1438(5)
90
C28H28OP2PtS3 *2 CHCl3
972.45
–90(2)
Monoclinic
P21/c
16.2108(4)
13.6271(4)
18.1346(4)
90
β [°]
100.185(1)
90
2686.62(9)
4
1.774
55.91
90
90
114.684(2)
90
3639.99(16)
4
1.775
45.8
γ [°]
V [Å3]
3449.01(16)
4
1.656
Z
ρ [gcm–3]
µ [cm–1]
43.73
Reflections collected
Reflections with IϾ2σ(I)
Independent reflections/Rint
wR2 (all reflections F2)[a]
R1 [IϾ2σ(I)][a]
GooF[b]
16519
4836
6118/0.0550
0.0999
0.0395
1.049
1.663/–2.147
20809
7050
7763/0.0440
0.0871
0.0379
14342
5172
8316/0.0806
0.1397
0.0544
0.954
1.754/–2.561
1.025
Extrema ∆F [eÅ–3]
Flack parameter
Absorption correction
Tmin/max
1.844/–1.366
–0.006(7)
multi-scan
0.2080/0.2891
634396
multi-scan
0.8764/0.9064
634395
multi-scan
0.8140/0.9456
634397
CCDC no.
[a] Definition of R indices: R1 = (Σ||Fo| – |Fc||)/Σ|Fo| wR2 = {Σ[w(Fo – Fc ) ]/Σ[w(Fo2)2]}1/2 with w–1 = σ2(Fo2) + (aP)2. [b] GooF =
2
2 2
2
2 2
{Σ[w(Fo – Fc ) ]/(No – Np)}1/2
.
The product was washed with a diethyl ether/pentane mixture and
C28H28OP2PtS3 (733.74): calcd. C 45.83, H 3.85, S 13.11; found C
dried in vacuo to yield 62.0 mg (74.3%) of 11 as a colourless solid. 46.47, H 4.02, S 12.54.
M. p. 218 °C (dec.); 1H{31P} NMR [J(H,P) by comparison with 1H
Supporting Information (see footnote on the first page of this arti-
3
NMR] (400 MHz, CD2Cl2): δ = 7.39 [d, J(H,H) = 8.4 Hz, 12 H],
cle): Low-temperature 31P{1H} NMR spectra for the reaction of
4b with 1a as well as data on the kinetic investigation for the reac-
tion of 11 with dppe.
7.33 [t, 3J(H,H) = 8.0 Hz, 4 H], 7.18 [dd, 3J(H,H) = 8.4 Hz,
2
3
3J(H,H) = 8.0 Hz, 12 H], 4.18 {d, J(H,H) = 12.8 Hz, J(H,Pt) =
54.9 Hz, [4J(H,P) = 6.0 Hz], 2 H, -(S-CHH)2-S}, 3.89 {d, J(H,H)
2
= 12.8 Hz, 3J(H,Pt) = 64.4 Hz, [4J(H,P) = 7.6 Hz], 2 H, -(S-
CHH)2-S}. 31P{1H} NMR (81 MHz, CDCl3): δ = 26.3 [s, J(P,Pt)
1
Acknowledgments
= 2908 Hz] ppm. 195Pt{1H} NMR (58 MHz, CD2Cl2): δ = 167 [t,
1J(Pt,P) = 2920 Hz] ppm. IR (CsI): ν = 1032 (s, S=O), 542, 525,
˜
H. P. acknowledges financial support from Freistaat Thueringen
and the Fonds der Chemischen Industrie as well as the Deutscher
Akademischer Austausch Dienst (DAAD) (PKZ D/04/11451). The
authors gratefully acknowledge the donation of K2PtCl4 by
Heraeus GmbH. We are also grateful to Prof. Dr. K. Karagioshoff
for recording 13C{1H,31P} and 31P{1H} NMR spectra. G. M. is
grateful to the Alexander-von-Humboldt Foundation for financial
support. We also thank a reviewer for his valuable remarks.
515, 495 (PC3) cm–1. C28H28OP2PtS3 (733.74): calcd. C 53.08, H
3.99, S 11.19; found C 52.50, H 3.85, S 10.60.
[Pt(dppe){(SCH2)2S=O}] (12): 4-S-Oxide 10 (25 mg, 0.17 mmol)
was dissolved in toluene (10 mL). To this solution was added drop-
wise 8 (100 mg, 0.16 mmol) dissolved in toluene (10 mL). The solu-
tion immediately turned light green, and a white precipitate was
formed after a few minutes. The reaction mixture was stirred for
an additional 30 min, and the volume of the solvent was reduced
to ca. 3 mL. The yellow solid was separated by filtration and
washed with a pentane/ether mixture to yield 12 as crude product.
Crystallization from a chloroform/ether mixture yielded analyti-
cally pure complex 12 (60 mg, 50%) as yellow needles. M. p. 218 °C
(dec.); 1H{31P} NMR [J(H,P) from comparison with 1H NMR]
(400 MHz, CD2Cl2): δ = 7.78 {d, 3J(H,H) = 7.2 Hz, [J(H,P) =
11.6 Hz], 4 H}, 7.71 {d, 3J(H,H) = 7.6 Hz, [J(H,P) = 12 Hz, 4 H]},
7.48 (m, 12 H), 4.25 {d, 2J(H,H) = 12.6 Hz, 3J(H,Pt) = 51.6 Hz,
[4J(H,P) = 6.4 Hz], 2 H, -(S-CHH)2-S}, 4.01 {d, 2J(H,H) = 12.6 Hz,
3J(H,Pt) = 59.6 Hz, [4J(H,P) = 7.2 Hz], 2 H, -(S-CHH)2-S}, 2.35
{s, J(H,Pt) = 38.4 Hz, [2J(H,P) = 24 Hz], 4 H, P-CH2CH2-P}ppm.
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Received: December 20, 2009
Published Online: June 23, 2010
Eur. J. Inorg. Chem. 2010, 3636–3641
© 2010 Wiley-VCH Verlag GmbH & Co. KGaA, Weinheim
www.eurjic.org
3641