Double bond migration in S-allyl systems catalysed by [RuC1H(CO)(PPh3)3]

Article abstract of DOI:10.1016/S0022-328X(02)02111-3

Reactions of S-allyl systems (allyl sulphides of R-S-allyl type, where R = Et, allyl, Ph, Me₃C, Ph₃C, as well as of allyl phenyl sulphoxide, allyl phenyl sulphone, 2,5-dihydro-1,1-dioxothiophene) with [RuClH(CO) (PPh₃)

Full text of DOI:10.1016/S0022-328X(02)02111-3

Journal of Organometallic Chemistry 665 (2003) 167ꢁ175
/
www.elsevier.com/locate/jorganchem
Double bond migration in S ꢀ
/
allyl systems catalysed by
[RuClH(CO)(PPh3)3]
Nikodem Kuz´nik *, Stanis law Krompiec, Tadeusz Bieg, Stefan Baj, Krzysztof Skutil,
Anna Chrobok
Faculty of Chemistry, Silesian University of Technology, Krzywoustego 6, 44-100 Gliwice, Poland
Received 25 July 2002; accepted 30 October 2002
Abstract
Reactions of S ꢀ
/
allyl systems (allyl sulphides of Rꢀ
/
Sꢀ
/
allyl type, where RꢀEt, allyl, Ph, Me3C, Ph3C, as well as of allyl phenyl
/
sulphoxide, allyl phenyl sulphone, 2,5-dihydro-1,1-dioxothiophene) with [RuClH(CO)(PPh3)3] and other ruthenium compounds
have been investigated. Double-bond migration was observed in the case of allyl trityl sulphide, allyl t-butyl sulphide and both
sulphones, that is, where co-ordinating properties of sulphur were not too strong. High-yielded syntheses of (E)- and (Z)-Rꢀ
CHꢁCHCH3 (RꢀMe3C, Z:Eꢀ96:4 and Ph3C, Z:Eꢀ92:8), (E)ꢀPhꢀS(O2)ꢀCHꢁCHCH3 and 2,3-dihydro-1,1-dioxothiophene
from respective allyl systems are described. The binuclear Ru complex, formed in the model reaction of allyl phenyl sulphide with
allyl systems
/
Sꢀ
/
/
/
/
/
/
/
/
/
[RuClH(CO)(PPh3)3] has been isolated and its structure has been resolved. The mechanism of the reaction between S ꢀ
/
and [RuClH(CO(PPh3)3] is proposed.
# 2002 Elsevier Science B.V. All rights reserved.
Keywords: Isomerisation; S ꢀ
/
allyl compounds; CꢀS bond cleavage; Ruthenium complexes
/
1. Introduction
Al2O3 [25]. In our paper, we demonstrated a possibility
of the isomerisation of some allyl sulphides catalysed by
ruthenium complexes [26]. To our best knowledge, in the
literature there are no other reports of the isomerisations
S-(1-Propenyl), or generally, vinyl sulphides, sulph-
oxides and sulphones are attractive reagents in organic
synthesis. Among other applications, they are used as
of S ꢀ
/
allyl systems in the presence of transition metal
complexes. This is certainly a consequence of very
strong co-ordinating properties of sulphur atoms and
reagents for addition to Cꢁ
[2ꢂ2] [5ꢁ7], cycloaddition [2ꢂ
tion [9,11], as well as donors of 1-propenyl fragment
[12ꢁ15], what is of particular interest. It should be
emphasised that unlike S-(1-propenyl), S ꢀallyl systems
are not propenyl donors [13,14]. S ꢀ(1-Propenyl) sys-
tems (vinyl systems generally) are easy to synthesise via
catalytic isomerisation of respective S ꢀallyl systems.
/
C [1ꢁ
/
4] bond, cycloaddition
/
/
/
4] [8ꢁ
/10], dipolar addi-
the resulting tendency of Sꢀ/C(allyl) bond cleavage. This,
in turn, leads to transformation of the catalyst pre-
cursors into inactive complexes for the double-bond
/
/
migration. The cleavage of Cꢀ
transition metal complexes (oxidative addition of O ꢀ
and S ꢀallyl compounds to low valent transition metal
complexes) such as Ru has been studied intensively [27ꢁ
29]. In this paper, however, the results of investigating
the reactions between S ꢀallyl systems and various
/
O and Cꢀ
/
S bonds by
/
/
/
/
/
Previously known reactions of the isomerisation of allyl
sulphides were carried out in the presence of t-BuOK
/
[16ꢁ
transformed into vinyl sulphones using Et3N [20], KOH
[21], NaOH [22], NaH [23], NaOHꢁBu4NOH [24],
/
18], KOH [18] or EtONa [19]. Allyl sulphones were
ruthenium complexes (particularly [RuClH(CO)-
(PPh3)3]) are discussed. New methods of the synthesis
of some vinyl sulphides and sulphones via isomerisation
/
of
respective
S ꢀ/allyl systems
catalysed
by
[RuClH(CO)(PPh3)3] are presented. The structure of
the complex isolated from the products of the model
reaction between allyl phenyl sulphide and
* Corresponding author. Tel.: ꢂ
2277.
E-mail address: nikodem@zeus.polsl.gliwice.pl (N. Kuz´nik).
/
48-32-237-1707; fax: ꢂ48-32-237-
/
0022-328X/02/$ - see front matter # 2002 Elsevier Science B.V. All rights reserved.
PII: S 0 0 2 2 - 3 2 8 X ( 0 2 ) 0 2 1 1 1 - 3

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N. Kuz´nik et al. / Journal of Organometallic Chemistry 665 (2003) 167ꢁ175
/
[RuClH(CO)(PPh3)3] is described. Furthermore, the
allyl systems
and [RuClH(CO)(PPh3)3] is discussed.
phenyl sulphoxide, practically no products of double-
bond migration were observed. For S ꢀallyl systems,
mechanism of the reaction between S ꢀ
/
/
which successfully undergo isomerisation no by-pro-
ducts were detected. Therefore, the conversion of allyl
systems (o) in the Table 1 was practically equal the yield
of double-bond migration product (y). On the other
hand, a decrease of Z/E ratio in the course of the
isomerisation of allyl t-butyl sulphide and allyl trityl
2. Results and discussion
The results of our investigation of the isomerisation of
some sulphides, allyl phenyl sulphoxide, allyl phenyl
sulphone and 2,5-dihydro-1,1-dioxothiophene catalysed
by [RuClH(CO)(PPh3)3] are presented in Table 1.
As it is shown in the Table 1, the isomerisation to 1-
propenyl (vinyl) derivatives was successful for allyl
sulphides with bulky groups (R), as well as for both
sulphones. In the case of other allyl sulphides and allyl
sulphide indicates that the Z ꢁ
consecutive reaction. However, double-bond migration
is faster than Z ꢁE isomerisation. Therefore, it was
/
E isomerisation is a
/
possible to obtain 1-propenyl sulphides, which con-
tained no more than 8% of the E-isomer (product) and
less than 0.4% of allyl system (substrate). We have tried
modifying several reaction conditions including: prolon-
Table 1
Isomerisation of Sꢀallyl compounds catalysed by [RuClH(CO)(PPh3)3]
/
t, reaction temperature; t, reaction time; [Ru], catalyst concentration in (%) mol; Solv., solvent (4 cm3 per 1 mmol of substrate); o , reagent
conversion; y, yield of isomerisation product; B, benzene; (a) determined by 1H-NMR; (b) an increase of the reaction temperature up to 140 8C or/
and prolonging the reaction time up to 6 h, or an increase of catalyst concentration up to 10% mol does not improve the double-bond migration
product yield; (c) not determined, but probably no other products formed; (d) reactions carried out in benzene and in THF, in both cases propene was
released; (e) ꢀ
scale, see Section 3; (h) the reactions carried out in benzene and in THF, in both cases propene release was not observed; (i) benzeneꢂ
100% (E); (k) equilibrium composition: 6% (Z) and 94% (E) [16]; (l) equilibrium conversion in accordance with [36]*42%.
/
0.5% allyl sulphide in equilibrium [16]; (f) equilibrium composition: 29% (Z) and 71% (E) [16]; (g) also carried out on preparative
/THF 1:1; (j)
/

N. Kuz´nik et al. / Journal of Organometallic Chemistry 665 (2003) 167ꢁ
/
175
169
gation of the reaction time, increasing the temperature
up to 140 8C, changing the solvent (for Cl2CꢁCCl2,
THF, xylene, 1,4-dioxane) and use of other ruthenium
complexes as catalysts, like: [RuClH(PPh3)3],
[RuCl2(PPh3)3], [Ru(acac)3], [RuCl2(NBD)]x, [RuCl2(p-
the mentioned complex. The research has revealed that
propene is released in the course of heating allyl phenyl
sulphide with [RuClH(CO)(PPh3)3] in boiling THF or
benzene. Such release had previously been observed in
the reactions of allyl methyl sulphide and allyl benzyl
/
cymene)]2,
[Ru(CO)3(PPh3)2],
[RuH2(CO)(PPh3)3],
sulphide
with
[RuClH(CO)(PPh3)3]
[30]
and
[RuH2(PPh3)4], but it has not increased the isomerisa-
tion yield. It should be noted that the isomerisation of
allyl trityl sulphide with [RuClH(CO)(PPh3)3] occurred
at ambient temperature (but the proportion of [Ru] to
the substrate was 1:1). In this reaction, we did not
observe any complexes, which were the products of
[RhH(CO)(PPh3)3] [34,35]. Moreover, we found that in
both reactions (in THF and in benzene) coloured
ruthenium complexes were formed (what was observed
as coloured bands on preparative TLC plates); at the
same time, in both discussed cases a yellow complex (3)
constituted ꢀ90% of the mass of the separated com-
/
insertion of Ph3Cꢀ
complexes, like [Ru(C,S ꢀ
(PPh3)2] were described by Hiraki et al. [30] as the
products of insertion of [RuClH(CO)(PPh3)3] to RꢀSꢀ
allyl, where RꢀMe, CH2Ph or allyl (in a THF solution
at 10ꢁ28 8C). It is important to indicate that we
observed propene release in the reactions of the systems
that did not isomerise (EtꢀSꢀallyl, PhꢀSꢀallyl, allyl2S,
PhꢀS(O)ꢀallyl). Moreover, we demonstrated that the
precursor, i.e. [RuClH(CO)(PPh3)3], was transformed
into an inactive complex (for isomerisation) in those
reactions which did not lead to the migration of the
double bond. This has been further proved by the
/
Sꢀ
/
allyl into Ruꢀ
/
H bond. Such
plexes. This complex (3) (from the reaction in benzene)
was isolated using preparative TLC. An attempt to
isolate this complex by means of column chromatogra-
phy (on silica gel) failed. The structure of 3 was
determined by an X-ray method (Fig. 1). The X-ray
analysis result is fully consistent with its spectroscopy
data (1H and 13C-NMR, IR) and elemental analysis.
The separated complex (3) does not contain any hydride
ligand, what was proved by spectroscopy data. Hiraki et
al. in their investigations on the reaction of allyl alkyl
/
CH2CH2CH2SR)Cl(CO)-
/
/
/
/
/
/
/
/
/
/
sulphides
(alkylꢀ/Me,
CH2Ph,
allyl)
with
[RuClH(CO)(PPh3)3] had previously suggested the for-
mation of binuclear complexes containing hydride
ligand [30]. However, they had not separated the
mixture of the formed complexes and had not evaluated
their structure by X-ray. The structures of other
observed impact of ‘external’ S ꢀ/allyl systems (and
similar solvents containing sulphur) on the isomerisa-
tion of 1-allyl-3,4-methylenedioxybenzene and allyl
phenyl ether. Their double bond migration is successful
(conditions: 0.1 M of the allyl system, 0.005 M
[RuClH(CO)(PPh3)3], 80 8C) in benzene (100% conver-
sion of allylbenzene or allyl phenyl ether after 5 min),
1,1-dioxotetrahydrothiophene and allyl t-butyl sul-
phide. On the other hand, no double bond migration
in similar conditions (molar 1:1 allyl system: solvent) in
complexes formed in the reaction between Phꢀ
and [RuClH(CO)(PPh3)3] and seen on TLC plates were
not analysed due to very low yields (1ꢁ3%; Table 2).
/
Sꢀ
/
allyl
/
The determination of the structure of the complex (3)
formed in the reaction between allyl phenyl sulphide and
[RuClH(CO)(PPh3)3] made it possible to present a more
generalised proposal of the mechanism of the reaction
between Q-allyl and [RuClH(CO)(PPh3)3]: see Fig. 3.
It has been assumed that the double-bond migration
is a typical hydride mechanism. This assumption has
strong support by our previous findings with deuterated
species [31,32] as well as those made by other authors
Et2S, Phꢀ
/
Sꢀ
/
allyl, DMSO, allyl2S, Phꢀ
/
S(O)ꢀ
/
allyl. S ꢀ
/
Allyl systems which do not undergo isomerisation in
the presence of [RuClH(CO)(PPh3)3], if added to other
usually easily isomerising allyl systems, i.e. allyl phenyl
ether (1) and 1-allyl-3,4-methylenedioxybenzene (2)
completely block their isomerisation by ruthenium
complexes [31,32]. Also, the solvents with strong co-
[37ꢁ
triphenylphosphine from [RuClH(CO)(PPh3)3] to pro-
duce the active form [Ru]ꢀH (4) [31]. Next, an is formed
from [Ru]ꢀH and Qꢀallyl. For clarity, the evident
/39]. The reaction begins with dissociation of
ordinating properties (Et2S as allyl2S, DMSO as Phꢀ
/
/
S(O)ꢀ
(1) and (2).
On the other hand, addition of S ꢀ
/
allyl) disable the double-bond migration both in
/
/
contribution of all p-olefin complexes produced in the
consecutive reaction steps has not been shown on Fig. 2,
however the proposed structures of the p-olefin com-
plexes are depicted on Fig. 4. After that, by a typical 1,2-
/allyl systems which
themselves easily undergo isomerisation (allyl t-butyl
sulphide, allyl trityl sulphide and sulphones), as well as
using 1,1-dioxotetrahydrothiophene as the solvent,
blocks neither the isomerisation of (1) nor of (2).
Similar solvent behaviour had been previously ob-
served in the reactions between various strong co-
insertion of co-ordinated alkene to the Ruꢀ
/H bond,
complexes 5, 6, 7 or 8 and 10 are formed, respectively. It
is our opinion that if the sulphur atom in the functional
group Q has strong co-ordinating properties (like S
atom in sulphides not shielded by a bulky group),
functional group Q (via S atom) in complexes 8 and
10 interacts strongly with Ru atom. Consequently, this
ordinating S ꢀ
/
and N ꢀ
/
allyl systems and [Ru(acac)3]
[33]. To learn more about the reactions between Sꢀ
/allyl
systems and [RuClH(CO)(PPh3)3] we investigated thor-
oughly the reaction between allyl phenyl sulphide and
leads to Cꢀ
/
Q (Cꢀ/S) bond cleavage easily occurring in

170
N. Kuz´nik et al. / Journal of Organometallic Chemistry 665 (2003) 167ꢁ175
/
Fig.
1. Structure
of
the yellow complex (3) isolated from the reaction between allyl phenyl sulphide and [RuClH(CO)(PPh3)3].
chlorocarbonyl(triphenylphosphine)ruthenium
(II)-m-chloro-di(thiophenolato)-carbonyl-bis(triphenylphosphine)-
ruthenium(II)*
/
presented in Fig. 3 are reversible with the exception of
Table 2
Selected bond lengths (A) and angles (8) for complex 3
non-reversible transformations 8 and 10 into 9 (with
propene release) and consequently into 11. Thus, the
isomerisation product may always be subjected to a
non-reversible transformation (even if it occurs rela-
tively slowly and most likely has higher activation
˚
Bond lengths
Bong angles
Ru1ꢀ
Ru2ꢀ
Ru1ꢀ
Ru1ꢀ
/
C2
C1
S1
S2
1.83(2)
1.82(2)
2.376(5)
2.439(5)
1.126(19)
1.3(2)
Ru2ꢀ
Ru1ꢀ
O2ꢀC2ꢀ
O1ꢀC1ꢀ
/
S2ꢀ
S1ꢀ
/
Ru1
Ru2
87.3(2)
88.8(2)
/
/
/
energy, so is more temperature sensitive)*and even
/
/
/
/
Ru1
Ru2
177.4(2)
176.5(2)
/
/
/
despite the fact that sulphur co-ordinates only weakly
with Ru atom in complexes 8 and 10.
Furthermore, we have observed that in the reaction
between allyl phenyl selenide and [RuClH(CO)-
O1ꢀ
/
C1
O2ꢀ
/
C2
(PPh3)3]*under the same conditions as in the case of
allyl phenyl sulphide propene is also released. At the
same time, no double-bond migration products were
/
complex 8. Propene is released and monomeric complex
9 is formed consecutively, dimerizing to binuclear
complex 11; as thiolate ligands are prone to co-ordinate
in a bridging fashion [40]. This idea is based on the
structure of the separated complex 3. On the other hand,
if Q does not have strong co-ordinating properties (for
sulphones), complexes 5 and 6 (and in the case of
observed*
tionally, we have observed that the presence of Phꢀ
allyl blocks the isomerisation of PhꢀOꢀallyl and Phꢀ
allyl*likewise in the presence of sulphides and sulph-
oxides (see Fig. 1). Basing on our previous research, we
have found that PhꢀOꢀallyl and other allyl ethers
/
similarly to the case of Phꢀ
/
Sꢀ
/
allyl. Addi-
/
Sꢀ
/
/
/
/
/
sulphones*
toward formation of double-bond migration product
and [Ru]ꢀH: product of (Z) configuration from com-
/
complex 8 as well) undergo b-elimination
/
/
isomerise very easily to 1-propenyl ethers in the absence
/
of sulphur compounds [31,32]. In our previous research
plex 5, and product of (E) configuration from complex 6
(for sulphides) or complex 8 (in the case of sulphone).
This occurs when the sulphur atom present in Q is
shielded by a bulky group disabling or, at least, limiting
the co-ordination of Ru atom. One could imagine that a
similar situation takes place when the sulphur is of
‘sulphone’ type (also having weak co-ordination proper-
ties). On the grounds of the proposed reaction mechan-
ism, it is also possible to explain why an increase in the
reaction temperature results in lowered double-bond
migration product yield. In any case, the reactions
in this field neither Cꢀ
observed in ethers nor blocking of the catalytic activity
of [Ru]ꢀH by solvents containing an oxygen atom (like
Et2O, THF, MeCOMe) [31,32]. It turns out that the
bond cleavage of Qꢀallyl in S ꢀ and Se ꢀallyl systems
/
O bond cleavage was ever
/
/
/
/
results from a strong co-ordination of S or Se atoms to
Ru. The co-ordination effect leads to the lengthening
and weakening of Cꢀ
facilities CꢀQ bond cleavage. In the case of allyl ethers
(Oꢀallyl systems) the co-ordination of O atom to Ru is
/Q bond what in consequence
/
/

N. Kuz´nik et al. / Journal of Organometallic Chemistry 665 (2003) 167ꢁ
/
175
171
Fig. 2. Proposal of the mechanism of the reaction between S ꢀ
above scheme does not take into account the step of [Ru]ꢀH formation as well as the contribution of triphenylphosphine (also Cl and CO*
liable under the conditions assumed) and a solvent in the co-ordination of Ru atom in all complexes.
/
allyl systems (Qꢀ
/
allyl) and [RuClH(CO)(PPh3)3] in a benzene or THF solution. The
/
/non-
might locate on one side of the plane (Ruꢀ
/
Hꢀ/Calkyl
ꢀ
/
Calkyl), while the other substituants may locate on the
other side in order to reduce the steric hindrance. This
might lead to the observed Z isomer. For sulphones (17)
Sꢁ
well as Ruꢀ
our previous Quantum chemical calculations*
This should lead to E isomer.
/
O. . .H interations might have important impact, as
arene co-ordination, which is supported by
Fig. 4.
/
/
Similar effect, i.e. the production of (E) isomers had
been previously exclusively observed in the isomerisa-
tion of N-allyl-N-arylethanamides [41]. Quantum calcu-
lations performed are fully consistent with the
explanation that such selectivity of the isomerisation
of the above amides is caused by the co-ordination of
the Ru atom by the arene ring and not merely by steric
factors.
Fig. 3. Probable transition states of b-elimination resulting in (Z)-(1-
propenyl) trityl sulphide 16 and (E)-(1-propenyl) phenyl sulphone 17.
too weak to enable the Cꢀ
/
O bond cleavage. Therefore,
only fast double-bond migration is observed.
It should also be emphasised that the isomerisation of
Ph3Cꢀ
/
Sꢀ
/
CH2CHꢁ
/
CH2 and Me3Cꢀ
/
Sꢀ
/
CH2CHꢁ/CH2
On the other hand, the formation of (Z) isomers in
the isomerisation of sulphides is, in our opinion, a result
of steric interactions. The interaction of such a bulky
group like trityl or tert-butyl with other ligands co-
ordinated by ruthenium atom leads to complex 5 being
generally leads to 1-propenyl derivatives of (Z) config-
uration; whereas the isomerisation of allyl phenyl
sulphone results solely in a product of (E) configuration.
We claim that in the case of a sulphone (within the
transition state of this reaction) the ruthenium atom is
co-ordinated by the oxygen atom or by the benzene ring.
Such co-ordination leads toward (E)-product. Fig. 3
depicts the most probable transition states during
formation of the respective 1-propenyl products. In the
case of bulky sulphones (16), the bulky PPh3 ligands
the product of [Ru]ꢀ
/
H addition to Cꢁ
/
C. As a result, b-
H from complex 5 leads to (Z)-1-
elimination of [Ru]ꢀ
/
propenyle sulphide. Moreover, we claim that in the case
of allyl trityl sulphide, steric hindrance disables the co-
ordination of Ru atom by the benzene ring*which
/

172
N. Kuz´nik et al. / Journal of Organometallic Chemistry 665 (2003) 167ꢁ175
/
Restek. In the course of the analysis, a programmed
increase of temperature was applied (from 80 to 180 8C).
3.1. Materials
Allyl trityl sulphide, t-butyl mercaptan, allyl phenyl
sulphide, allyl phenyl sulphoxide, allyl phenyl sulphone,
2,5-dihydro-1,1-dioxothiophene (butadiene sulphone),
allyl phenyl selenide-from Aldrich, [RuCl2(p-cymene)]2
and [RuH2(CO)(PPh3)3] from STREM. Allyl t-butyl
sulphide [42], [RuClH(CO)(PPh3)3] [43,44], [RuClH-
(PPh3)3] [45], [RuCl2(PPh3)3] [46], [Ru(acac)3] [47],
[RuCl2(NBD)x]
[48],
[Ru(CO)3(PPh3)2]
[49],
[RuH2(PPh3)4] [50] were synthesised as described in the
literature.
Fig. 4. The co-ordination of ruthenium to benzene ring might be an
important factor to Z ꢁE regioselectivity. The co-ordination of N-
alliloamides and N-(1-propenylo)amides is supported by quantum
calculation [41].
/
3.2. Synthesis of allyl trityl sulphide
Triphenylmenanothiole (0.04 mol) was added to the
solution of 0.05 mol of sodium methanolate in 150 cm3
of methanol, stirred with a mechanical stirrer. The
mixture was refluxed for 10 min, and next 0.08 mol of
allyl bromide was added. Then the mixture was heated
for 1 h; after that volatile fractions were evaporated on a
rotary evaporator. The obtained precipitate was washed
by water on a fritted funnel and crystallised from
ethanol (with the addition of activated coal). Allyl trityl
would lead to the isomerisation product of (E) config-
uration (such as in the case of sulphone).
3. Experimental
All reactions were performed under dry argon atmo-
sphere. Solvents were dried with appropriate drying
agents (molecular sieves, CaH2 or Na) and distilled prior
to use. Infrared spectra were measured on a Karl Zeiss
Jena M-80 spectrometer (in KBr). NMR spectra were
obtained on a Varian Unity Inova 300 MHz spectro-
meter. MS analysis for [Ru2Cl2(PhS)2(CO)2(PPh3)3] by
sulphide (10.3 g) was obtained (81%); m.p.ꢀ
1H-NMR (CDCl3) 2.81 (ddd, 2H, J1ꢀ
7.3 Hz; J2ꢀ
Hz; J3ꢀ1.0 Hz); 4.97 (ddt, 1H, J1ꢀ10.5 Hz; J2ꢀ
Hz; J3ꢀ1.0 Hz); 5.05 (ddt, 1H, J1ꢀ17.2 Hz; J2ꢀ
Hz; J3ꢀ1.4 Hz); 5.67 (ddt, 1H, J1ꢀ17.2 Hz; J2ꢀ
Hz; J3ꢀ7.3 Hz); 7.17ꢁ
7.43 (m, 15H). 13C-NMR
/
74ꢁ75 8C.
/
/
/
1.4
1.8
1.8
/
/
/
ꢄ
/
/
/
/
ꢄ
/
/
/
/10.0
/
/
ESJꢁMS method was carried out in the Centre of
/
(CDCl3, 75.4 MHz, 293 K) 35.56 (s); 66.95 (s); 117.63
(s); 126.54 (s); 127.93 (d); 129.59 (d); 133.10; 144.76.
Anal. Calc. for C22H20S: C, 83.50; H, 6.37; S, 10.13%.
Found: C, 83.47; H, 6.38; S, 10.15. MS m/z (%): 243
(100); 165 (72); 228 (11); 74 (7); 215 (6); 152 (5); 120 (5);
115 (4); 119 (4); 77 (3); 275 (1); 316 (1).
Polymer Chemistry at the Polish Academy of Sciences
in Zabrze. The mass spectra of the organic compounds
were recorded on HPLCꢁMS Waters Integrity Systems
/
with Termabeam Mass Detector (EI, 70 eV), Photo-
diode Array Detector on a cartridge column (Nova-Pak
C18, 2ꢃ
/
150 mm); methanolꢁwater mixture (75:25; flow
/
0.25 ml minꢄ1) used as the solvent. Elemental analyses
of ruthenium complexes were made by CP-AES method,
on a Thermo Jamell Ash spectrometer, in the elemental
analysis lab at Polish Chemical Reagents Co. (POCh) in
Gliwice. Before the analysis, ruthenium complexes were
mineralised in boiling 60% HNO3. Elemental analyses of
sulphides were carried out in the elemental analysis lab
at Silesian University of Technology. GC of the gas
3.3. Isomerisation of S ꢀ
/
allyl compounds in the presence
of ruthenium or rhodium complexes
a) Allyl compounds were heated with a ruthenium
complex (with or without a solvent) in high-pressure
glass ampoules, which were put in a thermostat (9
/
0.1 8C). The proportions of the substrate, the
catalyst and the solvent have been given in the
description of Fig. 1 and Table 1. Before the
reaction, oxygen had been removed from the reac-
tion system and the system had been saturated with
argon. After the reaction was completed, the
products of the reaction between S ꢀ
/
allyl systems and
[RuCl(H)(CO)(PPh3)3] was obtained by GC 505 (pro-
duced by INCO, Wroc law) equipped with flame-ionisa-
tion detector and argon as carrier gas. The composition
of the carrier gas was analysed with a packed column
(length: 2 m, diameter: 3 mm) filled with modified
composition of the reaction mixture was analysed
1
by H-NMR and/or by GCꢁ
/MS method.
aluminium oxide, as well as on a capillary column Rtꢁ
Q-Plot (length: 15 m, diameter: 0.32 mm) produced by
/
b) The post-reaction mixture consisting in: allyl com-
pounds, solvent (benzene or THF) and catalyst was

N. Kuz´nik et al. / Journal of Organometallic Chemistry 665 (2003) 167ꢁ
/
175
173
refluxed with argon flow. The proportions of the
substrate: catalyst; solvent have been given in the
description of Fig. 1 and Table 1. The outlet gas
from the reaction system was collected and analysed
by GC.
with 50 cm3 pentane. After the filtration of the catalyst
(as well as triphenylphosphine and its oxide) the pentane
solution was chromatographed on a column containing
5 g silicagel (200ꢁ
the residue contained 72% of (E)- Phꢀ
CHCH3 and 28% of allyl phenyl sulphone with the
yield of 95%. Pure (E)- PhꢀS(O2)ꢀCHꢁCHCH3 was
isolated from the mixture by preparative TLC method
(the plates were developed with diethyl etherꢁchloro-
form mixture in the proportion of 1:1). M.p.ꢀ70ꢁ71 8C
(ethanol); 67ꢁ
68 8C (ethanol) according to [53]. 1H-
/400 mesh). After pentane evaporated,
/
S(O2)ꢀCHꢁ
/
/
3.4. Preparation of (E)- and (Z)-Me3Cꢀ
/
Sꢀ
/
CHꢁ
/
/
/
/
CHCH3
/
Allyl t-butyl sulphide (100 mmol),
2
mmol
/
/
[RuClH(CO(PPh3)3] and 50 cm3 benzene was refluxed
for 3 h. Next, the reaction mixture was rectified with a
30 cm column packed with Fensky helixes under the
pressure of 60 mmHg. The obtained distillate contained
0.4% of allyl sulphide and 4% of (E)- and 96% of (Z)-
/
NMR spectrum of the obtained product was consistent
with the one described in literature [24].
3.7. Preparation of 1,2-dihydro-1,1-dioxothiophene
Me3Cꢀ
/
Sꢀ
/
CHꢁ
/
CHCH3 with the yield of 92%. B.p.: 60ꢁ
/
62 8C. The spectroscopy data of both isomeric products
were consistent with those quoted in literature (1H and
13C-NMR [51], MS [52]).
2,5-Dihydro-1,1-dioxothiophene (100 mmol), 2 mmol
[RuClH(CO(PPh3)3] and 50 cm3 benzene was refluxed
for 6 h. Next, benzene was distilled off on a vacuum
rotary evaporator, and the mixture of 2,5-dihydro-1,1-
dioxothiophene and 2,3-dihydro-1,1-dioxothiophene
(58:42) was rectified under the pressure of 0.5 mmHg
3.5. Preparation of (E)- and (Z)-Ph3Cꢀ
CHCH3
/
Sꢀ
/
CHꢁ
/
(b.p.ꢀ
/
117ꢁ120 8C) with the yield of 90%. Pure 1,2-
/
Allyl-trityl sulphide (10 mmol), 0.25 mmol
[RuClH(CO(PPh3)3] and 40 cm3 benzene were heated
in 60 8C for 2 h, with vigorous stirring on a magnetic
stirrer. Benzene was distilled off on a vacuum rotary
evaporator, whereas the light-yellow residue was ex-
tracted three times with 30 cm3 hexane. The extract
(containing the product and some yellow Ru complex)
was filtered, and then chromatographed by on a column
dihydro-1,1-dioxothiophene was isolated from the ob-
tained mixture by preparative TLC method, with the
yield of 93% (the plates were developed in chloroform).
M.p.ꢀ
/
50ꢁ
/
51 8C (recrystallised from Et2O); 50ꢁ52 8C
/
(recrystallised from Et2O) according to [54]. The spec-
troscopy data were consistent with those given in the
literature (1H, 13C-NMR and MS [55]).
containing 5 g silicagel (200ꢁ
was eluted with hexane. After hexane evaporated, the
residue contained 8% of (E)- and 92% of (Z)-Ph3CꢀSꢀ
CHCH3 and it practically did not contain any allyl
system with the yield of 95%. Anal. Calc. for C22H20S:
C, 83.50; H, 6.37; S, 10.13%. Found: C, 83.46; H, 6.38;
/
400 mesh). The product
3.8. Isolation of [Ru2Cl2(PhS)2(CO)2(PPh3)3]*(3)
/
/
/
[RuClH(CO)(PPh3)3] (1 mmol), 10 mmol allyl phenyl
sulphide and 20 cm3 benzene were refluxed in argon
flow. The outlet gas was collected and analysed by GC.
After the reaction, benzene was evaporated on a rotary
evaporator, and 50 cm3 pentane was added to the oily
residue. The mixture was intensively shaken until a
suspension of ruthenium complexes was obtained; then
CHꢁ
/
1
S, 10.16. H-NMR (CDCl3): (E) 1.56 (dd, 3H, J1ꢀ
/
6.6
1.65);
7.40 (m,
1.7 Hz); 5.51
6.6); 5.61 (dq, 1H, J1ꢀ9.3 Hz;
7.40 (m, 15H). 13C-NMR (CDCl3,
Hz; J2ꢀ
5.86 (dq, 1H, J1ꢀ
15H); (Z) 1.76 (dd, 3H, J1ꢀ
(dq, 1H, J1ꢀ9.3; J2ꢀ
J2ꢀ1.7 Hz); 7.05ꢁ
/
1.6 Hz); 5.55 (dq, 1H, J1ꢀ
15.4 Hz; J2ꢀ6.6 Hz); 7.05ꢁ
6.6 Hz; J2ꢀ
/
15.38; J2ꢀ
/
/
/
/
/
/
it was left for 24 h in the temperature of ꢄ
orangeꢁyellow precipitate was filtered off on a fritted
funnel and washed three times with pentane. After
drying under vacuum, the obtained yellowꢁorange
/
10 8C. The
/
/
/
/
/
/
75,4 MHz, 293 K): (E) 18.59 (s); 67.32 (s); 126.68 (s);
127.74 (s); 129.75 (s); 145.00 (s); (Z) 14.85 (s); 67.27 (s);
124.66 (s); 124.89 (s); 126.79 (s); 127.80 (s) 129.82 (s);
145.08 (s). MS m/z (%): 165 (100); 243 (94); 244 (49); 74
(11); 228 (10); 152 (9); 215 (7); 115 (6); 77 (5); 120 (5);
275 (1); 316 (1).
/
ruthenium complexes mixture (also containing triphe-
nylphosphine and its oxide) was separated with pre-
parative TLC method. The plates were first developed in
benzene and next in dichloromethane. Yellow complex 1
was extracted from the gel with acetone. The TLC
analysis indicated that the extract does not contain any
other ruthenium complexes. After acetone was evapo-
rated on a rotary evaporator and dried under vacuum,
260 mg of 1 were obtained in the form of tiny, yellow
crystals (bigger crystals take an orange colouring).
3.6. Preparation of (E)- Phꢀ
/
S(O2)ꢀ
/
CHꢁ/CHCH3
Allyl phenyl sulphone (100 mmol),
2
mmol
[RuClH(CO(PPh3)3] and 50 cm3 benzene were refluxed
for 6 h. Benzene was distilled off on a vacuum rotary
evaporator, and the residues were extracted two times
M.p.: within the temperature range of 60ꢁ
gradually changes the colour to red; in 153ꢁ
/
140 8C it
155 8C
/

174
N. Kuz´nik et al. / Journal of Organometallic Chemistry 665 (2003) 167ꢁ175
/
decomposes. Solubility: very good in CH2Cl2, CHCl3,
benzene, Et2O; good in acetone; insoluble in hexane,
cyclohexane. Stability in solutions: stable in CH2Cl2,
acetone, less stable in CHCl3, benzene, decomposes fast
in Et2O. Stability in solutions under increased tempera-
ture: after heating in benzene up to about 60 8C it
partially decomposes into a red product. Anal. Calc. for
C68H55Cl2O2P3Ru2S2: C, 61.21; P, 6.96; Ru, 15.5; S,
4. Supplementary material
Crystallographic data have been deposited with the
Cambridge Crystallographic Data Centre as deposition
No. CCDC 175161. Copies of the data can be obtained,
free of charge, on application to The Director, CCDC,
12 Union Road, Cambridge CB2 1EZ, UK (Fax: ꢂ44-
1223-336033; e-mail: deposit@ccdc.cam.ac.uk or www:
http://www.ccdc.cam.ac.uk).
/
1
4.81%. Found: C, 61.21; P, 6.60; Ru, 15.6; S, 4.60. H-
NMR: (ppm), (300 MHz, 293 K): (CD2Cl2): 2,12 (s);
6.5ꢁ
31P-NMR: (CD2Cl2, 121.5 MHz, 293 K): 39.75 (dd, Jꢀ
12.2; Jꢀ15.9 Hz); 43,32 (dd, Jꢀ3.7; Jꢀ15.9); 52.28
(dd, Jꢀ12.2 Hz; Jꢀ
3.7 Hz); 13C-NMR: (CDCl3, 75.4
/
7.8 (m); (CDCl3): 2.14 (s); 5, 24 (s); 6.38ꢁ
/
7.60 (m).
/
/
/
/
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/
/
MHz, 293 K): 30.91 (s); 3.45 (s); 124.92 (s); 125.69 (s);
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/
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/
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3
˚
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31.24(2), cꢀ
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/
18.23(2) A, bꢀ
/
94.09(3)8, Vꢀ
/
6652(2) A ,
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/
/
Ka)ꢀ
/
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ꢀ
/
1.437 g
ꢀ
/
/
100
/
10, k: 00
/
20, l: 00
/
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/
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ꢄ3
˚
0.95 e A
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