Ring opening reactions of thiiranes by alkoxo- and aryloxo-gold(I) complexes

Article abstract of DOI:10.1039/a907574g

Alkoxo- and aryloxo-gold(I) complexes [Au(OR)L] [R = CH(CF₃)₂, L = PPh₃ 1a or PCy₃ 1b; R = Ph, L = PPh₃ 1c, PCy₃ 1d or PMe₃ 1e] smoothly reacted with ethylene sulfide to give the corresponding 2-(alkoxy- or -aryloxy)ethyl-sulfanylgold(I) complexes [Au(SCH₂CH₂OR)L] 2 at room temperature. Similar treatments of 1a-1e with propylene sulfide, isobutylene sulfide, or styrene sulfide selectively cleaved the less hindered C-S bond of thiiranes to give corresponding 2-(alkoxy- or -aryloxy)ethylsulfanylgold(I) complexes. Reactions of 1a with cis- and trans-2-butene sulfide gave syn- and anti-[Au(SCHMeCHMeOR)L], respectively, suggesting a mechanism involving an S_N2 type trans addition of alkoxogold(I) complexes toward thiiranes. The Royal Society of Chemistry 1999.

Full text of DOI:10.1039/a907574g

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Ring opening reactions of thiiranes by alkoxo- and aryloxo-gold(I)
complexes
Yoko Usui, Junko Noma, Masafumi Hirano and Sanshiro Komiya*
Department of Applied Chemistry, Faculty of Technology, Tokyo University of Agriculture and
Technology, 2-24-16 Nakacho, Koganei, Tokyo 184-8588, Japan. E-mail: komiya@cc.tuat.ac.jp;
Fax: ϩ81-42-387-7500
Received 20th September 1999, Accepted 29th October 1999
Alkoxo- and aryloxo-gold() complexes [Au(OR)L] [R = CH(CF3)2, L = PPh3 1a or PCy3 1b; R = Ph, L = PPh3 1c,
PCy3 1d or PMe3 1e] smoothly reacted with ethylene sulfide to give the corresponding 2-(alkoxy- or -aryloxy)ethyl-
sulfanylgold() complexes [Au(SCH2CH2OR)L] 2 at room temperature. Similar treatments of 1a–1e with propylene
sulfide, isobutylene sulfide, or styrene sulfide selectively cleaved the less hindered C–S bond of thiiranes to give
corresponding 2-(alkoxy- or -aryloxy)ethylsulfanylgold() complexes. Reactions of 1a with cis- and trans-2-butene
sulfide gave syn- and anti-[Au(SCHMeCHMeOR)L], respectively, suggesting a mechanism involving an SN2 type
trans addition of alkoxogold() complexes toward thiiranes.
room temperature resulted in ring opening giving the novel
Introduction
[2-(1,1,1,3,3,3-hexafluoro-2-propoxy)ethylsulfanyl]gold() com-
plex [Au{SC2H4OCH(CF3)2}(PPh3)] 2a in 66% yield. Results of
the reactions of alkoxo- and aryloxo-gold() complexes with
various thiiranes are summarised in Scheme 1 and Table 1.
The A2X2 pattern at δ 3.46 (t, JH-H = 7.9 Hz, 2 H) and 4.02 (t,
Alkoxo and aryloxo complexes of late transition metals have
received much attention because of their intrinsic ability as
tools in both stoichiometric and catalytic chemical transform-
ation.1 While the metal–oxygen bonds in early transition-metal
complexes are quite robust, those in late transition-metal
complexes are generally weak leading to high nucleophilicity of
their alkoxo and aryloxo ligands.2 Among these alkoxo and
aryloxo complexes of late transition metals, gold complexes
were less explored to date. We have reported syntheses and
chemical reactions of alkoxo- and aryloxo-gold-() and -()
complexes which are highly basic showing hydrogen bonding
with free alcohol,3 hydrogen abstraction from active methylene
compounds,4 and transition metal hydrides5 to give corre-
sponding alkyl and heterodinuclear gold complexes. These gold
complexes were also found to catalyse Knöevenagel reactions
of aryl aldehydes with active methylene compounds under
neutral and ambient conditions.6 As an extension of our con-
tinuous study on alkoxogold complexes, we focused on the
reactions with thiiranes. Thiiranes are considered to be versatile
starting chemicals toward various sulfur containing com-
pounds7 and are known to be polymerised by Lewis acids and
bases such as TiCl4 and KOH,7 and are desulfurised by tertiary
phosphines8 as well as by heating.9 Ring opening reactions of
thiiranes by primary alcohols are also known to be catalysed
by BF3 giving 2-alkoxyethanethiols,10 though their yields and
regio- and stereo-selectivities are poor. Although reactions of
transition-metal complexes with thiiranes have also been exten-
sively studied for desulfurisation,11 the introduction of a sulfur
atom into the complex,12 formation of a thiametallacycle,13 and
cyclooligomerisation,14 reactions of alkoxo and aryloxo com-
plexes of transition metals with thiiranes are still unexplored so
far. In this paper we report the regio- and stereo-selective ring
opening reactions of thiiranes by alkoxo- and aryloxo-gold()
complexes.
1
JH-H = 7.9 Hz, 2 H) in the H NMR spectrum of complex 2a
shows the presence of a couple of magnetically inequivalent
methylene groups suggesting cleavage of a C–S bond of ethyl-
ene sulfide. A septet at δ 3.42 (sep, JH-F = 6.6 Hz, 1 H) is assign-
able to the methine proton coupled to six equivalent fluorine
nuclei of the 1,1,1,3,3,3-hexafluoro-2-propoxy group. A singlet
at δ 36.8 in the 31P-{1H} NMR spectrum and multiplets
1
between δ 6.9 and 7.3 (15 H) in the H NMR indicate the
presence of the PPh3 ligand. Acidolysis of 2a with gaseous HCl
and the reaction of 2a with MeI gave HSC2H4OCH(CF3)2 and
MeSC2H4OCH(CF3)2 with concomitant formation of [AuCl-
(PPh3)]15 and [AuI(PPh3)]16 in quantitative yields, respectively.
These facts support the formation of 2a. Similar ring opening
reactions of ethylene sulfide by other alkoxo- or aryloxo-gold()
complexes [Au(OR)L] [R = CH(CF3)2, L = PCy3 1b; R = Ph,
L = PPh3 1c, PCy3 1d or PMe3 1e] proceeded to form corre-
sponding [2-(alkoxy- or aryloxy-)ethylthio]gold() complexes
having tertiary phosphine ligands, [Au(SC2H4OR)L]
[R = CH(CF3)2, L = PCy3 2b; R = Ph, L = PPh3 2c, PCy3 2d;
L = PMe3 2e].
When unsymmetric thiiranes such as propylene sulfide,
isobutylene sulfide and styrene sulfide were employed in this
reaction the ring opening took place at the less hindered
carbon with high regioselectivity. For example, the reaction of
1a with propylene sulfide gave a mixture of two regioisomers of
[Au{SCHMeCH2OCH(CF3)2}(PPh3)] 3a and [Au{SCH2-
CHMeOCH(CF3)2}(PPh3)] 3aЈ in 90:10 ratio. These complexes
could not be separated by recrystallisation because of their
similar solubility. They were characterised by NMR, elemental
analysis, and chemical reactions without isolation. The mixture
of 3a and 3aЈ coincidentally shows only one singlet at δ 40.0 in
1
31P-{1H} NMR. The H NMR spectrum of the major product
Results and discussion
Ring opening reaction of thiiranes by alkoxo- and aryloxo-gold(I)
complexes
3a shows a doublet at δ 1.80 (d, JH-H = 6.6 Hz, 3 H) and a
doublet of quartets of doublets at δ 3.94 (dqd, JH-H = 9.9, 6.6,
4.2 Hz, 1 H) assignable to the methyl and the methine protons,
respectively. Diastereotopic methylene protons appear as a trip-
let at δ 3.82 (t, JH-H = 9.9 Hz, 1 H) and a doublet of doublets at
The reaction of the (1,1,1,3,3,3-hexafluoro-2-propoxo)gold()
complex [Au{OCH(CF3)2}(PPh3)] 1a with ethylene sulfide at
J. Chem. Soc., Dalton Trans., 1999, 4397–4406
This journal is © The Royal Society of Chemistry 1999
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Scheme 1
Table 1 Yield of (2-alkoxyethylsulfanyl)gold() complexes and their
products MeSCHMeCH2OCH(CF3)2 and MeSCH2CHMe-
OCH(CF3)2 in 90:10 ratio with concomitant formation
regioselectivity in the ring opening reaction of unsymmetric thiirane
with alkoxo- or aryloxo-gold() complex
of [AuI(PPh3)] (99% yield), Scheme 2. These sulfides were
1
characterised by H NMR, GLC and GC-MS in which these
(2-Alkoxyethylsulfanyl)gold() complex
regioisomers were clearly distinguished by their fragmentation
patterns. Consistently, the reaction of the mixture of 3a and
3aЈ with HCl gas also gave HSCHMeCH2OCH(CF3)2 and
HSCH2CHMeOCH(CF3)2 in 90:10 ratio with formation of
[AuCl(PPh3)], quantitatively. These data suggest that 3a and
3aЈ are [Au{SCHMeCH2OCH(CF3)2}(PPh3)] and [Au{SCH2-
CHMeOCH(CF3)2}(PPh3)], respectively. Similarly, regioselec-
tive ring opening reaction of propylene sulfide by a series of the
alkoxo- and aryloxo-gold complexes 1b–1e gave [Au{SCH-
MeCH2OCH(CF3)2}(PCy3)]/[Au{SCH2CHMeOCH(CF3)2}-
(PCy3)] (3b:3bЈ = 82:18), [Au(SCHMeCH2OPh)(PPh3)]/[Au-
(SCH2CHMeOPh)(PPh3)] (3c:3cЈ = 67:33), [Au(SCHMeCH2-
OPh)(PCy3)]/[Au(SCH2CHMeOPh)(PCy3)] (3d:3dЈ = 87:13)
Product ratio
Complex
Substrate
Yield (%)
1a
1b
1c
1d
1e
47
88
65
73
100
90:10 (3a:3aЈ)
82:18 (3b:3bЈ)
67:33 (3c:3cЈ)
87:13 (3d:3dЈ)
68:32 (3e:3eЈ)
1a
1b
1c
1d
1e
88
94
74
52
95
98:2 (4a:4aЈ)
96:4 (4b:4bЈ)
98:2 (4c:4cЈ)
97:3 (4d:4dЈ)
86:14 (4e:4eЈ)
and
[Au(SCHMeCH2OPh)(PMe3)]/[Au(SCH2CHMeOPh)-
(PMe3)] (3e:3eЈ = 68:32). In all cases, the major products were
found to be the 1-methyl derivatives [Au(SCHMeCH2OR)L].
Ring opening reactions of other unsymmetrical thiiranes such
as isobutylene sulfide and styrene sulfide with 1a–1e similarly
proceeded to yield [(2-alkoxy-1,1-dimethyl)ethylsulfanyl]gold()
complexes 4a–4e and [2-alkoxy-1-phenyl)ethylsulfanyl]gold()
complexes 5a–5d as major products, respectively. These results
reveal that the alkoxo group dominantly attacks the less
hindered carbon atom of thiiranes in these ring opening
reactions. It is worthwhile to note that in the case of reactions
of unsymmetric thiiranes with alcohols the alkoxo group is
reported to attack the secondary or tertiary carbon atom of
thiiranes by a proton-induced mechanism.10
1a
1b
1c
1d
83
65
34
57
77:23 (5a:5aЈ)
97:3 (5b:5bЈ)
65:35 (5c:5cЈ)
73:27 (5d:5dЈ)
Conditions: thiirane = 1 equivalent per Au, r.t., solvent = thf, reaction
time = 4 h.
1
δ 4.32 (dd, JH-H = 9.9, 4.2 Hz, 1 H). Similarly the H NMR
spectrum of the minor species 3aЈ shows signals at δ 1.63 (d,
JH-H = 6.0 Hz, 3 H) for the methyl group, δ 3.18 (dd, JH-H
=
In order to obtain further insights concerning the ring
opening reaction, similar reactions with cis- and trans-2-butene
sulfide were carried out. As a typical example, the reaction
of complex 1c with cis-2-butene sulfide exclusively gave syn-
[Au(SCHMeCHMeOPh)(PPh3)] 6c in 89% yield, indicating
complete inversion at the carbon atom of cis-2-butene sulfide.
The two methine protons of 6c appeared at δ 4.37 (qd, J = 6.3,
3.3 Hz, 1 H) and 5.08 (qd, J = 6.3, 3.3 Hz, 1 H) in the 1H NMR
12.5, 9.3 Hz, 1 H) and 3.67 (dd, JH-H = 12.5, 3.9 Hz, 1 H) for
diastereotopic methylene protons, although the resonance of
the methine proton of the ethylthio fragment was obscured by
overlapping with the signals of the major species.
The regioselectivity of the reaction was further confirmed by
the following chemical reactions with this mixture. Treatment
with MeI in benzene afforded a mixture of the S-methylated
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Scheme 2
Table 2 Yield of syn- and anti-[2-(alkoxy- or -aryloxy-1,1-dimethyl)-
ethylsulfanyl]gold() complexes and their stereoselectivity in the ring
opening reaction of cis- or trans-2-butene sulfide with alkoxo- or
aryloxo-gold() complexes
[2-(Alkoxy- or -aryloxy-1,1-dimethyl)ethyl-
sulfanyl]gold() complex
Product ratio
Complex
Substrate
Yield (%)
1a
1b
1c
1d
1e
75
66
89
61
99
100:0 (6a:6aЈ)
100:0 (6b:6bЈ)
100:0 (6c:6cЈ)
100:0 (6d:6dЈ)
100:0 (6e:6eЈ)
Fig. 1 Effect of the concentration of isobutylene sulfide on the reac-
tions of [Au(OPh)(PPh3)] 1c with isobutylene sulfide. [1c] = 0.033 M,
[isobutylene sulfide] = 0.066 (᭹), 0.033 (᭡), 0.017 M (᭿), Ϫ10 ЊC,
solvent = toluene-d8.
1a
1b
1c
1d
1e
88
66
93
49
95
13:87 (6a:6aЈ)
12:88 (6b:6bЈ)
1:99 (6c:6cЈ)
5:95 (6d:6dЈ)
2:98 (6e:6eЈ)
Mechanism of the ring opening reaction
In order to shed some light on the reaction mechanism, time
courses of the reaction of alkoxo- or aryloxo-gold() complexes
with isobutylene sulfide were examined. The reactions were
a Conditions as in Table 1.
1
followed by H NMR with a thermostatted probe at Ϫ10 ЊC
spectrum, showing a typical syn vicinal coupling constant.17
On the other hand, reaction of 1c with trans-2-butene sulfide
yielded
using constant initial concentrations of gold complexes and
thiiranes under N2 in the presence of CHPh3 as an internal
standard.
a diastereomeric mixture of syn- and anti-[Au-
(SCHMeCHMeOPh)(PPh3)] 6c and 6cЈ, whose syn:anti ratio is
1:99. The two methine protons of the anti isomer 6cЈ were
observed at δ 4.10 (qd, J = 7.2, 6.6, 1 H) and 4.62 (dq, J = 6.6,
6.0 Hz, 1 H) in the 1H NMR spectrum, where the vicinal
coupling constant (J = 6.6 Hz) is clearly larger than that of 6c
(J = 3.3 Hz), suggesting the anti configuration. Other reactions
of cis- and trans-2-butene sulfide with 1b–1e also resulted in
inversion at the carbon of 2-butene sulfide with high selectivity,
suggesting an SN2 type mechanism for these ring opening
reactions (Table 2).
Without exception, reactions of complexes 1a–1e with cis-2-
butene sulfide exclusively gave syn forms 6a–6e, while those
with trans-2-butene sulfide gave diastereomeric mixtures
though anti forms 6aЈ–6eЈ were always dominant products. The
observed high stereoselectivity in the reaction of cis-2-butene
sulfide is most likely due to the smaller steric congestion at
the carbon of cis-2-butene sulfide than that of trans-2-butene
sulfide.
The relative initial rates of the reaction of complex 1c with
different concentrations of isobutylene sulfide are shown in
Fig. 1. When the concentration of isobutylene sulfide was
increased from 0.017 to 0.033 and 0.066 M the initial rate for
the formation of 4c increased approximately twice and three
times faster than that for 0.017 M, respectively. This fact
suggests that the ring opening reaction is first order in the con-
centration of thiirane. On the other hand, when the concen-
tration of 1c was increased from 0.017 to 0.033 and 0.066 M
in the presence of isobutylene sulfide (0.033 M) the initial
rate increased approximately by factors of 4 and 9, respectively
(Fig. 2).
This behaviour can be rationalised as second order rather
than first order in the concentration of aryloxogold complex.
Addition of KOPh (0.033 M) to a mixture of 1c (0.033 M) and
isobutylene sulfide (0.034 M) also increased the initial rate,
although KOPh itself is inactive for the ring opening reac-
tion of thiiranes under these conditions. The results suggest a
J. Chem. Soc., Dalton Trans., 1999, 4397–4406
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Fig. 4 Solvent effect for the reactions of [Au(OPh)(PPh3)] 1c with
Fig. 2 Effect of the concentration of aryloxogold() complex on the
reactions of [Au(OPh)(PPh3)] 1c with isobutylene sulfide. [1c] = 0.066
(᭹), 0.033 (᭡), 0.017 M (᭿), [isobutylene sulfide] = 0.034 M, Ϫ10 ЊC,
solvent = toluene-d8.
isobutylene sulfide. [1c] = 0.033 M, [isobutylene sulfide] = 0.034 M,
Ϫ10 ЊC, solvent = chloroform-d1 (᭹), toluene-d8 (᭡), thf-d8 (᭿), tetra-
hydrothiophene (᭺).
at δ 19.1 (half width = 136 Hz) in the 31P-{1H} NMR. This fact
indicates that the ligand exchange process, which is much faster
than the ring opening reaction, is taking place. However, the
observed chemical shift is far downfield in comparison with
that expected from the simple fast exchange between 1a and free
PPh3 (ca. δ 11.7). This suggests the associative formation of
unreactive [Au(OR)L2] species in the presence of free PPh3. If
the 31P chemical shift of [Au(OR)L2] is assumed to be similar
to that of 1a, approximately half of 1a is considered to be
converted into [Au(OR)L2], consistent with the observed
retardation effect of added PPh3. On the other hand, a possible
prior dissociation of PPh3 giving reactive species [Au(OR)]
is excluded, since addition of one equivalent PPh3 should
decrease such a minor dissociated species much more drastic-
ally under these conditions. (ii) As shown in Fig. 3, the reaction
rate is significantly dependent on the phosphine ligand in
gold() complex. Although PCy3 ligand is considered to be more
prone to dissociate than PMe3 due to its steric bulkiness, the
reaction rate of the PCy3 complex is slower, being inconsistent
with path a. This trend can be explained by prior association
of 1 with thiirane, where steric congestion at Au is larger in 1d
than 1e when thiirane co-ordinates. It is worth noting that
KOPh never reacts with thiiranes under these conditions. Thus,
thiirane is likely to co-ordinate to the alkoxogold() complex
giving [Au(OR)(thiirane)L] as a first step. The electron
donating phosphine ligand reduces the Lewis acidity of the
gold() complex, discouraging the co-ordination of thiirane.
Such initial co-ordination to the metal centre is also postulated
for the ring opening reaction of thiiranes promoted by Ir–Zr
and Ta complexes,12a,b and Adams and his co-workers14
reported isolation of a thiirane complex of tungsten. Therefore
prior co-ordination of thiiranes to the gold centre is considered
to be indispensable for the reaction. This is likely due to the
softness of the gold() fragment and the prior co-ordination
results in enhancement of electrophilicity of thiiranes. Com-
plete retardation in tetrahydrothiophene may be due to the
strong co-ordination ability of this solvent, preventing the prior
co-ordination of thiiranes to Au. Secondly, the external alkoxo
moiety of the alkoxogold complex or KOPh attacks the less
hindered carbon atom with inversion of configuration. This
may explain the second order dependence on the alkoxogold
complex concentration in the reaction. This would proceed via
an SN2 type mechanism because the stereochemistry at the
carbon of thiirane involves inversion of configuration. How-
ever, ionic dissociation of these alkoxides is less likely, since
no significant enhancement in polar solvent was observed. A
possible intramolecular concerted reaction is also excluded
for the ring opening reaction because this mechanism is incon-
sistent not only with the second order kinetics in the
concentration of alkoxogold() complexes, but also with the
Fig. 3 Ligand effect for the reactions of [Au(OPh)L] with isobutylene
sulfide. L = PPh3 (᭹), PCy3 (᭡), PMe3 (᭿). Other conditions as in
Fig. 2.
bimolecular process between co-ordinated thiirane and the
external alkoxide.
This reaction is strongly affected by the phosphine ligand
in the gold() complex (Fig. 3). Triphenylphosphine complex 1c
is the fastest, followed by trimethylphosphine complex 1e and
tricyclohexylphosphine complex 1d. The result may reflect
the importance of the electrophilicity of the gold() fragment to
co-ordinate the incoming thiirane. Addition of 1 equivalent of
PPh3 to the reaction mixture of 1c decreased the reaction rate
to approximately one third, suggesting the presence of a
prerequisite process such as dissociation of PPh3 or competitive
co-ordination of PPh3 and thiirane to the [Au(OR)(PPh3)]
complex (see below).
The reactions are significantly dependent on the solvent used
as seen in Fig. 4. The reaction is faster in chloroform-d1
(relative permittivity, εr = 4.81) than in toluene-d8 (εr = 2.38),
while tetrahydrofuran (thf)-d8 (εr = 7.20) significantly retarded
the reaction. It is worth noting that when tetrahydrothiophene
was employed as the solvent 1c remained unchanged.
From these kinetic results, a mechanism including co-
ordination of thiirane to Au has been proposed as shown in
Scheme 3. Suppression of the reaction by added PPh3 suggests
either dissociative path a or associative path b followed by the
ring opening reaction (see below). However, the dissociative
pathway (path a) is less likely because of the following reasons:
(i) the observed gold complexes were only the starting com-
pounds [Au(OR)L] 1, and the product complex [Au(SCH-
MeCHMeOR)L] under catalytic conditions throughout the
reaction according to 1H and 31P NMR. When 1 equivalent of
PPh3 was added to the reaction mixture at Ϫ10 ЊC, signals of 1c
(δ 27.8) and free PPh3 (δ Ϫ4.5) were observed as one broad peak
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J. Chem. Soc., Dalton Trans., 1999, 4397–4406

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Scheme 3
stereochemistry at the carbon of thiirane. Thus, a bimolecular
mixture was stirred at room temperature for 4 h. Then all
concerted mechanism (Scheme 3) is proposed for the ring open-
ing reaction.
As a summary, selective ring opening reactions of thiiranes
have been achieved by alkoxo- and aryloxo-gold complexes to
give new 2-(alkoxy- or aryloxy-)ethylsulfanylgold() complexes
under ambient conditions.
volatile matters were removed under reduced pressure and the
resulting white powder was washed with hexane and then
dried in vacuo. Recrystallisation of the residue from diethyl
ether–hexane gave a white powder of [Au{SCH2CH2OCH-
(CF3)2}(PPh3)] 2a (93.4 mg, 0.15 mmol, 66%). 1H NMR
3
(C6D6) δ 3.42 (sep, JH-F = 6.6, 1 H, CH(CF3)2), 3.46 (t,
3
3JH-H = 7.9, 2 H, SCH2CH2O), 4.02 (t, JH-H = 7.9 Hz, 2 H,
SCH2CH2O) and 6.9–7.3 (m, 15 H, PPh3); 31P-{1H} NMR
(C6D6) δ 36.8 (s); IR (KBr, cmϪ1) 1480m, 1435m, 1374s, 1293s,
1227m, 1186s and 982m; mp (decomp.) 124–125 ЊC; Found:
C, 40.55; H, 3.00; S, 4.36. Calc. for C23H20AuF6OPS: C, 40.25;
H, 2.94; S, 4.67%.
Experimental
All manipulations were performed under dry nitrogen using
standard Schlenk and vacuum-line techniques unless otherwise
noted. Benzene, toluene and hexane were dried over anhydrous
calcium chloride, Et2O and thf over calcium hydride and dis-
tilled from potassium–benzophenone or sodium wire prior to
use. Dimethyl sulfoxide (dmso) and tetrahydrothiophene were
dried over calcium hydride and distilled under reduced pressure,
and then kept under a nitrogen atmosphere. Chloroform was
dried over P2O5, and distilled under vacuum prior to use.
Alkoxo- and aryloxo-gold() complexes 1a–1e were prepared
according to the procedure published in our previous papers.3–6
Ethylene sulfide was purchased from Aldrich and used as
received. Other sulfides such as propylene sulfide, isobutylene
sulfide, styrene sulfide, and cis- and trans-2-butene sulfides were
prepared from corresponding epoxides by using the literature
[Au{SCH2CH2OCH(CF3)2}(PCy3)] 2b. From complex 1b
(22.2 mg, 0.034 mmol) and ethylene sulfide (0.002 10 cm3, 0.035
mmol). Yield 18.7 mg, 0.026 mmol, 77%. 1H NMR (C6D6)
3
δ 0.90–1.75 (m, 33 H, PCy3), 3.52 (t, JH-H = 7.8, 2 H,
3
SCH2CH2O), 3.59 (sep, JH-F = 6.0, 1 H, CH(CF3)2) and 4.13
3
(t, JH-H = 7.8 Hz, 2 H, SCH2CH2O); 31P-{1H} NMR (C6D6)
δ 57.0 (s); mp (decomp.) 135–136 ЊC; Found: C, 39.68; H, 5.01;
S, 4.51. Calc. for C23H28AuF6OPS: C, 39.21; H, 5.44; S, 4.55%.
[Au(SCH2CH2OPh)(PPh3)] 2c. From complex 1c (31.4 mg,
0.057 mmol) and ethylene sulfide (0.0064 cm3, 0.065 mmol).
Yield 25.4 mg, 0.041 mmol, 73%. 1H NMR (C6D6) δ 3.79
3
3
(t, JH-H = 7.5, 2 H, SCH2CH2O), 4.47 (t, JH-H = 7.5 Hz, 2 H,
SCH2CH2O) and 6.8–7.4 (m, 20 H, PPh3 and OPh); 31P-{1H}
NMR (C6D6) δ 35.7 (s); mp (decomp.) 159–160 ЊC; Found: C,
50.86; H, 4.06; S, 5.26. Calc. for C26H24AuOPS: C, 50.99; H,
3.95; S, 5.24%.
1
method.8 The H and 31P-{1H} NMR spectra were recorded
on a JEOL LA-300 (1H, 300.4 MHz; 31P, 121.55 MHz)
spectrometer and chemical shifts are reported in ppm from
1
tetramethylsilane and from external 85% H3PO4 for H and
31P-{1H} NMR spectra, respectively. The IR spectra were
recorded on a JASCO FT/IR-410 spectrometer. GLC analyses
were performed with Shimadzu GC-8A or 14B gas liquid phase
chromatographs using a glass packed PEG-20M or capillary
TC-wax column with a flame ionisation detector. GC-MS
spectra were recorded on a Shimadzu QP-2000 instrument at
70 eV. Elemental analyses were performed by a Perkin-Elmer
2400 series II CHNS analyser. Melting points were measured
by a YAMATO MP-21 apparatus, and the values were
uncorrected.
[Au(SCH2CH2OPh)(PCy3)] 2d. From complex 1d (15.3 mg,
0.027 mmol) and ethylene sulfide (0.0016 cm3, 0.027 mmol).
1
Yield 10.0 mg, 0.016 mmol, 66%. H NMR (C6D6) δ 1.0–1.8
3
(m, 33 H, PCy3), 3.84 (t, JH-H = 8.1, 2 H, SCH2CH2O), 4.56
3
3
(t, JH-H = 8.1,
2
H, SCH2CH2O), 7.22 (dd, JH-H = 7.8,
3JH-P = 6.9, 2 H, o-H of OPh), 7.02 (t, 3JH-H = 7.8, 2 H, m-H of
OPh) and 6.84 (t, JH-H = 7.8 Hz, 1 H, p-H of OPh); 31P-{1H}
3
NMR (C6D6) δ 54.5 (s); IR (KBr, cmϪ1) 2924s, 2849s, 1587m,
1484m, 1446m, 1238m and 1004m; mp (decomp.) 162–163 ЊC;
Found: C, 49.79; H, 6.84; S, 5.22. Calc. for C26H42AuOPS: C,
49.52; H, 6.71; S, 5.08%.
[Au(SCH2CH2OPh)(PMe3)] 2e. From complex 1e (9.5 mg,
0.025 mmol) and ethylene sulfide (0.001 50 cm3, 0.025 mmol).
Yield 0.025 mmol, 99%. 1H NMR (C6D6) δ 0.609 (d,
2JH-P = 10.2, 9 H, PMe3), 3.74 (t, 3JH-H = 7.5, 2 H, SCH2CH2O),
4.47 (t, 3JH-H = 7.5, 2 H, SCH2CH2O), 7.1–7.4 (m, 4 H, o-, m-H
of OPh) and 6.81 (t, 1 H, 3JH-H = 7.2 Hz, p-H of OPh). 31P-{1H}
NMR (C6D6) δ Ϫ0.98 (s).
Reactions of alkoxo- and aryloxo-gold(I) complexes
With ethylene sulfide. As a typical example, the reaction of
[Au{OCH(CF3)2}(PPh3)] 1a with ethylene sulfide giving
[Au{SCH2CH2OCH(CF3)2}(PPh3)] 2a is described. Ethylene
sulfide (0.0150 cm3, 0.250 mmol) was added to a thf solution
(5 cm3) of complex 1a (147.7 mg, 0.236 mmol) and the reaction
J. Chem. Soc., Dalton Trans., 1999, 4397–4406
4401

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2
With propylene sulfide. From the reaction of complex 1a
(107.0 mg, 0.171 mmol) with propylene sulfide (0.0140 cm3,
0.18 mmol) followed by similar work up to that described
above, two regioisomers [Au{SCHMeCH2OCH(CF3)2}(PPh3)]
3a and [Au{SCH2CHMeOCH(CF3)2}(PPh3)] 3aЈ were obtained
in 90:10 ratio, respectively. Yield 56.0 mg, 0.80 mmol, 47%. 3a:
CH2O), 4.15 (t, JH-H = 3JH-H = 9.3, 1 H, SCHMeCH2O), 4.22
2 3
(dqd, JH-H = 9.3, JH-H = 6.0, 3.6, 1 H, SCHMeCH2O), 4.66
3
2
(dd, JH-H = 9.3, 3.6, 1 H, SCHMeCH2O), 4.22 (dqd, JH-H
=
9.3, 3JH-H = 6.0, 3.8 Hz, 1 H, SCHMeCH2O) and 7.0–7.4 (m, 5
H, OPh); 31P-{1H} NMR (C6D6) δ Ϫ2.12 (s). 3eЈ: H NMR
1
2
3
(C6D6) δ 0.60 (d, JH-P = 10.5, 9 H, PMe3), 1.73 (d, JH-H = 6.3,
3
2
3
1H NMR (C6D6) δ 1.80 (d, JH-H = 6.6, 3 H, SCHMeCH2O),
3 H, SCH2CHMeO), 3.35 (dd, JH-H = 12.5, JH-H = 8.4, 1 H,
2 3
3
2
3.42 (sep, JH-F = 6.0,
1
H, CH(CF3)2), 3.82 (t, JH-H
=
SCH2CHMeO), 3.75 (dqd, JH-H = 12.5, JH-H = 8.4, 3.9, 1 H,
2 3
2
3JH-H = 9.9,
1
H, SCHMeCH2O), 3.94 (dqd, JH-H = 9.9,
SCH2CHMeO) and 3.83 (dd, JH-H = 12.6, JH-H = 3.9 Hz,
1 H, SCH2CHMeO); 31P-{1H} NMR (C6D6) δ Ϫ2.12 (s).
3JH-H = 6.6, 4.2, 1 H, SCHMeCH2O), 4.32 (dd, JH-H = 9.9, 4.2
3
Hz, 1 H, SCHMeCH2O) and 6.8–7.3 (m, 15 H, PPh3); 31P-{1H}
NMR (C6D6) δ 40.0 (s). 3aЈ: 1H NMR (C6D6) δ 1.63 (d,
With isobutylene sulfide. From the reaction of complex 1a
(101.4 mg, 0.161 mmol) and isobutylene sulfide (0.0140 cm3,
0.18 mmol) followed by similar work-up to that described
above, [Au{SCMe2CH2OCH(CF3)2}(PPh3)] 4a and [Au{SCH2-
CMe2OCH(CF3)2}(PPh3)] 4aЈ were obtained in 98:2 ratio,
respectively. Yield 101.0 mg, 0.141 mmol, 87.8%. 4a: 1H NMR
3JH-H = 6.0,
3
H, SCH2CHMeO), 3.18 (dd, JH-H = 12.5,
2
3JH-H = 9.3, 1 H, SCH2CHMeO) and 3.67 (dd, JH-H = 12.5,
3JH-H = 3.9 Hz, 1 H, SCH2CHMeO); the two methine protons in
the S{CH(CH3)CH2OCH(CF3)2} fragment and phenyl protons
are obscured by overlapping with the signals of the major
2
species 3a; 31P-{1H} NMR (C6D6) δ 40.0 (s); IR (KBr, cmϪ1
)
(C6D6) δ 1.92 (s, 6 H, SCMe2CH2O), 3.42 (sep, JH-F = 6.0 Hz,
3
1480m, 1460m, 1294s, 1232s, 1188s, 1101s and 980s; mp
(decomp.) 189–190 ЊC; Found C, 40.95; H, 2.98; S, 4.79; Calc.
for C24H22AuF6OPS C, 41.15; H, 3.17; S, 4.58%.
OCH(CF3)2), 4.12 (s, 2 H, SCMe2CH2O) and 6.8–7.3 (m, 15 H,
1
PPh3); 31P-{1H} NMR (C6D6) δ 39.9 (s). 4aЈ: H NMR (C6D6)
δ 1.64 (s, 6 H, SCH2CMe2O), 3.84 (s, 2 H, SCH2CMe2O) and
3
[Au{SCHMeCH2OCH(CF3)2}(PCy3)] 3b and [Au{SCH2CH-
MeOCH(CF3)2}(PCy3)] 3bЈ. From complex 1b (29.2 mg, 0.045
mmol) and propylene sulfide (0.003 60 cm3, 0.046 mmol). Yield
28.2 mg, 0.040 mmol, 88%. 3b:3bЈ = 82:18. 3b: 1H NMR
4.38 (sep, JH-F = 6.0 Hz, OCH(CF3)2); 31P-{1H} NMR (C6D6)
δ 39.9 (s); IR (KBr, cmϪ1) 1480m, 1435m, 1297s, 1230s, 1188m,
1109s and 998m; mp (decomp.) 163–164 ЊC; Found C, 42.25; H,
3.40; S, 4.45; Calc. for C25H24AuF6OPS C, 42.03; H, 3.39; S,
4.49%.
3
(C6D6) δ 0.8–1.7 (m, 33 H, PCy3), 1.81 (d, JH-H = 6.3, 3 H,
2
SCHMeCH2O), 3.82 (t, JH-H = 3JH-H = 9.6, 1 H, SCHMe-
[Au{SCMe2CH2OCH(CF3)2}(PCy3)] 4b and [Au{SCH2-
CMe2OCH(CF3)2}(PCy3)] 4bЈ. Reaction of complex 1b (23.1
mg, 0.035 mmol) with isobutylene sulfide (0.0035 cm3, 0.036
mmol). Yield 24.9 mg, 0.034 mmol, 94%. 4b:4bЈ = 96:4. 4b: 1H
NMR (C6D6) δ 0.9–1.7 (m, 33 H, PCy3), 1.94 (s, 6 H, SCMe2-
CH2O), 4.01 (dqd, 3JH-H = 9.6, 6.3, 4.9, 1 H, SCHMeCH2O) and
2
3
4.29 (dd, JH-H = 9.6, JH-H = 6.9 Hz, 1 H, SCHMeCH2O);
31P-{1H} NMR (C6D6) δ 57.0 (s). 3bЈ: H NMR (C6D6) δ 1.89
1
(d, 3JH-H = 6.3, 3 H, SCH2CHMeO), 3.84 (t, 2JH-H = 3JH-H = 9.5,
2
3
3
1 H, SCH2CHMeO) and 4.31 (dd, JH-H = 9.5, JH-H = 4.2 Hz,
1 H, SCH2CHMeO); 31P-{1H} NMR (C6D6) δ 57.0 (s); IR (KBr,
cmϪ1) 2929s, 2854s, 1448m, 1377m, 1286s, 1214s, 1191s, 1102s
and 978s; mp (decomp.) 175–176 ЊC; Found C, 40.18; H, 5.85;
S, 4.67; Calc. for C24H40AuF6OPS C, 40.12; H, 5.61; S, 4.46%.
[Au(SCHMeCH2OPh)(PPh3)] 3c and [Au(SCH2CHMe-
OPh)(PPh3)] 3cЈ. From complex 1c (42.1 mg, 0.077 mmol) and
propylene sulfide (0.0060 cm3, 0.077 mmol). Yield, 30.8 mg,
CH2O), 3.58 (sep, JH-F = 6.0, OCH(CF3)2) and 4.13 (s, 2 H,
SCMe2CH2O); 31P-{1H} NMR (C6D6) δ 57.0 (s). 4bЈ: 1H NMR
3
(C6D6) δ 3.76 (s, 2 H, SCH2CMe2O) and 4.62 (sep, JH-F
=
6.0 Hz, OCH(CF3)2); 31P-{1H} NMR (C6D6) δ 57.0 (s); mp
(decomp.) 147–148 ЊC; Found C, 40.88; H, 5.74; S, 4.68; Calc.
for C25H42AuF6OPS C, 40.99; H, 5.78; S, 4.38%.
[Au(SCMe2CH2OPh)(PPh3)] 4c and [Au(SCH2CMe2OPh)-
(PPh3)] 4cЈ. From complex 1c (36.2 mg, 0.065 mmol) and iso-
butylene sulfide (0.006 4 cm3, 0.065 mmol). Yield 31.4 mg, 0.048
mmol, 74%. 4c:4cЈ = 98:2. 4c: 1H NMR (C6D6) δ 2.00 (s, 6 H,
SCMe2CH2O), 4.48 (s, 2 H, SCMe2CH2O) and 6.7–7.3 (m, 20
H, OPh, PPh3); 31P-{1H} NMR (C6D6) δ 40.0 (s). 4cЈ: 1H NMR
(C6D6) δ 1.64 (s, 6 H, SCH2CMe2O) and 3.79 (s, 2 H, SCH2-
1
0.050 mmol, 65%. 3c:3cЈ = 67:33. 3c: H NMR (C6D6) δ 1.93
(d, 3JH-H = 6.6, 3 H, SCHMeCH2O), 4.22 (t, 2JH-H = 3JH-H = 9.4,
2
3
1 H, SCHMeCH2O), 4.31 (dqd, JH-H = 9.4, JH-H = 6.6, 3.9,
3
1 H, SCHMeCH2O), 4.74 (dd, JH-H = 3.9 Hz, 2 H, SCHMe-
CH2O) and 6.7–7.3 (m, 20 H, OPh, PPh3); 31P-{1H} NMR
(C6D6) δ 40.0 (s). 3cЈ: 1H NMR (C6D6) δ 1.84 (d, 3JH-H = 5.7, 3 H,
CMe2O); 31P-{1H} NMR (C6D6) δ 40.0 (s); IR (KBr, cmϪ1
)
2
3
SCH2CHMeO), 3.41 (dd, JH-H = 12.7, JH-H = 8.4, 1 H, SCH2-
1597m, 1580m, 1491m, 1435m, 1240m and 985m; mp (decomp.)
139–140 ЊC; Found C, 52.44; H, 4.46; S, 5.39; Calc. for C28H28-
AuOPS C, 52.50; H, 4.41; S, 5.01%.
2
3
CHMeO) and 3.89 (dd, JH-H = 12.7, JH-H = 3.6 Hz, 1 H,
SCH2CHMeO); 31P-{1H} NMR (C6D6) δ 40.0 (s); mp (decomp.)
153–154 ЊC; Found C, 52.09; H, 4.12; S, 5.09; Calc. for C27H26-
AuOPS C, 51.76; H, 4.18; S, 5.12%.
[Au(SCMe2CH2OPh)(PCy3)] 4d and [Au(SCH2CMe2OPh)-
(PCy3)] 4dЈ. From complex 1d (20.3 mg, 0.035 mmol) and iso-
butylene sulfide (0.0035 cm3, 0.035 mmol). Yield 12.1 mg, 0.018
[Au(SCHMeCH2OPh)(PCy3)] 3d and [Au(SCH2CHMe-
OPh)(PCy3)] 3dЈ. From complex 1d (20.9 mg, 0.037 mmol) and
propylene sulfide (0.0030 cm3, 0.038 mmol). Yield 18.3 mg,
1
mmol, 52%. 4d:4dЈ = 97:3. 4d: H NMR (C6D6) δ 0.9–1.7 (m,
33 H, PCy3), 2.13 (s, 6 H, SCMe2CH2O), 4.52 (s, 2 H, SCMe2-
1
0.027 mmol, 73%. 3d:3dЈ = 87:13. 3d: H NMR (C6D6) δ 0.9–
CH2O) and 6.8–7.2 (m, 5 H, OPh); 31P-{1H} NMR (C6D6)
3
1
1.7 (m, 33 H, PCy3), 1.98 (d, JH-H = 6.0, 3 H, SCHMeCH2O),
δ 56.8 (s). 4dЈ: H NMR (C6D6) δ 3.67 (s, SCH2CMe2O); 31P-
2
4.22 (t, JH-H = 3JH-H = 9.2, 1 H, SCHMeCH2O), 4.31 (dqd,
{1H} NMR (C6D6) δ 56.8 (s); mp (decomp.) 142–143 ЊC; Found
C, 50.98; H, 7.23; S, 4.66; Calc. for C28H46AuOPS C, 51.06; H,
7.04; S, 4.87%.
3
2JH-H = 9.2, JH-H = 6.0, 3.8, 1 H, SCHMeCH2O), 4.79 (dd,
3
3JH-H = 9.2, 3.8, 1 H, SCHMeCH2O), 6.81 (t, JH-H = 7.8 Hz,
1 H, p-H of OPh) and 7.0–7.2 (m, 4 H, o-, m-H of OPh); 31P-
[Au(SCMe2CH2OPh)(PMe3)] 4e and [Au(SCH2CMe2OPh)-
(PMe3)] 4eЈ. From complex 1e (11.1 mg, 0.020 mmol) and iso-
butylene sulfide (0.0020 cm3, 0.020 mmol). Yield 0.019 mmol,
95%. 4e:4eЈ = 86:14. 4e: 1H NMR (C6D6) δ 0.74 (d, 2JH-P = 10.2
Hz, 9 H, PMe3), 1.92 (s, 6 H, SCMe2CH2O), 4.33 (s, 2 H,
CMe2CH2O) and 6.8–7.3 (m, 5 H, OPh); 31P-{1H} NMR (C6D6)
δ Ϫ10.3 (s). 4eЈ: 1H NMR (C6D6) δ 0.74 (d, 2JH-P = 10.2 Hz, 9 H,
PMe3), 1.63 (s, 6 H, SCH2CMe2OPh) and 3.57 (s, 2 H, CMe2-
CH2O); 31P-{1H} NMR (C6D6) δ Ϫ10.3 (s).
1
{1H} NMR (C6D6) δ 56.8 (s). 3dЈ: H NMR (C6D6) δ 1.84 (d,
2
3JH-H = 5.7,
3
H, SCH2CHMeO), 3.41 (dd, JH-H = 12.3,
2
3JH-H = 3.3, 1 H, SCH2CHMeO) and 4.02 (dd, JH-H = 12.3,
3JH-H = 9.3 Hz, 1 H, SCH2CHMeO); 31P-{1H} NMR (C6D6)
δ 56.8 (s); mp (decomp.) 112–113 ЊC; Found C, 50.86; H, 6.78;
S, 5.03; Calc. for C27H44AuOPS C, 50.31; H, 6.88; S, 4.97%.
[Au(SCHMeCH2OPh)(PMe3)] 3e and [Au(SCH2CHMe-
OPh)(PMe3)] 3eЈ. From complex 1e (10.0 mg, 0.026 mmol) and
propylene sulfide (0.0021 cm3, 0.027 mmol). Yield 0.026
1
mmol, 100%. 3e:3eЈ = 68:32. 3e: H NMR (C6D6) δ 0.60 (d,
With styrene sulfide. From the reaction of complex 1a
(70.3 mg, 0.101 mmol) with styrene sulfide (15.5 mg, 0.11
2JH-P = 10.5, 9 H, PMe3), 1.90 (d, JH-H = 6.0, 3 H, SCHMe-
3
4402
J. Chem. Soc., Dalton Trans., 1999, 4397–4406

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3
mmol) followed by similar work-up to that described above,
[Au{SCHPhCH2OCH(CF3)2}(PPh3)] 5a and [Au{SCH2CH-
PhOCH(CF3)2}(PPh3)] 5aЈ were obtained in 77:23 ratio,
4.31 (qd, JH-H = 8.0, 3.9 Hz, 1 H, CHMe). 31P-{1H} NMR
(C6D6) δ 57.1 (s); mp (decomp.) 144–145 ЊC; Found: C, 41.32;
H, 5.54; S, 4.32. Calc. for C25H42AuF6OPS: C, 40.99; H, 5.78; S,
4.38%.
1
respectively. Yield 69.4 mg, 0.091 mmol, 83%. 5a: H NMR
(C6D6) δ 3.74 (dd, 3JH-H = 12.9, 3JH-H = 9.0, 1 H, SCHPhCH2O),
syn-[Au(SCHMeCHMeOPh)(PPh3)] 6c. From complex 1c
(49.3 mg, 0.089 mmol) and cis-2-butene sulfide (0.0086 cm3,
0.091 mmol). Yield 51.0 mg, 0.080 mmol, 89%. 1H NMR
(C6D6) δ 1.70 (d, 3JH-H = 6.3, 6 H, CHMe), 4.37 (qd, 3JH-H = 6.3,
2
3
4.02 (dd, JH-H = 12.9, JH-H = 4.8, 1 H, SCHPhCH2O), 4.16
3
2
(sep, JH-F = 6.3, 1 H, OCH(CF3)2), 5.02 (dd, JH-H = 9.0,
3JH-H = 4.8 Hz, 1 H, SCHPhCH2O) and 6.9–7.8 (m, 20 H,
SCHPhCH2O, PPh3); 31P-{1H} NMR (C6D6) δ 37.29 (s). 5aЈ: 1H
3
3.3, 1 H, SCHMe), 5.08 (qd, JH-H = 6.3, 3.3 Hz, 1 H, CHMe)
2
3
NMR (C6D6) δ 4.58 (dd, JH-H = 9.0, JH-H = 4.5, 1 H, SCH2-
and 6.7–7.5 (m, 20 H, OPh, PPh3). 31P-{1H} NMR (C6D6)
δ 36.0 (s); mp (decomp.) 171–172 ЊC; Found: C, 52.38; H, 4.58;
S, 5.10. Calc. for C28H28AuOPS: C, 52.50; H, 4.41; S, 5.01%.
syn-[Au(SCHMeCHMeOPh)(PCy3)] 6d. From complex 1d
(20.3 mg, 0.035 mmol) and cis-2-butene sulfide (0.0033 cm3,
0.035 mmol). Yield 14.1 mg, 0.021 mmol, 61%. 1H NMR
3
CHPhO) and 4.45 (sep, JH-F = 5.4 Hz, 1 H, OCH(CF3)2);
31P-{1H} NMR (C6D6) δ 37.29 (s). mp (decomp.) 127–128 ЊC;
Found C, 46.06; H, 3.04; S, 4.30; Calc. for C29H24AuF6OPS C,
45.68; H, 3.17; S, 4.21%.
[Au{SCHPhCH2OCH(CF3)2}(PCy3)] 5b and [Au{SCH2CH-
PhOCH(CF3)2}(PCy3)] 5bЈ. From complex 1b (69.0 mg, 0.11
mmol) and styrene sulfide (16.3 mg, 0.12 mmol). Yield 54.6 mg,
0.70 mmol, 65%. 5b:5bЈ = 97:3. 5b: 1H NMR (C6D6) δ 0.7–1.7
3
(C6D6) δ 0.9–1.7 (m, 33 H, PCy3), 1.72 (d, JH-H = 6.9, 3 H,
CHMe), 1.83 (d, 3JH-H = 6.0, 3 H, CHMe), 4.43 (qd, 3JH-H = 6.0,
3
3.3, 1 H, CHMe), 5.13 (qd, JH-H = 6.9, 3.3, 1 H, CHMe), 6.81
3
3
(m, 33 H, PCy3), 3.72 (dd, JH-H = 12.8, JH-H = 7.9, 1 H,
(t, 3JH-H = 6.8, 1 H, p-H of OPh), 7.02 (t, 3JH-H = 6.8, 2 H, m-H
of OPh) and 7.19 (t, 3JH-H = 6.8 Hz, 2 H, o-H of OPh). 31P-{1H}
NMR (C6D6) δ 56.9 (s); mp (decomp.) 129–130 ЊC; Found: C,
50.89; H, 7.13; S, 4.92. Calc. for C28H46AuOPS: C, 51.06; H,
7.04; S, 4.87%.
2
3
SCHPhCH2O), 4.03 (dd, JH-H = 12.8, JH-H = 5.1,
1 H,
3
SCHPhCH2O), 4.16 (sep, JH-F = 6.3, 1 H, OCH(CF3)2), 5.08
(dd, 2JH-H = 7.9, 3JH-H = 5.1 Hz, 1 H, SCHPhCH2O) and 7.0–7.5
(m, 5 H, CHPh); 31P-{1H} NMR (C6D6) δ 54.24 (s). 5bЈ: H
1
NMR (C6D6) δ 4.35 (t, 2JH-H = 3JH-H = 10.2, 1 H, SCH2CHPhO)
and 4.97 (dd, 2JH-H = 10.2, 3JH-H = 4.5 Hz, 1 H, SCH2CHPhO);
31P-{1H} NMR (C6D6) δ 54.24 (s); mp (decomp.) 156–157 ЊC;
Found C, 44.99; H, 5.74; S, 4.25; Calc. for C29H42AuF6OPS C,
44.62; H, 5.42; S, 4.11%.
syn-[Au(SCHMeCHMeOPh)(PMe3)] 6e. From complex 1e
(9.6 mg, 0.025 mmol) and cis-2-butene sulfide (0.0026 cm3,
1
0.027 mmol). Yield 0.025 mmol, 99%. H NMR (C6D6) δ 0.57
2
3
(d, JH-P = 10.5, 9 H, PMe3), 1.74 (d, JH-H = 3.6, 6 H, CHMe),
4.27 (qd, 3JH-H = 6.9, 3.0, 1 H, CHMe), 5.03 (qd, 3JH-H = 6.9, 3.6
Hz, 1 H, CHMe) and 6.8–7.2 (m, 5 H, OPh). 31P-{1H} NMR
(C6D6) δ Ϫ0.41s.
[Au(SCHPhCH2OPh)(PPh3)] 5c and [Au(SCH2CHPhOPh)-
(PPh3)] 5cЈ. From complex 1c (68.9 mg, 0.12 mmol) and styrene
sulfide (18.3 mg, 0.13 mmol). Yield 28.1 mg, 0.041 mmol, 34%.
2
5c:5cЈ = 65:35. 5c: 1H NMR (C6D6) δ 3.82 (dd, JH-H
=
With trans-2-butene sulfide. From the reaction of complex 1a
(92.3 mg, 0.147 mmol) and trans-2-butene sulfide (0.0160 cm3,
0.150 mmol) followed by similar work-up to that described
3
3
12.9, JH-H = 6.9, 1 H, SCHPhCH2O), 4.60 (t, JH-H = 6.9, 1 H,
2
3
SCHPhCH2O), 5.08 (dd, JH-H = 12.9, JH-H = 6.9 Hz, 1 H,
SCHPhCH2O) and 6.9–7.8 (m, 25 H, SCHPhCH2O, OPh,
above,
a mixture of syn-[Au{SCHMeCHMeOCH(CF3)2}-
PPh3); 31P-{1H} NMR (C6D6) δ 38.3 (s). 5cЈ: H NMR (C6D6)
(PPh3)] 6a and anti-[Au{SCHMeCHMeOCH(CF3)2}(PPh3)]
1
2
3
δ 3.55 (dd, JH-H = 12.3, JH-H = 9.3, 1 H, SCH2CHPhO) and
6aЈ was obtained in 13:87 ratio, respectively. Yield 93.2 mg,
2
3
1
3
4.12 (dd, JH-H = 12.3, JH-H = 7.2 Hz, 1 H, SCH2CHPhO);
31P-{1H} NMR (C6D6) δ 38.3 (s); mp (decomp.) 166–167 ЊC.
[Au(SCHPhCH2OPh)(PCy3)] 5d and [Au(SCH2CHPhOPh)-
(PCy3)] 5dЈ. From complex 1d (20.5 mg, 0.036 mmol) and
styrene sulfide (5.04 mg, 0.037 mmol). Yield 14.5 mg, 0.020
mmol, 57%. 5d:5dЈ = 73:27. 5d: 1H NMR (C6D6) δ 0.7–1.7
(m, 33 H, PCy3), 3.72 (dd, 3JH-H = 12.8, 3JH-H = 7.9, 1 H, SCHPh-
CH2O), 4.03 (dd, 2JH-H = 12.8, 3JH-H = 5.1, 1 H, SCHPhCH2O),
0.13 mmol, 88%. 6aЈ: H NMR (C6D6) δ 1.62 (d, JH-H = 5.4,
3
3 H, SCHMeCHMeO), 2.01 (d, JH-H = 5.7, 3 H, SCHMeCH-
MeO), 3.84 (sep, 3JH-F = 6.0 Hz, 1 H, OCH(CF3)2), 3.72 (m, 2 H,
CHMe), 6.8–6.9 (m, 9 H, m-, p-H of OPh) and 7.2–7.3 (m, 6 H,
o-H of Ph). 31P-{1H} NMR (C6D6) δ 39.8 (s). Following data
were measured for the mixture of 6a and 6aЈ. IR (KBr, cmϪ1):
1463m, 1438m, 1286s, 1235m, 1210s, 1101s and 967m; mp
(decomp.) 138–139 ЊC; Found: C, 42.16; H, 3.25; S, 4.68%.
syn-[Au{SCHMeCHMeOCH(CF3)2}(PCy3)] 6b and anti-
[Au{SCHMeCHMeOCH(CF3)2}(PCy3)] 6bЈ. From complex 1b
(50.0 mg, 0.078 mmol) and trans-2-butene sulfide (0.0100 cm3,
0.080 mmol). Yield 48.3 mg, 0.065 mmol, 66%. 6b:6bЈ = 12:88.
2
3
5.08 (dd, JH-H = 7.9, JH-H = 5.1 Hz, 1 H, SCHPhCH2O) and
6.9–7.4 (m, 10 H, SCHPhCH2O, OPh); 31P-{1H} NMR (C6D6)
δ 53.8 (s) 5dЈ: H NMR (C6D6) δ 4.35 (t, JH-H = 3JH-H = 10.2,
1
2
2
3
1 H, SCH2CHPhO) and 4.97 (dd, JH-H = 10.2, JH-H = 4.5 Hz,
1 H, SCH2CHPhO); 31P-{1H} NMR (C6D6) δ 53.8 (s); mp
(decomp.) 134–135 ЊC.
1
6bЈ: H NMR (C6D6) δ 0.8–1.7 (m, 39 H, CHMe, PCy3), 3.78
3
3
(qui, JH-H = 6.3, 1 H, SCHMeCHMeO), 3.94 (qui, JH-H = 6.0,
3
1 H, SCHMeCHMeO) and 4.13 (sep, JH-F = 6.0 Hz, 1 H,
With cis-2-butene sulfide. From the reaction of complex 1a
(103.2 mg, 0.164 mmol) and cis-2-butene sulfide (0.0160 cm3,
0.180 mmol) followed by work-up as above, syn-[Au{SCH-
MeCHMeOCH(CF3)2}(PPh3)] 6a was exclusively obtained.
CH(CF3)2). 31P-{1H} NMR (C6D6) δ 57.0 (s); mp (decomp.) 153–
154 ЊC; Found: C, 40.78; H, 5.67; S, 4.21. Calc. for C25H42-
AuF6OPS: C, 40.99; H, 5.78; S, 4.38%.
syn-[Au(SCHMeCHMeOPh)(PPh3)] 6c and anti-[Au-
(SCHMeCHMeOPh)(PPh3)] 6cЈ. From complex 1c (50.2 mg,
0.090 mmol) and trans-2-butene sulfide (0.0090 cm3, 0.091
mmol). Yield 54.2 mg, 0.084 mmol, 93%. 6c:6cЈ = 1:99. 6cЈ: 1H
NMR (C6D6) δ 1.82 (d, 3JH-H = 6.0, 3 H, SCHMeCHMeO), 1.94
1
Yield 90.4 mg, 0.13 mmol, 75%. H NMR (C6D6) δ 1.62 (d,
3JH-H = 6.0, 3 H, CHMe), 1.74 (d, 3JH-H = 6.9, 3 H, CHMe), 3.72
3
3
(sep, JH-F = 6.0, 1 H, OCH(CF3)2), 4.13 (qd, JH-H = 6.9, 3.6,
1 H, CHMe), 4.32 (qd, JH-H = 6.0, 3.6 Hz, 1 H, CHMe), 6.8–
6.9 (m, 9 H, m-, p-H of OPh) and 7.2–7.3 (m, 6 H, o-H of
OPh); 31P-{1H} NMR (C6D6) δ 39.5 (s); IR (KBr, cmϪ1) 1481m,
1436m, 1217s, 1191s, 1131m, 1102s and 968m; mp (decomp.)
141–142 ЊC; Found: C, 41.89; H, 3.38; S, 4.45. Calc. for C25H24-
AuF6OPS: C, 42.03; H, 3.39; S, 4.49%.
3
3
3
(d, JH-H = 7.2, 3 H, SCHMeCHMeO), 4.10 (qd, JH-H = 7.2,
3
6.6 Hz, 1 H, SCHMeCHMeO), 4.62 (dq, JH-H = 6.6, 6.0 Hz,
1 H, SCHMeCHMeO) and 6.7–7.3 (m, 20 H, OPh, PPh3).
31P-{1H} NMR (C6D6) δ 40.0 (s); mp (decomp.) 172–173 ЊC;
Found: C, 52.36; H, 4.25; S, 5.22. Calc. for C28H28AuOPS: C,
52.50; H, 4.41; S, 5.01%.
syn-[Au{SCHMeCHMeOCH(CF3)2}(PCy3)] 6b. From com-
plex 1b (53.2 mg, 0.082 mmol) and cis-2-butene sulfide (0.0100
syn-[Au(SCHMeCHMeOPh)(PCy3)] 6d and anti-[Au-
(SCHMeCHMeOPh)(PCy3)] 6dЈ. From complex 1d (21.4 mg,
0.036 mmol) and trans-2-butene sulfide (0.0036 cm3, 0.036
mmol). Yield 12.4 mg, 0.018 mmol, 49%. 6d:6dЈ = 5:95. 6dЈ:
1
cm3, 0.085 mmol). Yield 40.2 mg, 0.054 mmol, 66%. H NMR
(C6D6) δ 0.8–1.7 (m, 39 H, CHMe, PCy3), 3.90 (sep, 3JH-F = 6.0,
3
1 H, CH(CF3)2), 4.12 (qd, JH-H = 6.8, 3.9, 1 H, CHMe) and
J. Chem. Soc., Dalton Trans., 1999, 4397–4406
4403

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1H NMR (C6D6) δ 0.9–1.7 (m, 33 H, PCy3), 1.92 (d, 3JH-H = 5.7,
3c/3cЈ. MeSCHMeCH2OPh and MeSCH2CHMeOPh. Yield
3
3 H, SCHMeCHMeO), 2.02 (d, JH-H = 6.3, 3 H, SCHMeCH-
98%, ratio = 69:31 (GLC). GC-MS (EI: 70 eV): MeSCHMe-
CH2OPh (major species), m/z = 182 (Mϩ, MeSCHMe-
CH2OPh), 135 (PhOCH2CHMeϩ) and 107 (PhOCH2ϩ);
MeSCH2CHMeOPh (minor species), m/z = 182 (Mϩ,
MeSCH2CHMeOPh), 121 (PhOCHMeϩ) and 61 (MeSCH2ϩ).
3
MeO), 4.08 (qd, JH-H = 8.0, 6.3, 1 H, SCHMeCHMeO), 4.57
3
(qd, JH-H = 8.0, 5.7 Hz, 1 H, SCHMeCHMeO), 6.8 (m, 1 H,
p-H of OPh), 7.0 (m, 2 H, m-H of OPh) and 7.21 (t, 3JH-H = 6.3,
2 H, o-H of OPh); 31P-{1H} NMR (C6D6) δ 56.1 (s); mp
(decomp.) 120–121 ЊC; Found: C, 52.34; H, 4.28; S, 5.01. Calc.
for C28H28AuOPS: C, 52.50; H, 4.41; S, 5.01%.
3d/3dЈ. MeSCHMeCH2OPh and MeSCH2CHMeOPh. Yield
97%, ratio = 84:16 (GLC).
syn-[Au(SCHMeCHMeOPh)(PMe3)] 6eЈ and anti-[Au-
(SCHMeCHMeOPh)(PMe3)] 6eЈ. From complex 1e (9.7 mg,
0.026 mmol) and trans-2-butene sulfide (0.0026 cm3, 0.026
4a/4aЈ. MeSCMe2CH2OCH(CF3)2 and MeSCH2CMe2-
OCH(CF3)2. Yield 98%, ratio = 98:2 (GLC), 99:1 (NMR).
GC-MS (EI: 70 eV): MeSCMe2CH2OCH(CF3)2 (major
species), m/z = 270 [Mϩ, MeSCMe2CH2OCH(CF3)2], 255
1
mmol). Yield 0.025 mmol, 95%. 6e:6eЈ = 2:98. 6eЈ: H NMR
(C6D6): δ 0.56 (d, 2JH-P = 10.2, 9 H, PMe3), 1.75 (d, 3JH-H = 6.0,
3
3 H, SCHMeCHMeO), 1.92 (d, JH-H = 6.6, 3 H, SCHMeCH-
[(CF3)2CHOCH2CMe2Sϩ], 223 [(CF3)2CHOCH2CMe2ϩ], 181
MeO), 4.03 (qui, 3JH-H = 6.6, 1 H, SCHMeCHMeO), 4.60 (qui,
3JH-H = 6.0 Hz, 1 H, SCHMeCHMeO) and 6.8–7.4 (m, 5 H,
OPh); 31P-{1H} NMR (C6D6) δ Ϫ2.03 (s).
ϩ
[(CF3)2CHOCH2
]
and 89 (MeSCMe2ϩ); MeSCH2CMe2-
OCH(CF3)2 (minor species), m/z = 270 [Mϩ, MeSCH2CMe2-
OCH(CF3)2], 255 [(CF3)2CHOCMe2CH2Sϩ], 209 [(CF3)2-
CHOCMe2ϩ] and 61 (MeSCH2ϩ). MeSCMe2CH2OCH(CF3)2:
1H NMR (C6D6) δ 1.10 (s, 6 H, SCMe2CH2O), 1.79 (s, 3 H,
SMe), 3.26 (s, 2 H, SCMe2CH2O) and 3.56 (sep, 3JH-F = 6.0 Hz,
OCH(CF3)2). MeSCH2CMe2OCH(CF3)2: 1H NMR (C6D6)
δ 1.67 (s, 6 H, SCH2CMe2O), 1.96 (s, 3 H, SMe) and 3.20 (sep,
3JH-F = 6.0, OCH(CF3)2).
Reaction of compounds 2–6 with MeI
As a typical example, the reaction of a mixture of complexes 3a
and 3aЈ with MeI is described. Methyl iodide (0.0140 cm3,
0.180 mmol) was added into the mixture of 3a and 3aЈ (107.2
mg, 0.171 mmol) in thf (2 cm3). After stirring for 2 h at room
temperature two peaks appeared in 90:10 integration ratio
by GLC, which were also characterised by GC-MS. The inte-
gration ratio 3a:3aЈ was estimated as equal as to the molar
ratio, since they are regioisomers. GC-MS (EI: 70 eV):
MeSCHMeCH2OCH(CF3)2 (major species), m/z = 256 [Mϩ,
MeSCHMeCH2OCH(CF3)2], 241 [(CF3)2CHOCH2CHMeSϩ],
209 [(CF3)2CHOCH2CHMeϩ], 181 [(CF3)2CHOCH2ϩ] and 75
(MeSCH2ϩ); MeSCH2CHMeOCH(CF3)2 (minor species),
m/z = 256 [Mϩ, MeSCH2CHMeOCH(CF3)2], 241 [(CF3)2-
CHOCH2CHMeSϩ], 209 [(CF3)2CHOCH2CHMeϩ] and 195
[(CF3)2CHOCH2ϩ]. This reaction was also carried out in a
NMR tube. Methyl iodide (0.0011 cm3, 0.018 mmol) was added
to a mixture of 3a and 3aЈ (11.9 mg, 0.0170 mmol, 3a:3aЈ =
90:10) and CHPh3 as an internal standard (10.3 mg, 0.042
4b/4bЈ. MeSCMe2CH2OCH(CF3)2 and MeSCH2CMe2-
OCH(CF3)2. Yield 97%, ratio = 96:4 (GLC), 90:10 (NMR).
4c/4cЈ. MeSCMe2CH2OPh and MeSCH2CMe2OPh. Yield
89%, ratio = 98:2 (GLC), 96:4 (NMR). GC-MS (EI: 70 eV):
MeSCMe2CH2OPh (major species), m/z = 196 (Mϩ, MeSC-
Me2CH2OPh), 149 (PhOCH2CMe2ϩ) and 107 (PhOCH2ϩ);
MeSCH2CMe2OPh (minor species), m/z = 196 (Mϩ, MeSCH2-
CMe2OPh), 135 (PhOCMe2ϩ) and 61 (MeSCH2ϩ). MeSCMe2-
CH2OPh: 1H NMR (C6D6) δ 1.10 (s, 6 H, SCMe2CH2O), 1.79 (s,
3 H, SMe) and 3.26 (s, 2 H, SCMe2CH2O). MeSCH2CMe2OPh:
1H NMR (C6D6) δ 1.22 (s, 6 H, SCH2CMe2O), 1.73 (s, 3 H,
SMe) and 3.74 (s, 2 H, SCH2CMe2O).
1
mmol) in benzene-d6 (0.6 cm3), and H and 31P-{1H} NMR
spectra were measured at room temperature. The NMR spectra
showed formation of two sulfides MeSCHMeCH2OCH(CF3)2
and MeSCH2CHMeOCH(CF3)2 in 90:10 ratio, and known
[AuI(PPh3)].16 MeSCHMeCH2OCH(CF3)2: 1H NMR (C6D6)
4d/4dЈ. MeSCMe2CH2OPh and MeSCH2CMe2OPh. Yield
89%, ratio = 97:3 (GLC), 95:5 (NMR).
5a/5aЈ. MeSCHPhCH2OCH(CF3)2 and MeSCH2CH-
PhOCH(CF3)2. Yield 87%, ratio = 75:25 (GLC). GC-MS (EI:
70 eV): MeSCHPhCH2OCH(CF3)2 (major species), m/z = 318
[Mϩ, MeSCHPhCH2OCH(CF3)2], 271 [(CF3)2CHOCH2-
CHPhϩ] and 181 [(CF3)2CHOCH2ϩ]; MeSCH2CHPhOCH-
(CF3)2 (minor species), m/z = 318 [Mϩ, MeSCH2CH-
PhOCH(CF3)2], 303 [(CF3)2CHOCHPhCH2Sϩ] and 257
[(CF3)2CHOCHPhϩ].
3
δ 1.70 (s, 3 H, SMe), 1.77 (d, JH-H = 6.3, 3 H, SCHMeCH2O),
3
2
3.41 (sep, JH-F = 6.0 Hz, 1 H, CH(CF3)2), 3.77 (t, JH-H
=
3JH-H = 10.2, 1 H, SCHMeCH2O), 3.92 (dqd, JH-H = 10.2,
2
3JH-H = 6.3, 4.5, 1 H, SCHMeCH2O) and 4.27 (dd, 3JH-H = 10.2,
1
4.5 Hz, 2 H, SCHMeCH2O). MeSCH2CHMeOCH(CF3)2: H
NMR (C6D6) δ 1.05 (d, 3JH-H = 6.9, 3 H, SCH2CHMeO), 1.57 (s,
3 H, SMe), 3.25 (t, 2JH-H = 3JH-H = 9.5, 1 H, SCH2CHMeO) and
3.34 (sep, 3JH-F = 6.0 Hz, 1 H, OCH(CF3)2).
5b/5bЈ. MeSCHPhCH2OCH(CF3)2 and MeSCH2CH-
PhOCH(CF3)2. Yield 89%, ratio = 95:5 (GLC).
2a. MeSCH2CH2OCH(CF3)2. Yield 96%. GC-MS (EI: 70
eV): m/z = 242 [Mϩ, MeSCH2CH2OCH(CF3)2], 195 [(CF3)2-
CHOCH2CH2ϩ], 181 [(CF3)2CHOCH2ϩ] and 61 (MeSCH2ϩ).
5c/5cЈ. MeSCHPhCH2OPh and MeSCH2CHPhOPh. Yield
95%, ratio = 70:30 (GLC). GC-MS (EI: 70 eV): MeSCHPh-
CH2OPh (major species), m/z = 244 (Mϩ, MeSCHPhCH2OPh),
197 (PhOCH2CHPhϩ) and 107 (PhOCH2ϩ); MeSCH2CH-
PhOPh (minor species), m/z = 244 (Mϩ, MeSCHPhCH2OPh),
224 (PhOCHPhCH2Sϩ) and 183 (PhOCHPhϩ).
3
1H NMR (C6D6): δ 1.65 (s, 3 H, SMe), 3.24 (sep, JH-F = 6.6,
1 H, CH(CF3)2), 2.17 (t, 3JH-H = 8.4, 2 H, SCH2CH2O) and 3.32
(t, 3JH-H = 8.4 Hz, 2 H, SCH2CH2O).
2b. MeSCH2CH2OCH(CF3)2. Yield 98%.
5d/5dЈ. MeSCHPhCH2OPh and MeSCH2CHPhOCPh.
Yield 77%, ratio = 70:30 (GLC).
2c. MeSCH2CH2OPh. Yield 96%. GC-MS (EI: 70 eV):
m/z = 168 (Mϩ, MeSCH2CH2OPh), 121 (PhOCH2CH2ϩ) and
1
61 (MeSCH2ϩ). H NMR (C6D6) δ 1.76 (s, 3 H, SMe), 2.49
3
3
6a. syn-MeSCHMeCHMeOCH(CF3)2. Yield 99%. GC-MS
(EI: 70 eV): m/z = 270 [Mϩ, MeSCHMeCHMeOCH(CF3)2],
223 [(CF3)2CHOCHMeCHMeϩ] and 195 [(CF3)2CHOCH-
Meϩ]. 1H NMR (C6D6) δ 0.96 (d, 3JH-H = 6.3, 3 H, CHMe), 1.06
(t, JH-H = 7.2, 2 H, SCH2CH2O), 3.75 (t, JH-H = 7.2 Hz, 2 H,
SCH2CH2O) and 7.0–7.4 (m, 5 H, OPh).
2d. MeSCH2CH2OPh. Yield 97%.
3
(d, JH-H = 7.2, 3 H, CHMe), 1.70 (s, 3 H, SMe), 2.53 (qd,
3
3b/3bЈ. MeSCHMeCH2OCH(CF3)2 and MeSCH2CHMeO-
CH(CF3)2. Yield 96%, ratio = 82:18 (GLC), 80:20 (NMR).
3JH-H = 7.2, 3.9, 1 H, CHMe), 3.38 (sep, JH-F = 6.0, 1 H,
OCH(CF3)2) and 3.46 (qd, 3JH-H = 6.3, 3.9 Hz, 1 H, CHMe).
4404
J. Chem. Soc., Dalton Trans., 1999, 4397–4406

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6b. syn-MeSCHMeCHMeOCH(CF3)2. Yield 98%.
3d/3dЈ. HSCHMeCH2OPh and HSCH2CHMeOPh. Yield
91%, ratio = 85:15 (GLC).
6a/6aЈ. anti-MeSCHMeCHMeOCH(CF3)2. Yield 95%. GC-
MS (EI: 70 eV): m/z = 270 [Mϩ, MeSCHMeCHMeOCH-
(CF3)2], 223 [(CF3)2CHOCHMeCHMeϩ] and 195 [(CF3)2-
4a/4aЈ. HSCMe2CH2OCH(CF3)2 and HSCH2CMe2O-
CH(CF3)2. Yield 100%, ratio = 99:1 (GLC), 99:1 (NMR).
GC-MS (EI: 70 eV): HSCMe2CH2OCH(CF3)2 (major species),
m/z = 256 [Mϩ, HSCMe2CH2OCH(CF3)2], 223 [(CF3)2-
CHOCH2CMe2ϩ], 209 [(CF3)2CHOCH2ϩ], 181 [(CF3)2-
CHOCH2ϩ] and 89 (MeSCMe2ϩ); HSCH2CMe2OCH(CF3)2
(minor species), m/z = 256 [Mϩ, HSCH2CMe2OCH(CF3)2],
223 [(CF3)2CHOCMe2CH2ϩ], 209 [(CF3)2CHOCMe2ϩ] and
47 (HSCH2ϩ). HSCMe2CH2OCH(CF3)2: 1H NMR (C6D6)
δ 1.07 (s, 6 H, SCMe2CH2O), 1.61 (s, 1 H, SH), 3.12 (s, 2 H,
1
CHOCHMeϩ]. H NMR (C6D6) δ 1.41 (s, 3 H, SMe), 1.56 (d,
3
3JH-H = 6.9, 3 H, SCHMeCHMeO), 1.90 (d, JH-H = 6.0, 3 H,
SCHMeCHMeO), 3.76 (m, 2 H, CHMe) and 3.86 (sep,
3JH-F = 6.0, 1 H, OCH(CF3)2). The syn isomer was not detected.
6b/6bЈ. anti-MeSCHMeCHMeOCH(CF3)2. Yield 98%.
Protonolysis of compounds 2–6 with HCl
3
SCMe2CH2O) and 3.31 (sep, JH-F = 6.0 Hz, OCH(CF3)2).
As a typical example, the reaction of a mixture of complexes 3a
and 3aЈ with HCl is described. Hydrogen chloride gas (0.733
ml, 0.030 mmol) was introduced into a mixture of 3a and 3aЈ
(10.2 mg, 0.015 mmol) in thf (2 cm3). After stirring for 2 h at
room temperature, two peaks were observed in 90:10 inte-
gration ratio by GLC, which were also characterised by
GC-MS. GC-MS (EI: 70 eV): HSCHMeCH2OCH(CF3)2
(major species), m/z = 242 [Mϩ, HSCHMeCH2OCH(CF3)2],
209 [(CF3)2CHOCH2CHMeϩ], 181 [(CF3)2CHOCH2ϩ] and 61
(MeSCH2ϩ); HSCH2CHMeOCH(CF3)2 (minor species), m/z =
242 [Mϩ, HSCH2CHMeOCH(CF3)2], 209 [(CF3)2CHOCH-
MeCH2ϩ] and 181 [(CF3)2CHOCHMeϩ]. This reaction was also
carried out in a NMR tube: HCl (0.486 ml, 0.020 mmol) was
added to the mixture of 3a and 3aЈ (10.2 mg, 0.015 mmol) and
(Me3Si)2O as an internal standard (0.0010 cm3, 0.0047 mmol)
HSCH2CMe2OCH(CF3)2: 1H NMR (C6D6) δ 0.77 (s, 6 H,
3
SCH2CMe2O), 1.22 (s, 1 H, SH), 3.07 (d, JH-H = 6.8, 2 H,
SCH2CMe2O).
4b/4bЈ. HSCMe2CH2OCH(CF3)2 and HSCH2CMe2-
OCH(CF3)2. Yield 95%, ratio = 96:4 (GLC), 98:2 (NMR).
4c/4cЈ. HSCMe2CH2OPh and HSCH2CMe2OPh. Yield 98%,
ratio = 98:2 (GLC), 99:1 (NMR). GC-MS (EI: 70 eV): HS-
CMe2CH2OPh (major species), m/z = 182 (Mϩ, HSCMe2-
ϩ
CH2OPh), 149 (PhOCH2CMe2
)
and 107 (PhOCH2ϩ);
HSCH2CMe2OPh (minor species), m/z = 182 (Mϩ, HSCH2-
CMe2OPh) and 135 (PhOCMe2ϩ). HSCMe2CH2OPh: 1H NMR
(C6D6) δ 1.26 (s, 6 H, SCMe2CH2O), 1.90 (s, 3 H, SH), 3.54 (s,
2 H, SCMe2CH2O) and 7.03 (m, 5 H, OPh). HSCH2CMe2OPh:
1H NMR (C6D6) δ 1.05 (s, 6 H, SCH2CMe2O) and 3.46 (d,
3JH-H = 8.1 Hz, HSCH2).
1
in benzene-d6 (0.6 cm3). The H NMR and 31P-{1H} spectra
were immediately measured at room temperature. They showed
formation of two sulfides HSCHMeCH2OCH(CF3)2 and
HSCH2CHMeOCH(CF3)2 in 90:10 ratio, and known
[AuCl(PPh3)].15 HSCHMeCH2OCH(CF3)2: 1H NMR (C6D6)
4d/4dЈ. HSCMe2CH2OPh and HSCH2CMe2OPh. Yield 89%,
ratio = 97:3 (GLC), 95:5 (NMR).
3
3
δ 0.93 (d, JH-H = 6.9, 3 H, CHMe), 1.29 (d, JH-H = 6.9, 1 H,
3
2
SH), 2.52 (sep, JH-F = 6.9, 1 H, CH(CF3)2), 3.03 (t, JH-H
=
6a. syn-HSCHMeCHMeOCH(CF3)2. Yield 99%. GC-MS
(EI: 70 eV): m/z = 256 [Mϩ, HSCHMeCHMeOCH(CF3)2], 223
[(CF3)2CHOCHMeCHMeϩ] and 195 [(CF3)2CHOCHMeϩ].
3JH-H = 8.1, 1 H, SCHMeCH2O) and 3.23 (m, 2 H, SCH-
MeCH2O, SCHMeCH2O). HSCH2CHMeOCH(CF3)2: 1H
3
NMR (C6D6) δ 0.80 (d, JH-H = 6.3, 3 H, SCH2CHMeO),
3
3
1.12 (d, JH-H = 6.3, 1 H, SH), 2.12 (sep, JH-F = 6.0, 1 H,
OCH(CF3)2) and 3.39 (t, JH-H = 3JH-H = 8.3 Hz, 1 H, SCH2-
2
6b. syn-MeSCHMeCHMeOCH(CF3)2. Yield 98%.
CHMeO).
6a/6aЈ. anti-HSCHMeCHMeOCH(CF3)2. Yield 95%. GC-
MS (EI: 70 eV): m/z = 256 [Mϩ, HSCHMeCHMeOCH(CF3)2],
223 [(CF3)2CHOCHMeCHMeϩ] and 195 [(CF3)2CHO-
2a. HSCH2CH2OCH(CF3)2. Yield 98%. GC-MS (EI: 70 eV):
m/z = 196 [Mϩ, HSCH2CH2OCH(CF3)2], 163 [(CF3)2CHOCH2-
1
3
1
CHMeϩ]. H NMR (C6D6) δ 0.85 (d, JH-H = 6.0, 3 H, SCH-
CH2ϩ] and 149 [(CF3)2CHOCH2ϩ]. H NMR (C6D6) δ 1.10 (t,
3
MeCHMeO), 0.93 (d, 3JH-H = 12.6, 3 H, SCHMeCHMeO), 1.36
3JH-H = 8.5, 1 H, SH), 2.00 (q, JH-H = 8.5, 1 H, SCH2CH2O),
3
3
3.11 (t, 3JH-H = 8.5, 1 H, SCH2CH2O) and 3.17 (sep, 3JH-F = 6.0
(d, JH-H = 6.0, 3 H, SH), 2.56 (sex, JH-H = 6.0, 1 H, SCH-
MeCHMeO), 3.11 (qui, 3JH-H = 6.0, 1 H, SCHMeCHMeO) and
3.46 (sep, 3JH-F = 6.0 Hz, 1 H, OCH(CF3)2). The syn isomer was
not detected.
Hz, 1 H, OCH(CF3)2).
2b. HSCH2CH2OCH(CF3)2. Yield 89%.
6b/6bЈ. anti-MeSCHMeCHMeOCH(CF3)2. Yield 98%. The
syn isomer was not detected.
2c. HSCH2CH2OPh. Yield 96%. GC-MS (EI: 70 eV):
m/z = 154 (Mϩ, HSCH2CH2OPh), 121 (PhOCH2CH2ϩ) and 107
1
3
(PhOCH2ϩ). H NMR (C6D6) δ 1.31 (t, JH-H = 8.1, 1 H, SH),
3
3
Time course of the ring opening reaction of thiiranes by
alkoxogold(I) complexes
2.33 (q, JH-H = 8.1, 1 H, SCH2CH2), 3.53 (t, JH-H = 8.5, 1 H,
SCH2CH2O), 6.8 (m, 3 H, m-, p-H of OPh) and 7.09 (d,
3JH-H = 6.8, 2 H, o-H of OPh).
The phenoxogold() complex (0.020 mmol) and CHPh3 (0.020
mmol) as an internal standard were placed in a 5 mm diameter
NMR tube with a silicon rubber septum under nitrogen
and freshly distilled toluene-d8 (0.600 cm3) was introduced
by a hypodermic syringe. The NMR tube was placed in a
thermostatted NMR probe at Ϫ10 1 ЊC and a spectrum was
measured. Immediately after ejection of the NMR tube a
settled amount of isobutylene sulfide was injected by a micro-
syringe through a rubber septum to start the reaction and then
the NMR tube was re-inserted into the thermostatted probe.
Product yields were estimated periodically by comparing the
peak areas of signals due to the product and the methine peak
of CHPh3 (δ 5.43) in the 1H NMR spectra. The reactions finally
2d. HSCH2CH2OPh. Yield 98%.
3a/3aЈ. HSCHMeCH2OCH(CF3)2 and HSCH2CHMeO-
CH(CF3)2. Yield 89%, ratio = 91:9 (GLC).
3c/3cЈ. HSCHMeCH2OPh and HSCH2CHMeOPh. Yield
94%. GC-MS (EI: 70 eV): HSCHMeCH2OPh (major species),
m/z = 168 (Mϩ, HSCHMeCH2OPh), 135 (PhOCH2CHMeϩ)
and 107 (PhOCH2ϩ); HSCH2CHMeOPh (minor species),
ϩ
m/z = 168 (Mϩ, HSCH2CHMeOPh), 135 (PhOCHMeCH2
)
and 121 (PhOCHMeϩ).
J. Chem. Soc., Dalton Trans., 1999, 4397–4406
4405

View Article Online
10 H. R. Snyder, J. M. Stewart and J. B. Ziegler, J. Am. Chem. Soc.,
proceeded to 80–100% yields in most cases. The reactions in
other solvents were carried out in a similar way.
1947, 69, 2675.
11 B. M. Trost and S. D. Ziman, J. Org. Chem., 1973, 38, 932; U. Riaz,
O. J. Curnow and M. D. Curtis, J. Am. Chem. Soc., 1994, 116, 4357;
M. D. Curtis and S. H. Druker, J. Am. Chem. Soc., 1997, 119, 1027.
12 (a) A. M. Baranger, T. A. Hanna and R. G. Bergman, J. Am.
Chem. Soc., 1995, 117, 10041; (b) G. Proulx and R. G. Bergman,
Organometallics, 1996, 15, 133; (c) W. Uhl, R. Graupner and
H. Reuter, J. Organomet. Chem., 1996, 523, 227.
References
1 R. C. Mehrotra, A. Singh and S. Sogani, Chem. Rev., 1994, 94, 215;
H. E. Bryndza, L. K. Fong, R. A. Paciello, W. Tam and J. E. Bercaw,
J. Am. Chem. Soc., 1987, 109, 1444; H. E. Bryndza and J. E. Bercaw,
Chem. Rev., 1988, 88, 1163.
2 K. G. Caulton and L. G. Hubert-Pfalzgraf, Chem. Rev., 1990, 90,
9969.
3 T. Sone, M. Iwata, N. Kasuga and S. Komiya, Chem. Lett., 1991,
1949.
4 S. Komiya, M. Iwata, T. Sone and A. Fukuoka, J. Chem. Soc.,
Chem. Commun., 1992, 1109.
5 Y. Usui, M. Hirano and S. Komiya, Chem. Lett., 1998, 981.
6 S. Komiya, T. Sone, Y. Usui, M. Hirano and A. Fukuoka, Gold
Bull., 1996, 29, 131.
7 M. Sander, Chem. Rev., 1966, 66, 297 and references therein.
8 N. P. Neureiter and F. G. Bordwell, J. Am. Chem. Soc., 1959, 81, 578.
9 C. G. Moore and M. Porter, J. Chem. Soc., 1958, 2062.
13 P. T. Matsunaga and G. L. Hillhouse, Angew. Chem., Int. Ed. Engl.,
1994, 33, 1748.
14 (a) R. D. Adams and S. B. Falloon, Organometallics, 1995, 14, 4594;
(b) R. D. Adams, J. A. Queisser and J. H. Yamamoto, J. Am. Chem.
Soc., 1996, 118, 10674.
15 C. A. McAuliffe, R. V. Parish and P. D. Randall, J. Chem. Soc.,
Dalton Trans., 1979, 1730.
16 B. J. Gregory and C. L. Ingold, J. Chem. Soc. B, 1969, 276.
17 D. Shaw, Fourier Transform N.M.R. Spectroscopy, Elsevier Science,
Amsterdam, 1976, p. 221.
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