The reactions of CpRu(PPh3)2SR with the electrophiles HBF4, [MeSSMe2]BF4 and MeSphth where R=CMe3, CHMe2, 4-C6H4Me and phth=phthalimide

Article abstract of DOI:10.1016/S0022-328X(00)00654-9

Reaction of the ruthenium thiolato complexes CpRu(PPh₃)₂SR (1), where R=CMe₃, CHMe₂, 4-C₆H₄Me with HBF₄ gave the corresponding thiol complex salts [CpRu(PPh₃)₂(HSR)]BF₄ (2) in very good yields. Treatment of the thiolato complexes with [MeSSMe₂]BF₄ gave the methyl thioether complex salt [CpRu(PPh₃)₂SMe₂]BF₄ (3). Reactions of 1 with MeSphth, where phth=phthalimide, gave CpRu(PPh₃)₂(phth) (4) and the dimers (μ-SMe)(μ-SR)[CpRu(phth)]₂ (5) for R=CMe₃ and CHMe₂, however, for R=4-C₆H₄Me the same reaction gave CpRu(PPh₃)(phth)(MeSS-4-C₆H₄Me) (6) and (μ-SMe)(μ-S-4-C₆H₄Me)[CpRu(S-4-C₆H ₄Me)]₂ (7). The crystal structure for 7 was determined: space group P2₁/c, a=8.805(2), b=13.668(3), c=26.026(6) A?, α=90, β=108.86(2), γ=90°, V=2964.0(12) A?³ and Z=4.

Full text of DOI:10.1016/S0022-328X(00)00654-9

www.elsevier.nl/locate/jorganchem
Journal of Organometallic Chemistry 622 (2001) 1–5
The reactions of CpRu(PPh3)2SR with the electrophiles HBF4,
[MeSSMe2]BF4 and MeSphth where R=CMe3, CHMe2,
4-C6H4Me and phth=phthalimide
Alan Shaver *, Mohammad El-khateeb 1, Anne-Marie Lebuis
Department of Chemistry, Otto Maass Chemistry Building, McGill Uni6ersity, 801 Sherbrooke Street West, Montreal PQ, Canada H3A 2K6
Received 24 July 2000; received in revised form 28 August 2000
Abstract
Reaction of the ruthenium thiolato complexes CpRu(PPh3)2SR (1), where R=CMe3, CHMe2, 4-C6H4Me with HBF4 gave the
corresponding thiol complex salts [CpRu(PPh3)2(HSR)]BF4 (2) in very good yields. Treatment of the thiolato complexes with
[MeSSMe2]BF4 gave the methyl thioether complex salt [CpRu(PPh3)2SMe2]BF4 (3). Reactions of 1 with MeSphth, where
phth=phthalimide, gave CpRu(PPh3)2(phth) (4) and the dimers (m-SMe)(m-SR)[CpRu(phth)]2 (5) for R=CMe3 and CHMe2,
however, for R=4-C6H4Me the same reaction gave CpRu(PPh3)(phth)(MeSS-4-C6H4Me) (6) and (m-SMe)(m-S-4-
C6H4Me)[CpRu(S-4-C6H4Me)]2 (7). The crystal structure for 7 was determined: space group P21/c, a=8.805(2), b=13.668(3),
3
,
,
c=26.026(6) A, h=90, i=108.86(2), k=90°, V=2964.0(12) A and Z=4. © 2001 Elsevier Science B.V. All rights reserved.
Keywords: Ruthenium; Thiolate; Electrophiles; Dimers; Structure
1. Introduction
and alkyl halides usually give complexes containing
thioether ligands [2,3].
Organometallic thiolato complexes, M–SR, possess
two sites which can react with electrophiles, namely the
sulfur atom of the thiolato ligand and the metal center
[1].
The reactivity of the thiolato ligand towards elec-
trophiles is due to the availability of lone pairs of
electrons on the sulfur atom [1]. Electrophilic attack at
the metal center is observed only when the metal center
is electron rich [2].
Protonation of thiolato complexes has been reported
to give complexes containing thiol as a ligand, but in
most cases the product thiol complexes were not iso-
lated [1a–d]. The reactions between thiolato complexes
The sulfur transfer reagents, RSphth where phth=
phthalimide are used in organic chemistry as a source
of an electrophilic ‘RS+’ group [4]. The applications of
such reagents in organometallic chemistry have been
demonstrated [5]. When the sulfur transfer reagents
were used with thiolato complexes, complexes contain-
ing disulfide ligands were obtained [6]. In some cases,
the formed disulfide ligand was substituted by another
ligand present in solution [7]. Also, the reaction of
[MeSSMe2]BF4 with metal thiolato complexes gave
complexes having monodentate organic disulfide lig-
ands [8].
We reported that the reaction of CpRu(PPh3)2SR (1)
with NOBF4 gave [CpRu(PPh3)(NO)SR]BF4 in which
the NO+ attacked the Ru-center. However, the reaction
of the carbonyl analogs CpRu(PPh3)(CO)SR with
NOBF4 gave dimeric salts of the type (m-
RSSR)[CpRu(PPh3)(CO)]2[BF4]2 in which NO oxidized
the sulfur atom of the thiolato group [9]. In this paper,
* Corresponding author. Tel.: +1-514-3986999; fax: +1-514-
3983797.
E-mail address: shaver@artsci.1an.mcgill.ca (A. Shaver).
1 Present address: Department of Chemistry, Jordan University of
Science and Technology, PO Box 3030, Irbid 22110, Jordan.
the reactions of
1 with the electrophiles HBF4,
[MeSSMe2]BF4 and phthSR are reported.
0022-328X/01/$ - see front matter © 2001 Elsevier Science B.V. All rights reserved.
PII: S0022-328X(00)00654-9

2
A. Sha6er et al. / Journal of Organometallic Chemistry 622 (2001) 1–5
2. Results and discussion
Treatment of 1 with [MeSSMe2]BF4 in THF at room
temperature gave the air stable thioether complex,
Treatment of CpRu(PPh3)2SR (1) with HBF4 (85% in
ether) gave the corresponding thiol complex salts,
[CpRu(PPh3)2(HSR)]BF4 (2) where R=CMe3 (a), 4-
C6H4Me (b), CHMe2 (c), in very good yields (80–88%)
(Eq. (1)).
[CpRu(PPh3)2(SMe2)]BF4 (3) in good yields (Eq. (2)).
The free alkylmethyl disulfide was detected in the H-
NMR spectra of the reaction mixture.
1
(2)
The reaction of 1 with MeSphth gave the substitution
product, CpRu(PPh3)2(phth) (4) and the dimers (m-
SMe)(m-SR)[CpRu(phth)]2 (5a,b) according to Eq. (3).
The IR spectra of 5a,b showed a carbonyl band in the
range 1658–1663 cm−1 indicative of the presence of a
(1)
The IR spectra of 2a–c showed a decrease in the SH
stretching frequency compared to that of the free thiols.
1
coordinated phthalimido ligand [10a]. Their H-NMR
1
In the H-NMR spectra of these complexes, the chemi-
spectra showed a multiplet in the aromatic region inte-
grating for eight protons due to two phthalimido lig-
ands. It also showed a singlet Cp-peak integrating for
ten protons, while the aliphatic protons appeared as
peaks in the expected region in the appropriate multi-
plicity and relative intensities. The free disulfide ligands,
cal shift of the SH proton was shifted downfield relative
to that of the free thiol. The peak for this proton
appeared as a triplet in 2a and 2b due to coupling with
the two equivalent phosphorus atoms. In 2c, this peak
appeared as a multiplet due to coupling with the me-
thine proton of the isopropyl group in addition to the
two equivalent phosphorus atoms.
1
RSSMe, were detected in the H-NMR spectra of the
reaction mixtures.
(3)
The reaction of CpRu(PPh3)2S-4-C6H4Me with
MeSphth gave the disulfide complex 6 and the dimer 7
(Eq. (4)) together with other unidentified compounds.
The IR spectrum of 6 showed a carbonyl band at 1652
cm−1
.
(4)
The structure of 7 was determined and is shown in
Fig. 1 [9]. The crstallographic data are presented in
Table 1. Molecule 7 is symmetric but its mirror plane is
not crystallographically required. The compound has a
Fig. 1. An ORTEP diagram of (m-SMe)(m-S-4-C6H4Me)[CpRu(S-4-
,
C6H4Me)]2 (5b). Selected bond lengths (A) and angles (°) are:
Ru(1)ꢀRu(2)=2.784(10)
Ru(1)ꢀS(1)=2.398(3),
Ru(1)ꢀS(3)=
,
RuꢀRu bond length of 2.784(1) A which is longer than
2.319(2), Ru(1)ꢀS(4)=2.325(2), Ru(2)ꢀS(2)=2.387(2), Ru(2)ꢀS(3)=
2.332(2), Ru(2)ꢀS(4)=2.30(2), Ru(2)ꢀRu(1)ꢀS(1)=115.58(6), Ru(2)ꢀ
Ru(1)ꢀS(3)=53.49(5), Ru(2)ꢀS(3)ꢀRu(1)=73.45(6), S(1)ꢀRu(1)ꢀS(3)
=93.75(5), S(1)ꢀRu(1)ꢀS(4)=80.08(7), S(3)ꢀRu(1)ꢀS(4)=92.25(7),
Ru(1)ꢀRu(2)ꢀS(2)=92.25(7), Ru(1)ꢀRu(2)ꢀS(3)=115.92(6), Ru(1)ꢀ
Ru(2)ꢀS(4)=53.06(5), S(2)ꢀRu(2)ꢀS(3)=53.31(5), S(2)ꢀRu(2)ꢀS(4)
=81.80(7), S(3)ꢀRu(2)ꢀS(4)=92.03(7), Ru(2)ꢀS(4)ꢀRu(1)=73.53(7),
S(3)ꢀRu(1)ꢀS(2)=92.36(7).
the corresponding bond lengths observed in the Ru(II)
,
trimer [10b] [CpRuS(C3H7)]3 (average=2.714 A) and in
,
[Cp*Ru(SPh)3RuCp*]C1 (2.630(1) A) (Cp*=C5Me5)
[11]. The RuꢀSb (bridge) bond lengths (average 2.326
,
A) are longer than the RuꢀSb bonds in the
,
Ru(II)ꢀtrimer (average 2.306 A). The terminal RuꢀS

A. Sha6er et al. / Journal of Organometallic Chemistry 622 (2001) 1–5
3
shifts are in ppm relative to TMS (1H) or 85% H3PO4
(31P) at 0 ppm. Infrared spectra were recorded on an
Analect AQS-20 FT-IR spectrophotometer. Low reso-
lution mass spectra were measured on a KRATOS
MS25RFA mass spectrometer. High resolution mass
spectra were measured on a ZAB 2F HS mass spec-
trometer at the McGill University Biomedical Mass
Spectrometry Unit. Elemental analyses were performed
by Canadian Microanalytical Service Ltd., Delta,
British Columbia. Melting points were obtained on a
Thomas Hoover capillary melting point apparatus and
were uncorrected.
Table 1
Crystallographic data for (m-SMe)( (m-S-4-C6H4Me)[CpRu(S-4-
C6H4Me) (7)
Chemical formula
Molecular weight
Crystal system
Space group
Unit cell dimensions
C32H34Ru2S4
748.97
Monoclinic
P21/c
,
a (A)
8.805(2)
13.668(3)
26.026(6)
90
108.86(2)
90
2964.0(12)
4
1.678
,
b (A)
,
c (A)
h (°)
i (°)
k (°)
3
,
V (A )
Z
3.1. General procedure for the formation of
[CpRu(PPh3)2(HSR)]BF4
Dcalc (g cm−3
F(000)
)
1512
Crystal size (mm)
Reflections measured
Unique reflections
aR1 (I\2|(I)/a11)
bwR2 (I/2|(I)/a11)
0.50×0.13×0.11
5588
5223
0.0501/0.1056
0.1038/0.1213
In a 100 ml Schlenk flask, CpRu(PPh3)2SR (0.25
mmol) was dissolved in THF (20.0 ml) and HBF4·Et2O
(0.052 ml, 0.30 mmol) was added. The reaction mixture
was stirred for 30 min. The yellow precipitate that
formed was isolated by the removal of the mother
liquor with a syringe. The precipitate was washed with
hexanes (3×5.0 ml) and recrystallized from methylene
chloride–hexanes to give the analytically pure products.
a R1=S(ꢀFoꢀ−ꢀFcꢀ)/SꢀFoꢀ.
b wR2={S[w[(F2o−Fc2)]2]/S[w(F2o)2}1/2
.
,
bond lengths (2.398(3), 2.391(3) A) are similar to those
observed in complexes of the type CpRu(PPh3)(CO)E,
where E=SSCHMe2 (2.393(3) A) [12], SSSC3H7
3.1.1. [CpRu(PPh3)2(HSCMe3)]BF4 (2a)
,
Orange crystals (0.19 g, 88%). m.p.: 144–146°C. IR
,
,
(2.370(2) A) [12], SS(O)CHMe2 (2.379(2) A) [13],
1
(KBr): w(SH) 2505(w) cm−1. H-NMR (CD2C12): l 1.39
,
SS(O)CH2Ph (2.377(3) A) [14] and SS(O)2-4-C6H4Me
(s, 9H, C(CH3), 2.60 (t, 1H, SH), 4.69 (s, 5H, Cp), 6.95
(m, 12H, PPh3), 7.40 (m, 18H, PPh3). Anal. Calc. for
C45H45BF4P2RuS: C, 62.28; H, 5.23; S, 3.69. Found: C,
61.86; H, 5.20; S, 3.34%.
,
(2.383(2) A) [13].
The electrophiles HBF4 and [MeSSMe2]BF4 attack
the sulfur atoms of 1 to give the thiol (2) and thioether
(3) complex salts, respectively; the later being formed
by ligand substitutions of the disulfides MeSSR by the
Me2S present in solution. The electrophilic MeS+ spe-
cies of MeSphth can attack the sulfur lone pairs of 1 as
shown by the presence of MeSSR. However presence of
the MeS− ligand attached to the ruthenium atoms of 5
and 7 shows that it can also attack the metal atom.
3.1.2. [CpRu(PPh3)2(HSCHMe2)]BF4 (2b)
Orange crystals (0.18 g, 81%). m.p.: 185–187°C. IR
1
(KBr): w(SH) 2512(w) cm−1. H-NMR (CD2C12): l 1.32
(d, 6H, CH(CH3)2), 2.72 (septet, 1H, CH(CH3)2), 2.93
(m, 1H, SH), 4.62 (s, 5H, Cp), 6.95 (m, 12H, PPh3),
7.22 (m, 18H, PPh3). Anal. Calc. for C44H43BF4P2RuS:
C, 61.90; H, 5.08; S 3.76. Found: C, 61.71; H, 5.34; S,
4.12%.
3. Experimental
3.1.3. [CpRu(PPh3)2(HS-4-C6H4Me)]BF4 (2c)
Yellow air sensitive crystals, that decomposed during
All experiments were performed under nitrogen using
vacuum line and Schlenk techniques. THF and hexanes
were refluxed over Na–benzophenone and distilled un-
der nitrogen just prior to use. Methylene chloride was
refluxed over phosphorus pentoxide and distilled under
nitrogen. Deuterated solvents (Isotec) were used as
received. The ruthenium thiolates CpRu(PPh3)2SR [15]
and methylthiophthalimide [16] were all prepared ac-
elemental analysis (0.20 g, 80%). m.p.: 138–140°C. IR
1
(KBr): w(SH) 2514(w) cm−1. H-NMR (CD2C12): l 2.38
(s, 3H, 4-C6H4CH3), 4.44 (s, 5H, Cp), 4.93 (t, 1H, SH),
6.92 (m, 16H, PPh3, C6H4CH3), 7.21 (m, 18H, PPh3).
Anal. Calc. for C48H43BF4P2RuS: C, 63.92; H, 4.80; S,
3.55. Found: C, 56.40; H, 4.25; S, 3.55%.
cording
to
published
procedures.
The
salt
3.2. [CpRu(PPh3)2SMe2]BF4 (3)
[MeSSMe2]BF4 (Aldrich) was used as received.
Nuclear magnetic resonance spectra (1H-NMR) were
recorded on a Varian XL-300 or a JEOL-270 spectrom-
eter. Samples were prepared under nitrogen. Chemical
In a 100 ml Schlenk flask, CpRu(PPh3)2SR (0.25
mmol) was dissolved in THF (10.0 ml). The salt
[MeSSMe2]BF4 (0.055 g, 0.28 mmol) was added and the

4
A. Sha6er et al. / Journal of Organometallic Chemistry 622 (2001) 1–5
1
resulting mixture was stirred for 3 h. The yellow precip-
itate was isolated by removal of the mother liquor with
a syringe. The precipitate was washed with hexanes
(3×5.0 ml) and recrystallized from methylene chlo-
ride–hexanes to give yellow crystals. Yields 85% (R=
CMe3); 70% (R=4-C6H4Me); 80% (R=CHMe2). m.p.:
removed PPh3. The H-NMR spectrum of the residue
from the orange band demonstrated the presence of
two compounds. Elution with THF in hexanes (1:2)
gave an orange fraction, which was collected and
stripped to dryness. Elution with THF in hexanes (2:1)
1
gave a red fraction whose H-NMR spectrum revealed
1
181–183°C. H-NMR (CD2C12): l 2.26 (s, 6H, CH3),
the presence of several unidentified compounds; this
band was discarded. The orange product was redis-
solved in THF and was chromatographed on another
alumina column (1×20 cm). Elution with THF in
hexanes (1:5) gave a yellow band, which was collected
and reduced to 10 ml. Storage at 0°C overnight gave 6
as a yellow solid (23.0 mg, 15%). m.p.: 97–99°C. IR
4.47 (s, 5H, Cp), 7.03 (m, 12H, PPh3), 7.38 (m, 18H,
PPh3). Anal. Calc. for C43H41BF4P2RuS: C, 61.50; H,
4.92; S, 3.82. Found: C, 61.17; H, 4.91; S, 3.99%.
3.2.1. CpRu(PPh3)2(phth) (4)
In a 100-ml Schlenk flask 1a or 1b (0.65 mmol) was
dissolved in THF (30.0 ml). MeSphth (0.13 g, 0.65
mmol) was added as a solid. The resulting mixture was
stirred at room temperature (r.t.) for 2 days. The
volume was concentrated to 3.0 ml under vacuum and
the concentrate placed on an alumina column (2×30
cm). Elution with hexanes removed PPh3. Elution with
THF in hexanes (1:2) gave a yellow fraction, which was
collected and reduced to 15.0 ml and cooled to 0°C
overnight. Yellow crystals of 4 are formed. Yields 78%
(R=CMe3); 84% (R=CHMe2). m.p.: 126–127°C. IR
(KBr): w(CO)=1652(s) cm−1. H-NMR (C6D6): l 2.02
1
(s, 3H, 4-C6H4CH3), 2.15 (s, 3H, CH3), 4.33 (s, 5H,
Cp), 6.94 (d, 2H, C6H4CH3), 6.95 (d, 2H, C6H4CH3),
6.97 (m, 8H, PPh3, C6H4), 7.45 (m, 11H, PPh3, C6H4).
Mass spectrum (FAB in NBA): m/e 744 (M +), 598
’
(M +−phth), 428 (M +−(phth+MeSSC6H4Me)),
’
’
166 (M +−(phth+MeSSC6H4Me+PPh3)). High res-
’
olution mass spectrum (FAB, Glycerol) for
C39H34O2NS2P
102Ru:
746.0892100
(Calc.:
746.0890342). Elution with THF in hexanes (1:2) gave a
red fraction, which was collected and stripped to dry-
ness. Recrystallization from methylene chloride–hex-
anes gave red crystals of 7 (see below).
1
(KBr): w(CO) 1651(s) cm−1. H-NMR (CDCl3): l 4.32
(s, 5H, Cp), 7.15 (m, 34H, PPh3, C6H4). Anal. Calc. for
C49H39NO2P2Ru: C, 70.32; H, 4.70; N, 1.67; Found: C,
69.52; H, 5.16; N, 1.63%. A red fraction was collected
by eluting the column with THF in hexanes (2:1).
Recrystallization of the crude solid from methylene
chloride–hexanes gave red crystals of 5a where R=
CMe3 or 5b where R=CHMe2 (see below).
3.2.5. (v-SMe)(v-S-4-C6H4Me)[CpRu(S-4-C6H4Me)]2
(7)
Yield (30.0 mg. 10%). m.p.: 160–162°C. 1H-NMR
(CD2C12): l 1.79 (s, 3H, C6H4CH3), 2.22 (s, 6H,
C6H4CH3), 2.33 (s, 3H, CH3), 5.05 (s, 10H, Cp), 6.85
(d, 2H, C6H4CH3), 7.10 (d, 2H, C6H4CH3), 7.30 (m,
3.2.2. (v-SMe)(v-SCMe3)[CpRu(phth)]2 (5a)
Yield (0.70 g, 43%). m.p.: 162–164°C. IR (KBr):
w(CO)=1658(s) cm−1. 1H-NMR (CDC13): l 1.90 (s, 9H,
C(CH3), 3.44 (s, 3H, SCH3), 5.22 (s, 10H, Cp), 7.41 (m,
4H, C6H4), 7.47 (m, 4H, C6H4). Anal. Calc. for
C31H30N2O4Ru2S2: C, 48.92; H, 3.97; N, 3.86; S, 8.68.
Found: C, 49.00; H, 4.12; N, 3.51; S, 8.16%.
8H, C6H4CH3). Mass spectrum (FAB in NBA): m/e 750
(M +),
627
(M +−SC6H4Me),
504
+
’
’
’
(M −
2(SC6H4Me)),489 (M +−(2(SC6H4Me)+Me)), 289
’
(M +(CpRu+2(SC6H4Me)+SMe)). High resolution
’
mass spectrum (FAB, Glycerol) for C32H34O2NS4
102Ru2: 750.9707100 (Calc.: 750.9708586).
3.2.3. (v-SMe)(v-SCHMe2)[CpRu(phth)]2 (5b)
Yield (0.05 g, 31%). m.p.: 171–173°C. IR (KBr):
1
w(CO)=1663(s) cm−1. H-NMR (CD2C12): l 1.98 (d,
3.3. Crystallographic analysis
6H, CH(CH3)2), 3.25 (septet, 1H, CH(CH3)2), 3.39 (s,
3H, SCH3), 5.17 (s, 10H, Cp), 7.48 (m, 8H, C6H4).
Anal. Calc. for C30H28N2O4Ru2S2: C, 48.23; H, 3.78; N,
3.75; S, 8.58. Found: C, 48.09; H, 3.73; N, 3.33; S,
6.98%.
Data for the rod shaped crystals of 7 were measured
on an Rigaku AFC65 diffractometer using Mo–Ka
radiation and ꢀ scan mode. The structure was solved
by the Patterson method and expanded using d4map
synthesis. Refinement was on F2 using SHELXL 96. The
assignment of the space group was confirmed by the
program PLATON, this was also used in the verification
of possible voids and missed symmetry. All non-hydro-
gen atoms were refined anisotropically, hydrogen atoms
are isotropic and were introduced at calculated posi-
tions. Final agreement factors and other details are
given in Table 1.
3.2.4. CpRu(PPh3)(phth)(MeSS–4-C6H4Me) (6)
In a 100 ml Schlenk flask, CpRu(PPh3)2S-4-C6H4Me
(0.50 g, 0.62 mmol) was dissolved in THF (30.0 ml) and
MeSphth (0.14 g, 0.68 mmol) was added. The resulting
mixture was stirred at r.t. for 6 days. The volume was
concentrated to 3.0 ml under vacuum and placed on an
alumina column (2×30 cm). Elution with hexanes

A. Sha6er et al. / Journal of Organometallic Chemistry 622 (2001) 1–5
5
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4. Supplementary material
Crystallographic data for the structural analysis have
been deposited with Cambridge Crystallographic Data
Center, CCDC no. 132 173 for 7. Copies of the infor-
mation can be obtained free of charge from the Direc-
tor, CCDC, 12 Union Road, Cambridge, CB2 1EZ,
UK (fax: +44-1223-336033; e-mail: deposit@ccdc.
cam.ac.uk or www: http://www.ccdc.cam.ac.uk).
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[5] (a) A. Shaver, J. Hartgerink, Can. J. Chem. 65 (1987) 1190. (b)
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Trojansek, Ph.D. Thesis, McGill University, Montreal, Quebec,
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Acknowledgements
We thank the Natural Science and Engineering Re-
search Council of Canada and the Quebec Department
of Education for financial support.
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