Chloride substitution of [CpRu(dppf)Cl] with sulfur-containing ligands

Article abstract of DOI:10.1016/j.jorganchem.2003.12.020

The reactions of CpRu(dppf)Cl (1) with the sulfur-containing ligands, thiophenol HSPh, 2-mercaptopyridine C₅H₄N(SH), thiourea SC(NH₂)₂, vinylene trithiocarbonate SCS(CH)₂S and ethylene trithiocarbonat

Full text of DOI:10.1016/j.jorganchem.2003.12.020

Journal of Organometallic Chemistry 689 (2004) 1444–1451
www.elsevier.com/locate/jorganchem
Chloride substitution of [CpRu(dppf)Cl] with
sulfur-containing ligands
*
*
Xiu Lian Lu, Jagadese J. Vittal, Edward R.T. Tiekink, Lai Yoong Goh , T.S. Andy Hor
Department of Chemistry, National University of Singapore, 3 Science Drive 3, Kent Ridge, Singapore 117543, Singapore
Received 17 November 2003; accepted 15 December 2003
Abstract
The reactions of CpRu(dppf)Cl (1) with the sulfur-containing ligands, thiophenol HSPh, 2-mercaptopyridine C5H4N(SH),
thiourea SC(NH2)2, vinylene trithiocarbonate SCS(CH)2S and ethylene trithiocarbonate SCS(CH2)2S, yielded chloro-substituted
derivatives, viz. the mono-ruthenium(II) complexes CpRu(dppf)(SPh) (2), [CpRu(dppf)(SC5H4NH)]BPh4 (3)BPh4, [CpRu(dppf)
(SC(NH2)2]PF6 (4)PF6, [CpRu(dppf)(SCS(CH)2S)]Cl (5)Cl and [CpRu(dppf)(SCS(CH2)2S)]Cl (6)Cl, respectively. Treatment of 1
with AuCl(SMe2) in the presence of NH4PF6 gave [(CpRu(dppf)(SMe2)]PF6 (7)PF6. The reaction of 1 or 6 with SnCl2 resulted in
cleavage of chloro and dithiocarbonate ligands, respectively, to give CpRu(dppf)SnCl3 (8). All complexes were spectroscopically
characterized and the structures of 2 and cationic complexes 4–7 were determined by single-crystal diffraction analyses.
Ó 2004 Elsevier B.V. All rights reserved.
Keywords: Ruthenium; 1,10-Bis(diphenylphosphino)ferrocene; Sulfur-containing ligands; Cyclopentadienyl; Crystal structures
1. Introduction
2. Results and discussion
There is continuing interest in the chemistry of tran-
sition-metal complexes with sulfur-containing ligands as
model compounds for biological systems and industrial
metal sulfide catalysts [1–5]. The chemistry of divalent
ruthenium complexes [CpRu(L)2]þ containing phos-
phines and sulfur ligands has been extensively studied
[6,7] but there are few examples of such complexes
containing ferrocene ligands, such as 1,10-bis(diph-
enylphosphino)ferrocene (dppf) [8–11]. Since dppf-con-
taining complexes are of interest on account of their
coordination versatility and catalytic potential [12,13],
we have investigated the reactivity of CpRu(dppf)Cl (1)
with some sulfur-based ligands. The results of this in-
vestigation are described herein.
2.1. Reactions of CpRu(dppf)Cl (1)
2.1.1. With thiophenol
The reaction of 1 with thiophenol HSPh at room
temperature gave air-stable orange precipitates of
[CpRu(dppf)(SPh)] (2) in 83% yield (Scheme 1). The
proton NMR spectrum of 2 shows the Cp ligand as a
singlet at d 3.96 and C5H4 in dppf as four equal-intensity
singlets at d 4.01, 4.23, 4.25 and 5.42; the 31P{1H}
spectrum shows a resonance at d 48.0 for the dppf li-
gand. The FABþ-mass spectrum displays the parent ion
at m=z 829, suggesting a mono-ruthenium complex,
which is verified by its X-ray crystal structure described
below. This neutral thiolate complex 2 is fairly stable
towards oxidation by atmospheric oxygen, both in the
solid state and in solution, and does not undergo di-
merization or trimerization with loss of phosphine
ligands, as observed by Shaver for the analogous com-
pound [CpRu(PPh3)2S(1-C3H7)] (Scheme 2) [14]. Un-
doubtedly, 2 owes its higher stability to the presence of
the robust bidentate dppf chelate.
* Corresponding authors. Tel.: +65-68742677; fax: +65-67791691.
E-mail addresses: chmgohly@nus.edu.sg (L.Y. Goh), andyhor@
nus.edu.sg (T.S.A. Hor).
0022-328X/$ - see front matter Ó 2004 Elsevier B.V. All rights reserved.
doi:10.1016/j.jorganchem.2003.12.020

X.L. Lu et al. / Journal of Organometallic Chemistry 689 (2004) 1444–1451
1445
+
+ HSPh
NH2
NH2
PF6-
Ru
P
Ru
Ru
P
S
C
P
P
(4)PF6
SPh
Cl
P
P
(1)
(2)
+
Scheme 1.
SCS(CH)2S
S
S
CH
CH
-
Ru
P
Cl
Ru
P
P
S
C
(5)Cl
(6)Cl
P
Cl
2.1.2. With 2-mercaptopyridine
The orange complex [CpRu(dppf)(SC5H4NH)]BPh4
(3)BPh4 was obtained in 80% yield from a reaction of 1
with 2-mercaptopyridine C5H4N(SH) (Scheme 3). Its 1H
NMR spectrum shows an N–H proton at d 9.66, in-
dicative of mono-coordination of SNC5H5 via its S
atom, as was previously observed for [CpRu(PPh3)2
(SNH(C5H4))]þ [7b]. The mN–H stretch is observed at
3758 cmꢀ1 in its IR spectrum. Unfortunately, X-ray
diffraction-quality crystals could not be obtained.
(1)
+
-
S
S
CH2
CH2
Ru
P
Cl
P
S
C
Scheme 4.
FABþ-mass spectrum of 4 shows the parent ion at m=z
796, followed by a fragment m=z 721, indicating loss of
the SC(NH2)2 ligand, while its FABꢀ-mass spectrum
shows the counter ion PFꢀ6 at m=z 145.
2.1.3. With thiourea and trithiocarbonates
Other sulfur-donors can be conveniently introduced
through a direct ligand (chloride) substitution reaction.
For example, complex 1 reacts with thiourea SC(NH2)2
in the presence of NH4PF6 to give 84% yield of
[CpRu(dppf)(SC(NH2)2]PF6 (4)PF6 (yellow) or with the
trithiocarbonates, SCS(CH)2S and SCS(CH2)2S, to give
[CpRu(dppf)(SCS(CH)2S]Cl (5)Cl (orange-red) and
[CpRu(dppf)(SCS(CH2)2S]Cl (6)Cl (orange-red), re-
spectively, in 95% yields (Scheme 4).
The H NMR spectrum of 5þ shows the CH reso-
1
nances of trithiocarbonate ligand at d 7.09–7.18 and d
7.68–7.98, Cp as a singlet at d 4.68 and C5H4 of dppf as
four equal-intensity singlets at d 4.14, 4.32, 4.40 and
1
4.75. The 31P{1H} resonance is seen at d 48.5. The H
NMR spectrum of 6 shows a Cp peak at d 4.15, CH2
resonances as two singlets at d 4.34 and 4.39, and C5H4
resonances of dppf as a broad apparent singlet at d 4.68
at 300 MHz, and as overlapping singlets at d 4.67 and
4.49 at 500 MHz. At this stage, we are unable to ra-
tionalize this difference from the normally observed four
equal-intensity singlets for the a and b Cp protons of the
ferrocenyl ligand, as observed in the other complexes in
this work. The 31P{1H} resonance is seen at d 49.6. The
FABþ-mass spectra of 5 and 6 show parent ions at m=z
855 and 857, respectively, and the fragment [CpRu
(dppf)]þ at m=z 721.
1
In the H NMR spectrum of complex 4þ, the proton
resonance of Cp is observed as a singlet at d 4.45 and of
C5H4 in dppf as four singlets of equal-intensity at d 4.13,
4.30, 4.38 and 4.87. The N–H proton is seen at d 9.72.
The 31P{1H} resonances are observed at d 47.7 (dppf)
and )144 (PF6). In the IR spectrum, mN–H stretching
frequencies are observed at 3382 and 3275 cmꢀ1 and P–
F stretching frequencies at 840 and 556 cmꢀ1. The
R
PPh3
dimerization
2.1.4. With AuCl(SMe2)
S
S
[CpRu(PPh3)2(SR)]
-PPh3
Ru
Ru
Ph3P
R =1-C3H7
Treatment of 1 with AuCl(SMe2) in the presence of
NH4PF6 in acetone gave [CpRu(dppf)(SMe2)]PF6
(7)PF6 in 70% yield (Scheme 5), together with the for-
mation of NH4AuCl2. This finding is in agreement with
the established lability of the thioether moiety in
R
Proposed structure
Scheme 2.
[CpRu(SR)]3
+
+
N
H
N
HS
−
NH4PF6
-
Ru
Ru
P
PF6-
BPh4
Ru
P
+ AuCl2
Ru
P
+ AuCl(SMe2)
P
Cl
P
S
NaBPh4
P
P
Cl
Me2CO
SMe2
P
(3)
(1)
(1)
(7)
Scheme 3.
Scheme 5.

1446
X.L. Lu et al. / Journal of Organometallic Chemistry 689 (2004) 1444–1451
Ru
P
P
SnCl2
Cl
Cl
Ru
(1)
P
Sn
Cl
Cl
+
P
-
Cl
SnCl2
(8)
S
S
Ru
P
S
P
(6)Cl
Scheme 6.
AuCl(SMe2); it is conceivable that the AuCl fragment
could abstract chloride from 1 to form the AuClꢀ2 anion
[15]. The NMR spectra of 7þ show proton resonances of
Me as a broad peak at d 2.26 (m1=2 ca. 91 Hz), Cp as a
singlet at d 4.79, C5H4 of dppf as four equal-intensity
resonances at d 4.72, 4.49, 4.32, 4.26 and 31P resonances
for dppf at d 48.4, and a septet for PF6 at d )144. The
FABþ-mass spectrum shows the parent ion at m=z 783
and a fragment at 721 indicating the loss of the SMe2
ligand. The FABꢀ-mass spectrum shows m=z 145 for the
counter ion PF6, the presence of which is also supported
by mP–F stretching frequencies at 842 and 557 cmꢀ1 in its
IR spectrum.
Fig. 1. (a) Molecular structures of the two independent molecules of
[CpRu(dppf)(SPh)] (2). (b) Superimposition of the two independent
molecules of (2).
2.1.5. With SnCl2
Treatment of 1 with SnCl2 gave [CpRu(dppf)SnCl3]
(8) in 90% yield (Scheme 6). The FABþ-mass spectrum
shows the parent ion at m=z 945 [M]þ, and fragments
indicating loss of SnCl2 and SnCl3 at 756 [M ) SnCl2]þ
and 721 [M ) SnCl3]þ, respectively. The NMR spectra
show the Cp proton resonance at d 4.68 and the C5H4
protons of dppf ligand as four equal-intensity singlets at
d 5.16, 4.38, 4.36 and 4.27, and a sharp 31P{1H} reso-
nance at d 50.5. The Cp resonance was observed at d 4.5
in the related compound [CpRu(PPh3)2SnCl3] prepared
by Siebald and co-workers [16] from the reaction of
[CpRu(PPh3)2Cl] with SnCl2. An in situ NMR spectral
study showed that the reaction of 6 with SnCl2 also gave
[CpRu(dppf)SnCl3] (8) together with free trithiocar-
bonate ligand SCS(CH2)2S.
Fig. 2. Molecular structure of [CpRu(dppf)(SC(NH2)2]þ (4).
Fig.1(b) which highlights the major differences in the
orientations of the P- and S-bound phenyl groups and
less major differences between the Cp rings in the two
independent molecules. Consistent with this, there are
no significant differences between the bond parameters
of the two molecules. The Ru centre is coordinated by a
Cp ring, that occupies one octahedral face, two P atoms
of the diphosphine ligand and the thiolate S of the
thiophenolate; the two P and S atoms define the second
octahedral face. The Ru–S bond distances in 2 are
2.2. Molecular structures
The molecular structures of the 2, 4–7 cations have
been determined by single-crystal X-ray diffraction
analyses, and are shown in Figs. 1–5; selected bond pa-
rameters of these complexes are summarized in Table 1.
The crystal structure of complex [CpRu(dppf)(SPh)]
(2) contains two independent molecules in the asym-
metric unit (Fig. 1(a)). The two independent molecules
of 2 are not superimposable as may be seen from
ꢀ
2.434(4) and 2.454(3) A which are significantly longer
than other examples of Ru(II)–S(thiolate) bonds, e.g.,
ꢀ
2.30 A (av.) in [CpRu(S-1-C3H7)]3 [14], 2.3763(13)–
ꢀ
2.3858(13)A in (arene)Ru(S(CH2CH2S)2) [17] and

X.L. Lu et al. / Journal of Organometallic Chemistry 689 (2004) 1444–1451
1447
þ
Fig. 3. Molecular structure of [CpRu(dppf)(SCS(CH)2S)] (5).
Fig. 5. Molecular structure of [CpRu(dppf)(SMe2)]þ (7).
long Ru–S bond is due to the destabilizing filled–filled
dp–pp orbital interaction between the p-type sulfur lone
pair and the formally occupied metal dp orbitals of the
Ru(II) low spin d6-centre, as sustantiated by Fenske-
Hall molecular orbital calculations coupled with
gas-phase photoelectron spectroscopy for CpFe thio-
phenolate complexes by Ashby et al. [19].
A diffraction-quality crystal of 3 has not been ob-
tained. Its formulation with a 1H-pyridinethione ligand
as presented in Scheme 3, is consistent with the
þ
Fig. 4. Molecular structure of [CpRu(dppf)(SCS(CH2)2S)] (6).
ꢀ
2.320(2)–2.4155(8)A in similar thiolate/thioether com-
plexes [18], as well as those in other sulfur-containing
complexes described in this paper (seen in Table 1). The
Table 1
a
ꢀ
Selected bond lengths (A) and bond angles (°) of complex 2 , and cations 4–7
Complexes
Ru–P
Ru–S
C–S
P–Ru–P
P–Ru–S
[CpRu(dppf)(SPh)] (2)
2.284(3)A
2.302(3)A
2.295(3)B
2.306(3)B
2.434(4)A
2.454(3)B
1.779(8)
1.793(12)
99.02(10)A
98.52(10)B
89.29(11)A
85.75(12)B
[CpRu(dppf)(SC(NH2)2]PF6 (4)PF6
2.313(2);
2.309(2)
2.395(3)
1.719(11)
C–N:
96.74(9)
88.64(9)
86.24(9)
1.349(12)
1.315(12)
[CpRu(dppf)(SCS(CH)2S]Cl (5)Cl
[CpRu(dppf)(SCS(CH2)2S]PF6 (6)PF6
[CpRu(dppf)(SMe2)]PF6 (7)PF6
2.3076(14)
2.3156(13)
2.3863(13)
2.3417(10)
2.3605(11)
1.692(6)
1.695(7)
1.730(5)
97.35(5)
98.13(3)
97.40(3)
87.58(5)
86.72(5)
2.3207(9)
2.3231(10)
1.659(4)
1.687(4)
1.728(4)
85.96(4)
86.72(5)
2.3271(10)
2.3149(9)
1.799(4)
1.802(4)
84.66(3)
95.86(4)
a Contains two independent molecules A and B in the unit cell.

1448
X.L. Lu et al. / Journal of Organometallic Chemistry 689 (2004) 1444–1451
unipositive charge of the complex ion and in agreement
with postulations of Puerta for analogous complexes
containing monodentate phosphines [7b].
In complex 4, which crystallizes with 0.25CH2Cl2 and
0.5H2O molecules in the asymmetric unit, the CpRu
moiety is coordinated to a chelating dppf ligand and one
S atom of the thiourea ligand, as shown in Fig. 2, so that
the overall coordination geometry is the same as that
found in 2. The Ru–P and Ru–S distances are in the
expected ranges [17,18,20].
3. Experimental
All reactions were performed under dry nitrogen us-
1
ing Schlenk techniques. H and 31P{1H} NMR spectra
were recorded on a Bruker ACF300 or AMX500 FT
NMR spectrometer, with chemical shifts referenced to
residual non-deuterio solvent and external H3PO4, re-
spectively. IR spectra were obtained with KBr pellet on
a Perkin–Elmer 1600 spectrophotometer. Mass spectra
were obtained on a Finnigan MAT95XL-T spectrome-
ter. All elemental analyses were performed in-house,
using a Perkin–Elmer Model Number Series II CHNS/O
2400 analyser.
RuCl3 ꢁ 3H2O and AuCl(SMe2) were obtained from
Aldrich. PPh3, dppf, thiophenol, 2-mercaptopyridine,
vinylene trithiocarbonate, ethylene trithiocarbonate and
thiourea were supplied by Merck. [CpRu(PPh3)2Cl] [21]
and [CpRu(dppf)Cl] [22] were synthesized as described.
All solvents were freshly distilled from standard drying
agents before use.
The structures of cationic [CpRu(dppf)(SCS(CH)2S)]þ
(5) and [CpRu(dppf)(SCS(CH2)2S)]þ (6) are similar,
containing the trithiocarbonate ligands, SCS(CH)2S
and SCS(CH2)2S, respectively (Figs. 3 and 4). The unit
cell of 5 contains disordered solvent molecules so that
for each 5(Cl), there are 0.5EtOH, 0.5MeOH and
0.5H2O; chloride is not disordered, but two 1/4 of water
molecules were found near methanol. There is experi-
mental evidence that the Ru–S bond distance in 5þ is
significantly longer than that in 6þ and, conversely,
there is an indication that the Ru–P bond distances in 5þ
are shorter than those in 6þ. An examination of the
parameters associated with the S-containing ligands
reveals a plausible explanation forþthis. Thus, the C–C
3.1. Reactions of [CpRu(dppf)Cl] (1)
3.1.1. With thiophenol HSPh
ꢀ
bond length of 1.337(11) A in 5 is consistent with
To a yellow suspension of 1 (0.055 g, 0.07 mmol) in
EtOH (20 ml), HSPh (0.01 ml, 0.1 mmol) was added and
the mixture was stirred for 1 h. The resultant orange
suspension was filtered to collect an orange precipitate
of [CpRu(dppf)(SPh)] (2), which was washed twice with
EtOH (2 ꢂ 2 ml), followed by diethyl ether (2 ꢂ 2 ml)
and dried in vacuo (0.050 g, 0.06 mmol, 83% yield).
Anal. Calc. for C45H38P2SFeRu: C, 65.1; H, 4.6; P, 7.5;
S, 3.9. Found: C, 65.2; H, 4.5; P, 7.4; S, 3.8%. 1H NMR
(CDCl3): d 3.97 (s, 5H, C5H5), 4.01, 4.23, 4.25 and 5.42
(each s, 2H, C5H4), and for Ph protons d 6.84 (c.m.,
2H), 6.93 (c.m., 2H), 7.24–7.40 (m, 17H) and 7.80 (c.m.,
4H); 31P {1H}: d 48.0. FABþ-MS: m=z 829 [M]þ, 721
[M ) SPh]þ. IR(KBr, cmꢀ1): m 3048w, 2967w, 1573w,
1477w, 1433m, 1262m, 1157wsh, 1089vs, 1029vs, 802vs,
745s, 695vs, 626w, 546wsh, 502s, 475s and 440m.
significant double bond character in this bond. Also
noteworthy is that the two formally single C–S
bond distances in 5þ are identical (C1–S1 1.692(6) A
ꢀ
ꢀ
and C1–S2 1.695(7) A) indicative of substantial delo-
calization of p-electron density over the CS3 entity,
shown in Chart 1; this does not occur in 6þ with a
ꢀ
saturated C–C link (1.404(7) A) between the endocyclic
S atoms. The above results in the decreased donor-
capability of S1 in 5þ, with a weakening of the Ru–S
bond.
[CpRu(dppf)(SMe2)]PF6 (7) possesses an octahedral
coordination geometry at the Ru atom as found for the
other complex geometries described above; Fig. 5. The
structure crystallizes with 0.25CH2Cl2 and 0.5MeOH
molecules per 7(PF6) entity. As can be noted from the
data in Table 2, the Ru–S and Ru–P bond distances in
the cation are entirely consistent with the geometric
parameters reported for the complex cations previously
described.
3.1.2. With 2-mercaptopyridine (C5H4N)SH
To a yellow suspension of 1 (0.030 g, 0.04 mmol) in
MeOH (20 ml) was added 2-mercatopyridine (0.006 g,
+
+
S2
CH2
CH2
Ru
S2
CH
CH
Ru
P
P
-
PF6
-
Cl
S1
C1
1.692(6)
S1
C1
P
P
1.659(4)
S3
S3
(5)
(6)
Chart 1.

X.L. Lu et al. / Journal of Organometallic Chemistry 689 (2004) 1444–1451
1449
Table 2
Crystal and structure refinement data
Complexes
2
(4)PF6 ꢁ 0.25CH2Cl2 ꢁ (5)Cl ꢁ 0.5EtOH ꢁ
(6)PF6
(7)PF6 ꢁ 0.25CH2Cl2 ꢁ
0.5H2O
0.5MeOH ꢁ 0.5H2O
C43:5H41ClFeO1:5P2RuS3
0.5MeOH
Empirical formula
C45H38FeP2RuS
C40:25H38:5Cl0:5F6-
FeN2O0:5P2RuS
971.85
C42H37F6FeP3-
RuS3
C41:75H41:5Cl0:5F6-
FeO0:5P3RuS
964.86
Formula weight
Temperature (K)
Crystal system
Space group
829.67
293(2)
Monoclinic
P21
10.6928(6)
32.9248(19)
11.2853(7)
90
937.75
293(2)
Triclinic
1001.73
223(2)
Orthorhombic
223(2)
Monoclinic
223(2)
Monoclinic
ꢁ
P21=c
P1
Pbca
P21=c
ꢀ
a (A)
15.7683(11)
14.5401(11)
20.0040(14)
90
11.6049(11)
13.3588(13)
14.2870(14)
103.867(2)
96.888(2)
92.123(2)
2129.8(4)
2
15.8272(8)
18.7391(11)
27.5132(16)
90
10.1794(4)
30.3410(12)
14.0100(6)
90
ꢀ
b (A)
ꢀ
c (A)
a (°)
b (°)
c (°)
110.821(1)
90
112.570(2)
90
90
90
97.431(1)
90
3
ꢀ
V (A )
3713.6(4)
4
1.44
4235.1(5)
4
1.524
8160.1(8)
8
1.631
4290.7(3)
4
1.494
Z
Density (g/cm3)
Absorption efficient
1.462
1.014
0.972
0.952
1.056
0.938
(mmꢀ1
)
F ð000Þ
1696
1966
957
0.24 ꢂ 0.2 ꢂ 0.16
1.77–25.00
4048
1958
Crystal size (mm3)
h range for data
collection (°)
0.28 ꢂ 0.10 ꢂ 0.10 0.14 ꢂ 0.1 ꢂ 0.06
0.34 ꢂ 0.10 ꢂ 0.08 0.13 ꢂ 0.21 ꢂ 0.23
1.93–30.01
1.78–25.00
1.48–28.28
1.6–30.0
Index ranges
ꢀ15 6 h 6 14,
ꢀ46 6 k 6 46,
ꢀ9 6 l 6 15
30,068
ꢀ18 6 h 6 14,
ꢀ17 6 k 6 16,
ꢀ23 6 l 6 22
24,379
ꢀ10 6 h 6 13,
ꢀ15 6 k 6 15,
ꢀ16 6 l 6 15
11,828
ꢀ20 6 h 6 ꢀ21,
ꢀ24 6 k 6 24,
ꢀ36 6 l 6 18
58,991
ꢀ14 6 h 6 14,
ꢀ37 6 k 6 42,
ꢀ17 6 l 6 19
35,653
Reflections collected
Independent reflections
Maximum and minimum
transmission
19,947
0.9303 and
0.7656
7453
0.9391 and 0.8593
7477
0.8733 and 0.7804
10,122 12,497
0.9230 and 0.7154 0.844 and 1
Data/restraints/parameters 19947/1/813
Goodness-of-fit on F 2c
Final R indices
7453/171/485
1.018
7477/4/481
1.057
10122/0/505
1.041
8982/2/499
0.83
1.013
R1 ¼ 0:0646,
wR2 ¼ 0:1312
R1 ¼ 0:1431,
wR2 ¼ 0:1784
R1 ¼ 0:0749,
wR2 ¼ 0:1796
R1 ¼ 0:1371,
wR2 ¼ 0:2057
R1 ¼ 0:0519,
wR2 ¼ 0:1397
R1 ¼ 0:0664,
wR2 ¼ 0:1453
1.191 and )0.531
R1 ¼ 0:0536,
wR2 ¼ 0:1184
R1 ¼ 0:0830,
wR2 ¼ 0:1311
R1 ¼ 0:056,
wR2 ¼ 0:144
R1 ¼ 0:081,
wR2 ¼ 0:161
a;b
½I > 2rð1Þꢃ
R indices (all data)
Largest difference peak
ꢀ3
1.366 and )0.690 1.124 and )0.996
0.837 and )0.451 1.23 and )0.39
ꢀ
and hole (e A
)
P
P
a R1 ¼ ð jFoj ꢀ jFcjÞ jFoj.
P
P
2
2 1=2
b wR2 ¼ ½ð xjFoj ꢀ jFcjÞ = xjFoj ꢃ
.
P
2
1=2
c GoF ¼ ½ð xjFoj ꢀ jFcjÞ =ðNobs ꢀ NparamÞꢃ
.
0.05 mmol), followed by NaBPh4 (0.041 g, 0.1 mmol)
and the mixture was stirred for 15 min, leading to an
orange red mixture which was evacuated to dryness. The
residue was extracted with CH2Cl2 (5 ꢂ 2 ml) to remove
residual sodium salts; concentration of the combined
extracts to ca. 1 ml, followed by addition of hexane (2
ml), gave orange solids of [CpRu(dppf)(S(C5H4NH)]
BPh4 (3)BPh4 (0.036 g, 0.03 mmol, 80% yield). Anal.
Calc. for C68H58BNP2SFeRu0.5CH2Cl2: C, 68.9; H, 5.0;
N, 1.2; P, 5.2; S, 2.7. Found: C, 68.9; H, 5.1; N, 1.2; P,
2907vw, 2854vw, 1650w, 1565m, 1476w, 1427w, 1261w,
1122msh, 1089s, 1033m, 803m, 739m, 701s and 475s.
3.1.3. With thiourea, SC(NH2)2
A yellow suspension of 1 (0.062 g, 0.08 mmol) and
NH4PF6 (0.029 mg, 0.18 mmol) in MeOH (25 ml) was
stirred for 30 min, NH2C(S)NH2 (0.010 g, 0.13 mmol)
was then added and stirring continued for 3 h. The re-
sultant suspension was filtered to remove the white
precipitates of ammonium salts. The filtrate was evac-
uated to dryness and extracted with CH2Cl2 (5 ꢂ 2 ml)
to remove residual ammonium salts; concentration of
the combined extracts to ca. 1 ml, followed by addition
of hexane (3 ml), gave yellow crystals of [CpRu(dppf)
(SC(NH2)2)]PF6 (4)PF6 (0.065 g, 0.07 mmol, 84% yield)
obtained after cooling for 30 min at 0 °C. Anal. Calc. for
C40H37F6N2P3SFeRu ꢁ 0.5CH2Cl2: C, 49.4; H, 3.9; N,
1
5.2; S, 2.7%. H NMR (CDCl3): d 4.41 (s, 5H, C5H5);
4.11, 4.27, 4.33 and 4.85 (each s, 2H, C5H4); 5.81 (t, 1H),
6.13 (t, 1H), 6.89 (q, 6H), 7.02 (t,7H), 7.10 (d, 1H), 7.27
(c.m, 8H) and 7.42 (c.m., 20H) (8Ph + C5H4); 9.66 (br,
1H, NH); 31P {1H}: d 47.7(s, dppf). ESIþ-MS: m=z 831
[M]þ, 721 [M ) SC5H4NH]þ. ESIꢀ-MS: m=z 319
[BPh4]ꢀ. IR(KBr, cmꢀ1): mNH 3758w; m (others) 3053wbr,

1450
X.L. Lu et al. / Journal of Organometallic Chemistry 689 (2004) 1444–1451
2.9; P, 9.4; S, 3.3; F, 11.6. Found: C, 49.4; H, 3.8; N, 2.8;
P, 9.9; S, 3.2; F, 11.8%. 1H NMR (CDCl3): d 4.13, 4.30,
4.38 and 4.87 (each s, 2H, C5H4), 4.45 (s, 5H, C5H5),
7.25–7.50 (m, 20H, Ph), 5.9 (vbr, m1=2 ca. 50 Hz, ca.4H,
NH2);31P {1H}: d 47.7 (s, dppf); )144 (septet, JP–F 710
Hz, PF6). FABþ-MS: m=z 796 [M]þ, 721
[M ) NH2C(S)NH2]þ. FABꢀ-MS: m=z 145 [PF6]ꢀ.
IR(KBr, cmꢀ1): mNH 3382vs and 3275s; mPF6 840s and
556s; m (others) 3176s, 2683vw, 1616vs, 1471m, 1415vs,
1262vw, 1085s, 727m, 625m and 480vsbr.
3.1.5. With AuCl(SMe2)
To a yellow suspension of 1 (0.020 g, 0.03 mmol) in
acetone (20 ml), AuCl(SMe2) (0.010 g, 0.03 mmol) and
NH4PF6 (0.010 g, 0.06 mmol) were added and the
mixture was stirred for 10 h. The resultant brown yellow
suspension was filtered, to remove a yellow solid, which
is mainly insoluble. 1H and 31P{1H} NMR spectra of an
CDCl3 extract of this solid showed the presence of un-
reacted 1. Presumably the insoluble component is
NH4AuCl2 [15]. Concentration of the filtrate to ca. 1 ml,
followed by addition of diethyl ether (2 ml) gave brown
solids of [CpRu(dppf)(SMe2)]PF6 (7) PF6 (0.019 g,
70%). Anal. Calc. for C41H39F6P3SFeRu: C, 53.1; H,
4.2; P, 10.0; S, 3.5. Found: C, 53.0; H, 4.4; P, 9.8; S,
3.4%. 1H NMR (CDCl3): d 2.26 (m1=2 ¼ 91 Hz, 6H,
CH3), 4.79 (s, 5H, C5H5), 4.26, 4.32, 4.49 and 4.72 (s,
2H, C5H4), 7.21–7.23 (m, 4H, Ph), 7.32 (t, J ¼ 7 Hz, 4H,
Ph), 7.40–.47 (m, 12 H, Ph); 31P {1H}: d 48.4 (s) and
)144 (septet, JPF ¼ 710 Hz). FABþ-MS: m=z 783 [M]þ,
721 [M ) SMe2]þ. FABꢀ-MS: m=z 145 [PF6]ꢀ. IR(KBr,
cmꢀ1): mPF6 842 and 557.
3.1.4. With vinylene trithiocarbonate SCS(CH)2S and
ethylene trithiocarbonate SCS(CH2)2S
To a yellow solution of 1 (0.055 g, 0.07 mmol) in
MeOH (20 ml) and CH2Cl2 (10 ml), SCS(CH)2S
(0.009 g, 0.07 mmol) was added; the mixture turned
orange red immediately and was stirred for 30 min.
Concentration of the solution to ca. 1 ml, followed by
addition of hexane (2 ml), gave orange red solids of
[CpRu(dppf)(SCS(CH)2S)]Cl (5)Cl (0.061 g, 0.068
mmol, 95% yield). Anal. Calc. for C42H35
ClP2S3FeRu ꢁ 0.5(C6H14): C, 57.9; H, 4.5; P, 6.6; S,
10.3. Found: C, 58.1; H, 4.4; P, 6.3; S, 10.2%. 1H
NMR (CDCl3): d 4.68 (s, 5H, C5H5), 4.14, 4.32, 4.40
and 4.75 (each s, 2H, C5H4), 7.09–7.18 and 7.68–7.98
(m, 2H, CH), 7.41–7.50 (m, 20H, Ph); 31P {1H}: d
48.5 (s, dppf). FABþ-MS: m=z 855 [M]þ, 721
[M ) SCS(CH)2S]þ. IR(KBr, cmꢀ1): m 2922s, 2853m,
1648w, 1519w, 1459w, 1260vw, 1089s, 1029s, 808w
and 695w.
3.1.6. With SnCl2
To a yellow solution of 1 (0.037 g, 0.05 mmol) in
toluene (5 ml) and MeOH (5 ml), SnCl2 (0.011 g, 0.06
mmol) was added and the mixture was stirred for 6 h.
The yellow resultant solution was evacuated to dryness
and extracted with toluene (3 ꢂ 2 ml). The combined
extracts were concentrated to ca. 2 ml, hexane (2 ml) was
added, giving yellow solids of [CpRu(dppf)(SnCl3)] (8)
(0.041 g, 0.04 mmol, 90% yield). Anal. Calc. for
C39H33Cl3P2FeRuSn: C, 49.5; H, 3.5; P, 6.6; Cl, 11.3.
Found: C, 49.6; H, 3.6; P, 6.9; Cl, 10.9%. 1H NMR
(CDCl3): d 4.27, 4.36, 4.38 and 5.16 (each s, 2H, C5H4),
4.68 (s, 5H, C5H5), 7.37 and 7.42 (each, c.m., total 20H,
Ph); 31P {1H}: d 50.5 (s). FABþ-MS: m=z 945 [M]þ, 756
[M ) SnCl2]þ, 721 [M ) SnCl3]þ. IR(KBr, cmꢀ1): m
2928w, 1631w, 1563vw, 1433w, 1262m, 1162wsh,, 1089s,
1033s, 808m, 743m, 698s and 475s.
A similar reaction of 1 (0.055 g, 0.07 mmol) with
SCS(CH2)2S (0.010 g, 0.07 mmol) gave orange red solids
of [CpRu(dppf)(SCS(CH2)2S)]Cl (6)Cl (0.057 g, 0.066
mmol, 95% yield). Anal. Calc. for C42H37ClP2S3
FeRu ꢁ CH2Cl2: C, 52.9; H, 4.0; P, 6.3; S, 9.8. Found: C,
1
52.6; H, 4.2; P, 6.0; S, 9.9%. H NMR (CDCl3): d 4.15
(s, 5H, C5H5), 4.34, 4.39 (each s, 2H, CH2), 4.68 (ap-
parent s (br. m1=2 ¼ 10 Hz), which at 500 MHz is seen as
overlapping singlets at d 4.67 and 4.69, total 8H, C5H4),
7.39–7.51 (m, 20H, Ph); 13C: 45.5 (CH2); 84.3, 75.2, 74.2,
72.0 and 68.8 (Cp and Cp of dppf); 124.7, 127.8, 128.3,
130.2, 130.4, 133.3, 133.6 and 138.7 (Ph); 154.9 (C(S)S2).
31P{1H}: d 49.6 (s, dppf). FABþ-MS: 857 [M]þ, 721
1H NMR spectral monitoring of a reaction of 6 (6
mg, 0.006 mmol) with SnCl2 (1.2 mg, 0.006 mmol) in
CDCl3 (0.5 ml) showed that 8 was produced, together
with free SCS(CH)2S (d (CH) 7.10).
[M ) SCS(CH2)2S]þ. IR(KBr, cmꢀ1):
m
2985vw,
1625vwsh, 1615vw, 1478vw, 1432m, 1384vw, 1155msh,
1122m, 1089m, 1047s, 910w, 837m, 814msh, 751s, 698vs,
624m, 544msh, 507vs, 473s and 438s.
3.2. Structure determinations
6 was converted to its PF6 salt for obtaining single
crystals. To an orange red solution of 6 (0.010 g, 0.01
mmol) in MeOH (5 ml), NH4PF6 (0.002 g, 0.01 mmol)
was added and the mixture was stirred for 10 min. The
resultant suspension was filtered to remove the white
precipitates of ammonium salts. Concentration of the
filtrate to ca. 0.5 ml, followed by addition of ether (1 ml),
gave orange red crystals of [CpRudppf(SCS(CH2)2S)] PF6
(6)PF6.
Diffraction-quality single crystals were obtained
from solutions at 0 °C as follows: 2 and (4)PF6 ꢁ
0.25 CH2Cl2 ꢁ 0.5H2O as orange and yellow prisms, re-
spectively, from CH2Cl2-hexane after 2–3 h; (5) Cl0 ꢁ
5EtOH ꢁ 0.5MeOH ꢁ 0.5H2O as orange prisms from
EtOH/MeOH-ether after 30 min, (7) PF6 ꢁ 0.25CH2 Cl2 ꢁ
0.5MeOH as yellow-brown prisms from CH2Cl2-MeOH
after 2–3 h. (6)PF6 was obtained as orange red prisms
from acetone–ether after 3 days at room temperature.

X.L. Lu et al. / Journal of Organometallic Chemistry 689 (2004) 1444–1451
1451
X-ray data for 2, (4)PF6 ꢁ 0.25CH2Cl2 ꢁ 0.5H2O,
References
(5)Cl ꢁ 0.5EtOH ꢁ 0.5MeOH ꢁ 0.5H2O, (6)PF6 and (7)
PF6 ꢁ 0.25CH2Cl2 ꢁ 0.5MeOH were collected on a Sie-
mens SMART diffractometer, equipped with a CCD
detector, using Mo Ka radiation. Data were corrected
for Lorentz and polarization effects with the SMART [23]
program, and for absorption effects with SADABS [24].
Structure solution (heavy-atom methods) and refinement
(on F 2: anisotropic displacement parameters, H atoms in
calculated positions, and a weighting scheme of the form
w ¼ 1=½r2ðFo2Þ þ aP2 þ bPꢃ, where P ¼ ðFo2 þ 2Fc2Þ=3Þ
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CH2Cl2 molecule and 0.5 of a MeOH molecule. These
atoms were refined isotropically and with constrained
C–Cl bond distances in the former. Crystal data and
refinement details are collected in Table 1.
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NH (3); X ¼ PF6, L ¼ SC(NH2)2 (4); X ¼ Cl, L ¼ SCS
(CH2)2S (6); X ¼ Cl, L ¼ SCS(CH)2S (5)), were obtained
from chloride substitution in [CpRu(dppf)Cl] (1). Like-
wise, [CpRu(dppf)(SMe2)]PF6 (7) and [CpRu(dppf)
(SnCl3)] (8) were obtained from the reaction of 1 with
AuCl(SMe2) and SnCl2, respectively.
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Crystallographic data for 2 and 4–7 have been de-
posited at the Cambridge Crystallographic Data Centre
with deposition numbers 223100–223104, respectively.
Copies of the information may be obtained free of
charge from The Director, CCDC, 12 Union Road,
Cambridge CB2 1EZ, UK (fax: +44-1223-336033;
e-mail: deposit@ccdc.cam.ac.uk or http://www.ccdc.
cam.ac.uk).
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Acknowledgements
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[23] SMART and SAINT Software Reference Manuals, Version 5.0,
Bruker AXS Inc., Madison, WI, 1998.
Support of the National University of Singapore
in the form of Grant Nos. RP14300077112 and
RP143000135112 to LYG and a research scholarship to
XLL are gratefully acknowledged. The authors also
thank Ms. G.K. Tan for technical assistance.
[24] G.M. Sheldrick, SADABS Software for Empirical Absorption
€
Correction, University of Gottingen, Germany, 2000.
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