Stabilisation of alkynyl dithiocarboxylates at a ruthenium centre: X-ray crystal structures of [Ru(H)(CO)(S2CCCPh)(PPh3)2], [Ru(CO)(CPh=CHPh)(S2CCCPh)(PPh3)2] and [Ru(CO)(CCMes)(S2CCCPh)(PPh3)2]

Article abstract of DOI:10.1016/S0022-328X(00)00653-7

Solutions of the alkynyldithiocarboxylate anions RCC-CS₂^- (R=Mes, Ph, Bu^t), generated by treatment of the acetylides LiCCR with carbon disulfide, are sufficiently stable to allow reaction with haloruthenium(II) complexes. In this way, the complexes [Ru(H)(CO)(S₂CCCR)(PPh₃)₂] and [Ru(CO)(CPh=CHPh)(S₂CCCR)(PPh₃)₂] (R=Mes, Ph, Bu^t) have been prepared and characterised. The vinyl complexes react with additional terminal alkynes R¹CCH at room temperature to afford the acetylide complexes [Ru(CO)(CCR¹)(S₂CCCR)(PPh₃)₂]. The crystal structures of [Ru(H)(CO)(S₂CCCPh)(PPh₃)₂], [Ru(CO)(CPh=CHPh)(S₂CCCPh)(PPh₃)₂] and [Ru(CO)(CCMes)(S₂CCCPh)(PPh₃)₂] have been determined.

Full text of DOI:10.1016/S0022-328X(00)00653-7

www.elsevier.nl/locate/jorganchem
Journal of Organometallic Chemistry 619 (2001) 209–217
Stabilisation of alkynyl dithiocarboxylates at a ruthenium centre:
X-ray crystal structures of [Ru(H)(CO)(S2CCꢀCPh)(PPh3)2],
[Ru(CO)(CPhꢁCHPh)(S2CCꢀCPh)(PPh3)2] and
[Ru(CO)(CꢀCMes)(S2CCꢀCPh)(PPh3)2]
Harry Adams, Paul E. McHugh, Michael J. Morris *, Sharon E. Spey,
Penelope J. Wright
Department of Chemistry, Uni6ersity of Sheffield, Sheffield S3 7HF, UK
Received 3 August 2000; received in revised form 30 August 2000
Abstract
Solutions of the alkynyldithiocarboxylate anions RCꢀC–CS−2 (R=Mes, Ph, But), generated by treatment of the acetylides
LiCꢀCR with carbon disulfide, are sufficiently stable to allow reaction with haloruthenium(II) complexes. In this way, the
complexes [Ru(H)(CO)(S2CCꢀCR)(PPh3)2] and [Ru(CO)(CPhꢁCHPh)(S2CCꢀCR)(PPh3)2] (R=Mes, Ph, But) have been prepared
and characterised. The vinyl complexes react with additional terminal alkynes R1CꢀCH at room temperature to afford the
acetylide complexes [Ru(CO)(CꢀCR1)(S2CCꢀCR)(PPh3)2]. The crystal structures of [Ru(H)(CO)(S2CCꢀCPh)(PPh3)2],
[Ru(CO)(CPhꢁCHPh)(S2CCꢀCPh)(PPh3)2] and [Ru(CO)(CꢀCMes)(S2CCꢀCPh)(PPh3)2] have been determined. © 2001 Elsevier
Science B.V. All rights reserved.
Keywords: Ruthenium; Alkyne; Hydride; Vinyl; Crystal structures
1. Introduction
relatively acidic protons, we were intrigued to discover
that there are very few reports dealing with alkynyl
dithiocarboxylates, RCꢀC–CS−2 , or their derivatives. In
1973 Brandsma and co-workers mentioned that in con-
trast to alkyl and aryl Grignard reagents, alkynyl Grig-
nards are insufficiently nucleophilic to add to CS2 [2].
More recently, Hartke reported the preparation of sev-
eral dithioesters of the type RCꢀC–CS2Me, mainly by
indirect methods from acetylenic thioamides, and
showed that unless R was a bulky aryl group, these
compounds decomposed at room temperature within a
few hours. Only in the case of R=Mes was it possible
to prepare a stable dithioester by deprotonation of
MesCꢀCH, addition of CS2 and alkylation with MeI,
and even then the intermediate anion MesCꢀC–CS2−
was described as unstable [3]. Moreover, only one
transition metal complex of such a ligand is known:
[Ru(S2CCꢀCPh)(PPh3)(h-C5H5)] was prepared by inser-
tion of carbon disulfide into the metal–carbon bond of
the corresponding acetylide complex [Ru(CꢀCPh)-
(PPh3)2(h-C5H5)] [4]. We therefore set out to discover
Addition of an anion X− to carbon disulfide affords
species of the type XCS2− which can be coordinated to
metal centres as uninegative didentate ligands, the most
common examples being dithiocarbamates (X=NR2),
xanthates (X=OR) and dithiocarboxylates (X=alkyl,
aryl, etc.) [1]. Given that terminal alkynes RCꢀCH have
Scheme 1. Synthesis of complexes 2a–c.
* Corresponding author. Tel.: +44-114-2229363; fax: +44-114-
2738673.
E-mail address: m.morris@sheffield.ac.uk (M.J. Morris).
0022-328X/01/$ - see front matter © 2001 Elsevier Science B.V. All rights reserved.
PII: S0022-328X(00)00653-7

210
H. Adams et al. / Journal of Organometallic Chemistry 619 (2001) 209–217
son with related complexes, e.g. the starting material.
Peaks due to the alkyne carbons were observed at 105.5
and 87.8 ppm, similar to their position in the stable
dithioester.
We next attempted the same reaction sequence with
phenylacetylene. Gratifyingly, treatment of [Ru(H)(Cl)-
(CO)(PPh3)3] with the red solution prepared by stirring
CS2 with LiCꢀCPh produced an analogous complex
[Ru(H)(CO)(S2CCꢀCPh)(PPh3)2] (2b) in 51% yield,
proving that the PhCꢀC–CS−2 anion is sufficiently sta-
ble in solution at room temperature for 1 h to enable
the reaction to proceed in the same way. The spectro-
scopic data of 2b are very similar to those of 2a.
Moreover, the synthesis of analogous 2c from
ButCꢀCH was also successful, showing that the pres-
ence of an aryl substituent is not necessary. We did not
observe any interaction between the hydride ligand and
the alkynyl portion of the dithiocarboxylate, in contrast
to the reactions of 1 with alkynecarboxylic acids which
gave compexes containing alkenylcarboxylate ligands
[6].
Scheme 2. Synthesis of complexes 3–5.
whether alkynyl dithiocarboxylates could be prepared
by addition of acetylide anions to CS2 and stabilised by
coordination to ruthenium.
2. Results and discussion
It is known that [Ru(H)(Cl)(CO)(PPh3)3] readily hy-
droruthenates alkynes to produce vinyl complexes of
the type [RuCl(CR1ꢁCHR2)(CO)(PPh3)n] where n can
be 2 or 3 depending on the steric bulk of the alkyne [7].
The chloride ligands in these products can also be
readily replaced by dithiocarbamates [8]. Treatment of
In order to maximise kinetic stabilisation of the
intermediate species, we initially followed the lead of
Hartke et al. by preparing MesCꢀCH (1a). We were
able to confirm that deprotonation of 1a with one
equivalent of BuLi followed by addition of CS2 gave a
dark red solution containing MesCꢀC–CS−2 which
yielded the stable dithioester MesCꢀC–CS2Me on alky-
lation with MeI [3]. We then investigated coordination
of the same anion to ruthenium, in the form of
[Ru(H)(Cl)(CO)(PPh3)3]. This compound was chosen
because it is known to react readily with dithiocarba-
mates by replacement of the chloride ligand and loss of
one labile PPh3 to give [Ru(H)(CO)(S2CNR2)(PPh3)2]
[5].
the
red
diphenylacetylene
derivative
[Ru-
Cl(CPhꢁCHPh)(CO)(PPh3)2] with the red solutions of
RCꢀCCS−2 (R=Mes, Ph, But) described above gave
green–brown solutions from which the compounds
[Ru(CO)(CPhꢁCHPh)(S2CCꢀCR)(PPh3)2]
(3a–c)
(Scheme 2) could be isolated by chromatographic work-
up in yields of 78, 72 and 25%, respectively. Their IR
spectra showed the presence of the alkynyldithiocar-
boxylate ligand, and the continued presence of the vinyl
group was indicated by a broad signal at approximately
1
Addition of one equivalent of the MesCꢀC–CS2−
solution to a suspension of [Ru(H)(Cl)(CO)(PPh3)3] in
THF caused the rapid dissolution of the complex and a
colour change from grey to red. The new complex
[Ru(H)(CO)(S2CCꢀCMes)(PPh3)2] (2a) could be iso-
lated by column chromatography as an air- and mois-
ture-stable red powder in 63% yield (Scheme 1). Its
solution IR spectrum showed a carbonyl absorption at
1936 cm−1 and a weaker peak due to the alkyne
functionality at 2176 cm−1. The 1H-NMR spectrum
showed aryl protons and the methyl groups of the
mesityl substituent, together with a characteristic triplet
(J=20.2 Hz) at l −10.48 due to the hydride ligand,
thus also confirming the presence of two trans-PPh3
groups. In the 13C-NMR spectrum, two low field
triplets were observed, at 218.0 ppm (J=6 Hz) and
204.7 ppm (J=13 Hz) which are assigned to the CS2
carbon and the CO ligand respectively on the basis of
the size of the coupling constant and also by compari-
l 5.85 in the H-NMR spectrum due to the CPhꢁCHPh
proton.
Small amounts of orange products were also isolated
from these reactions. Based on the fact that their IR
spectra showed two alkyne peaks in addition to the CO
stretch, we assigned their formulae as [Ru(CO)-
(CꢀCR)(S2CCꢀCR)(PPh3)2] and postulated that they
arose through reaction of 3a and 3b with the small
excess of alkyne present. Indeed, stirring isolated 3b
with an excess of phenylacetylene in THF at room
temperature for
4
d
led to
a
61% yield of
[Ru(CO)(CꢀCPh)(S2CCꢀCPh)(PPh3)2] (4). To confirm
that the added alkyne was the source of the alkynyl
group, the mixed complex [Ru(CO)(CꢀCMes)-
(S2CCꢀCPh)(PPh3)2] (5) was made from 3b and mesityl
acetylene. The reaction presumably proceeds by an
oxidative addition and reductive elimination sequence
with loss of stilbene (not detected). Analogous reactions
were recently reported in the carboxylate species

H. Adams et al. / Journal of Organometallic Chemistry 619 (2001) 209–217
211
Fig. 1. Molecular structure of [Ru(H)(CO)(S2CCꢀCPh)(PPh3)2] (2b) in the crystal showing the atomic numbering scheme. The dichloromethanes
of solvation have been omitted.
[Ru(CO)(CPhꢁCHPh)(O2CR)(PPh3)2] [9] and in the
dithiocarbamate analogues of 3 [10].
C(40) displaying virtually linear geometry and the
,
C(38)–C(39) bond length being 1.204(7) A, typical of a
CꢀC bond.
Since the reactions here were all carried out at room
temperature or below with stoichiometric quantities of
alkyne, we did not observe any enynyl complexes con-
taining the Ru–{C(CꢀCR)ꢁCHR)} group, which are
known to be produced by extended reaction of
[Ru(H)(Cl)(CO)(PPh3)3] and related compounds with
terminal alkynes at elevated temperature.
The structures of complexes 3b and 5 are shown in
Figs. 2 and 3, respectively; the numbering scheme is the
same for both complexes, and their selected bond
lengths and angles are collected in Table 2 for ease of
comparison. The arrangement of dithiocarboxylate,
PPh3 and carbonyl ligands is the same as in 2b, and the
sixth position is occupied either by a 1,2-diphenylvinyl
group in 3b or by a mesitylethynyl ligand in 5. In 3b,
the two phenyl substituents occupy cis positions on the
vinyl group and the C(11)–C(12) bond length is
2.1. Crystal structure determinations
In order to define some structural parameters for the
alkynyldithiocarboxylate ligands, the crystal structure
of one example of each of the three types of complex
was determined. Well-formed red blocks of 2b were
obtained by crystallisation from CH2Cl2 and light
petroleum; the structure is shown in Fig. 1, with se-
lected bond lengths and angles collected in Table 1. As
expected the ruthenium(II) centre is octahedrally coor-
dinated with the two PPh3 ligands occupying trans
positions [the P(1)–Ru(1)–P(2) angle is 169.62(4)°].
The hydride ligand was not located directly but is
presumably situated in the vacant region trans to S(2).
The dithiocarboxylate ligand is asymmetrically coordi-
,
1.320(8) A. Again the dithiocarboxylate is coordinated
Table 1
,
Selected bond lengths (A) and angles (°) for 2b·2CH2Cl2
Ru(1)–C(46)
Ru(1)–P(2)
Ru(1)–S(1)
S(2)–C(37)
C(37)–C(38)
C(39)–C(40)
1.854(5)
2.3512(11) Ru(1)–S(2)
2.4855(12) S(1)–C(37)
Ru(1)–P(1)
2.3329(11)
2.4527(11)
1.681(5)
1.685(4)
1.430(6)
1.450(6)
O(1)–C(46)
C(38)–C(39)
1.147(6)
1.204(7)
C(46)–Ru(1)–P(1)
P(1)–Ru(1)–P(2)
P(1)–Ru(1)–S(2)
C(46)–Ru(1)–S(1)
P(2)–Ru(1)–S(1)
C(37)–S(1)–Ru(1)
C(38)–C(37)–S(1)
S(1)–C(37)–S(2)
92.38(14) C(46)–Ru(1)–P(2)
91.10(14)
101.18(14)
91.32(4)
169.62(4)
97.59(4)
C(46)–Ru(1)–S(2)
P(2)–Ru(1)–S(2)
,
nated, with the Ru(1)–S(1) bond [2.4855(12) A] being
170.56(14) P(1)–Ru(1)–S(1)
92.76(4) S(2)–Ru(1)–S(1)
86.91(15) C(37)–S(2)–Ru(1)
85.32(4)
70.14(4)
87.91(15)
119.9(3)
,
significantly longer than Ru(1)–S(2) [2.4527(11) A].
The same asymmetry is observed in the related car-
boxylate complexes [11]. The bite angle of the didentate
ligand is 70.14(4)°. The presence of the alkynyl portion
of the ligand is confirmed, with C(37), C(38), C(39) and
125.1(3)
114.9(2)
C(38)–C(37)–S(2)
C(39)–C(38)–C(37) 173.6(5)
O(1)–C(46)–Ru(1) 179.7(5)
C(38)–C(39)–C(40) 176.4(6)

212
H. Adams et al. / Journal of Organometallic Chemistry 619 (2001) 209–217
Fig. 2. Molecular structure of [Ru(CO)(CPhꢁCHPh)(S2CCꢀCPh)(PPh3)2] (3b) in the crystal showing the atomic numbering scheme.
Fig. 3. Molecular structure of [Ru(CO)(CꢀCMes)(S2CCꢀCPh)(PPh3)2] (5) in the crystal showing the atomic numbering scheme.
slightly asymmetrically, with a bite angle of 69.67(5)°,
and the alkynyl portion of the ligand is linear with a
distortion around the central ruthenium, manifested by
changes in bond angles of up to 4°. The geometrical
parameters of the mesitylethynyl ligand are very similar
to those found in the carboxylate complex [Ru(CO)-
(CꢀCPh)(O2CR)(PPh3)2] (R=CHꢁCHCHꢁCHMe) [9].
,
CꢀC bond length of 1.199(8) A. These structural fea-
tures are largely reproduced in 5, except that the pres-
ence of the bulky mesityl substituent causes a slight

H. Adams et al. / Journal of Organometallic Chemistry 619 (2001) 209–217
213
3. Conclusions
spectra were recorded in dichloromethane solution on a
1
Perkin–Elmer 1600 FTIR machine. H-, 13C- and 31P-
From the work described here, it is clear that alkynyl
lithium reagents are sufficiently nucleophilic to add to
carbon disulfide to produce dithiocarboxylates, and
that these are sufficiently stable in solution to undergo
coordination to a variety of ruthenium complexes. Fu-
ture work will examine the coordination of these lig-
ands to other metal centres and their potential for
linking centres together to form ‘molecular wires’.
NMR spectra were obtained in CDCl3 solution on a
Bruker AC250 machine with automated sample-
changer or an AMX400 spectrometer. Chemical shifts
are given on the l scale relative to SiMe4=0.0 ppm;
the 31P{1H}-NMR spectra were referenced to 85%
H3PO4=0.0 ppm with downfield shifts reported as
positive. The 13C{1H}-NMR spectra were routinely
recorded using an attached proton test technique
(JMOD pulse sequence). Mass spectra were recorded
on a Fisons/BG Prospec 3000 instrument operating in
fast atom bombardment mode with m-nitrobenzyl alco-
hol as matrix, except the electrospray mass spectrum of
4 which was run on a Micromass Platform in MeCN–
H2O (3:1). Elemental analyses were carried out by the
Microanalytical Service of the Department of
Chemistry.
4. Experimental
4.1. General
General experimental techniques were as described in
recent papers from this laboratory [12,13]. Infrared (IR)
Mesityl acetylene was prepared in 55% overall yield
from 2,4,6-trimethylacetophenone by chlorination with
PCl5 to give MesC(Cl)ꢁCH2 followed by elimination
with KOH in ethanol, according to a combination of
literature procedures [14]. The complexes [Ru(H)(Cl)-
(CO)(PPh3)3] and [RuCl(CPhꢁCHPh)(CO)(PPh3)2] were
prepared by the literature methods [7,15].
Table 2
,
Selected bond lengths (A) and angles (°) for 3b and 5
Bond
3b
5
Ru(1)–C(1)
Ru(1)–C(11)
Ru(1)–P(2)
Ru(1)–P(1)
Ru(1)–S(1)
Ru(1)–S(2)
S(1)–C(2)
1.840(5)
2.141(6)
2.3773(17)
2.3938(17)
2.4730(15)
2.5010(17)
1.699(6)
1.687(6)
1.157(6)
1.418(8)
1.199(8)
1.415(8)
1.320(8)
1.861(6)
2.039(5)
2.4029(14)
2.3626(14)
2.4940(15)
2.4244(14)
1.696(5)
1.678(6)
1.153(6)
1.415(8)
1.206(8)
1.466(9)
1.214(7)
4.2. Preparation of [Ru(H)(CO)(S2CꢀCMes)(PPh3)2]
(2a)
S(2)–C(2)
Mesityl acetylene (1.0 ml, 1.28 g, 8.88 mmol) was
dissolved in THF (10 ml) in a Schlenk tube and treated
dropwise with BuLi (5.56 ml of 1.6M solution) at
−10°C. After stirring for 30 min, the solution was
cannulated into a second Schlenk tube containing THF
(9 ml) and carbon disulfide (4.45 ml) and washed in
with a further 1 ml of THF. An immediate colour
change to dark red occurred. The solution was allowed
to stir at room temperature (r.t.) for 2 h. In a separate
Schlenk tube, [Ru(H)(Cl)(CO)(PPh3)3] (0.5 g, 0.525
mmol) was suspended in THF (50 ml). To this suspen-
sion was added 1.83 ml of the dark red Li[S2CCꢀCMes]
solution (the remaining solution was used for other
purposes) [16]. The suspended solid rapidly dissolved to
give a dark red solution. After stirring for 2 h the
solvent was removed. The remaining red oil was ab-
sorbed onto silica and loaded onto a chromatography
column. Elution with light petroleum–dichloromethane
(7:3) afforded a large red band which yielded a red
powder of [Ru(H)(CO)(S2CCꢀCMes)(PPh3)2] on re-
moval of the solvent. Yield 0.2881 g, 63%. M.p. 110°C
(dec.). IR (CH2Cl2): 2176 w (CꢀC), 1936 s (CO); IR
O(1)–C(1)
C(2)–C(3)
C(3)–C(4)
C(4)–C(5)
C(11)–C(12)
C(1)–Ru(1)–C(11)
C(1)–Ru(1)–P(2)
C(11)–Ru(1)–P(2)
C(1)–Ru(1)–P(1)
C(11)–Ru(1)–P(1)
P(2)–Ru(1)–P(1)
C(1)–Ru(1)–S(1)
C(11)–Ru(1)–S(1)
P(2)–Ru(1)–S(1)
P(1)–Ru(1)–S(1)
C(1)–Ru(1)–S(2)
C(11)–Ru(1)–S(2)
P(2)–Ru(1)–S(2)
P(1)–Ru(1)–S(2)
S(1)–Ru(1)–S(2)
C(2)–S(1)–Ru(1)
C(2)–S(2)–Ru(1)
O(1)–C(1)–Ru(1)
C(3)–C(2)–S(2)
90.0(2)
89.34(18)
92.26(15)
86.55(17)
91.58(15)
174.37(5)
173.13(16)
96.81(15)
90.75(5)
92.88(5)
103.47(17)
166.45(15)
88.90(5)
88.32(5)
69.67(5)
88.4(2)
91.8(2)
90.98(18)
89.97(15)
92.72(18)
87.62(15)
175.65(5)
168.53(17)
99.08(16)
92.54(5)
84.26(5)
99.11(17)
168.84(16)
87.61(5)
94.06(5)
70.16(5)
86.6(2)
87.8(2)
89.3(2)
177.9(5)
122.4(5)
123.4(4)
114.1(3)
174.9(7)
174.9(7)
124.9(4)
131.9(5)
178.2(5)
120.7(4)
125.3(4)
113.9(3)
172.6(6)
174.9(6)
177.9(5)
172.8(6)
C(3)–C(2)–S(1)
S(2)–C(2)–S(1)
C(4)–C(3)–C(2)
C(3)–C(4)–C(5)
C(12)–C(11)–Ru(1)
C(11)–C(12)–C(13)
1
(KBr): 2170, 1942 cm−1. H-NMR: l 7.77–7.38 (m, 30
H, Ph of PPh3), 6.80 (s, 2 H, Mes), 2.22 (s, 3 H, 4-Me
of Mes), 2.20 (s, 6 H, 2,6-Me of Mes), −10.48 (t,
J
PH=20.2 Hz, 1 H, RuH). 13C-NMR: l 218.0 (t,

214
H. Adams et al. / Journal of Organometallic Chemistry 619 (2001) 209–217
J
PC=6 Hz, S2C), 204.7 (t, JPC=13 Hz, CO), 141.1 (s,
2,6-C of Mes), 139.3 (s, 4-C of Mes), 135.4 (apparent t,
PC=22 Hz, Cipso of Ph), 134.0–127.7 (m, aryl), 118.8
suspension was added 4.2 ml of the dark orange
Li(S2CCꢀCBut) solution. The suspended solid rapidly
dissolved and a light orange–red solution was obtained
on stirring overnight. The solvent was removed and the
remaining solid was absorbed onto silica and loaded
onto a chromatography column. Elution with light
petroleum–dichloromethane (3:2) afforded a large or-
ange-red band, which yielded a bright orange powder
of [Ru(H)(CO)(S2CCꢀCBut)(PPh3)2] on removal of the
solvent. Yield 0.3105 g, 73%. M.p. 149–151°C.
J
(s, Cipso of Mes), 105.5 (s, CꢀC), 87.8 (s, CꢀC), 21.6 (s,
4-Me of Mes), 21.0 (s, 2,6-Me of Mes). 31P-NMR: l
51.7. Anal. Found: C, 62.63; H, 4.55; S, 6.77. Calc. for
C49H42OP2RuS2·CH2Cl2: C, 62.62; H, 4.62; S, 6.69%.
Mass spectrum: m/z 873 (M+), 846 (M–CO+).
4.3. Preparation of [Ru(H)(CO)(S2CꢀCPh)(PPh3)2] (2b)
IR(CH2Cl2): 2197 w (CꢀC), 1936 s (CO) cm−1 1H-
.
Phenylacetylene (0.29 ml, 0.27 g, 2.64 mmol) was
dissolved in THF (9 ml) in a Schlenk tube and treated
dropwise with BuLi (1.65 ml of 1.6 M soln) at −78°C.
After stirring for 30 min, the solution was cannulated
into a second Schlenk tube containing THF (8.9 ml)
and carbon disulfide (0.16 ml), also held at −78°C,
and washed in with a further 5 ml of THF. The pale
yellow solution was then allowed to warm to r.t. and
then stir for 1 h, producing a further colour change to
dark red. In a separate Schlenk tube, [Ru(H)(Cl)(CO)-
(PPh3)3] (0.5 g, 0.525 mmol) was suspended in THF (50
ml). To this suspension was added 5.0 ml of the dark
red Li[S2CCꢀCPh] solution (the remaining solution was
used for other purposes). The suspended solid rapidly
dissolved to give a dark red solution. After stirring for
2 h the solvent was removed. The remaining solid was
absorbed onto silica and loaded onto a chromatogra-
phy column. Elution with light petroleum–
dichloromethane (7:3) afforded a large red band which
yielded a red powder of [Ru(H)(CO)(S2CCꢀCPh)-
(PPh3)2] on removal of the solvent. Yield 0.2313 g, 53%.
M.p. 160°C (dec.). IR (CH2Cl2): 2183 w (CꢀC), 1934 s
NMR: l 7.75–7.25 (m, 30 H, Ph), 1.10 (s, 9 H, Me),
−10.55 (t, J=20.0 Hz, 1 H, RuH). 13C-NMR: l 220.6
(t, J=6 Hz, S2C), 205.1 (t, J=13 Hz, CO), 135.7
(apparent t, J=22 Hz, Cipso), 134.3–127.9 (m, Ph),
100.2, 89.4 (both s, CꢀC), 30.6 (s, Me), 28.3 (CMe3).
31P-NMR l 51.7. Anal. Found: C, 60.41; H, 4.59; S,
7.97. Calc. for C44H40OP2RuS2·CH2Cl2: C, 60.30; H,
4.69; S, 7.81%. Mass spectrum: m/z 812 (M+H+).
4.5. Preparation of
[Ru(CO)(CPhꢁCHPh)(S2CCꢀCMes)(PPh3)2] (3a)
A red solution of Li[S2CCꢀCMes] was prepared as
above from MesCꢀCH (0.25 ml, 0.32 g, 2.22 mmol) and
BuLi (1.40 ml of 1.6 M solution) in 18.2 ml of THF,
followed by addition of CS2 (0.15 ml, 2.5 mmol). The
total volume was therefore 20 ml. In a separate Schlenk
tube [Ru(Cl)(CO)(CPhꢁCHPh)(PPh3)2] (0.5 g, 0.576
mmol) was suspended in THF (50 ml), and to this was
added 5.2 ml of the Li[S2CCꢀCMes] solution.
Overnight stirring produced a brown–red solution
which was stripped to dryness. Column chromatogra-
phy, eluting with light petroleum–dichloromethane
(1:1) afforded a large brown-green band, which yielded
(CO) cm−1 1H-NMR: l 7.76–7.30 (m, 35 H, Ph),
.
−10.47 (t, JPH=19.9 Hz, 1 H, RuH). 13C-NMR: 217.4
(t, J=6 Hz, S2C), 204.6 (t, J=13 Hz, CO), 135.4
(apparent t, J=22 Hz, Cipso of PPh3), 133.9–127.6 (m,
Ph), 122.1 (s, Cipso of Ph), 97.4 (s, CꢀC), 89.1 (s, CꢀC).
31P-NMR: l 51.3. Anal. Found: C, 63.39; H, 4.29; S,
7.29. Calc. for C46H36OP2RuS2·0.5CH2Cl2: C, 63.87; H,
4.26; S, 7.33%. Mass spectrum: m/z 832 (M+), 804
(M–CO+).
a
dark brown powder of [Ru(CO)(CPhꢁCHPh)-
(S2CCꢀCMes)(PPh3)2] on removal of the solvent. Yield
0.4667 g, 78%. M.p. 178–180°C. IR (CH2Cl2): 2175 w
(CꢀC), 1930 s (CO) cm−1. H-NMR: l 7.47–6.78 (m,
1
Ph+Mes), 6.44 (d br, Ph), 5.83 (s br, CH), 2.24 (s, 3 H,
Me), 2.15 (s, 6 H, 2 Me). 13C-NMR: l 215.3 (t, J=5
Hz, S2C), 205.9 (t, J=15 Hz, CO), 166.5 (br s, CPh of
vinyl), 152.9 (br s, CHPh of vinyl), 141.0–123.0 (m,
Ph+Mes), 118.3 (s, Cipso of Mes), 104.1, 90.6 (both s,
CꢀC), 21.4 (s, Me), 21.0 (s, 2 Me). 31P-NMR: l 37.8.
Anal. Found: C, 71.81; H, 5.52; S, 6.01. Calc. for
C63H52OP2RuS2: C, 71.93; H, 4.95; S, 6.09%. Mass
spectrum: m/z 1053 (M+), 873, 762.
4.4. Preparation of [Ru(H)(CO)(S2CCꢀCBut)(PPh3)2]
(2c)
In a similar manner to the above, ButCꢀCH (0.31 ml,
0.205 g, 2.5 mmol) was dissolved in THF (17.96 ml) in
a Schlenk tube and treated dropwise with BuLi (1.58 ml
of 1.6 M solution) at −78°C. After stirring for 30 min
at r.t. the solution was cooled again to −78°C and
carbon disulfide (0.15 ml, 2.5 mmol) added dropwise.
The pale yellow solution was allowed to warm to r.t.
and then stir for 1 h, causing a change to dark orange.
In a separate Schlenk tube [Ru(H)(Cl)(CO)(PPh3)3] (0.5
g, 0.525 mmol) was suspended in THF (50 ml). To this
4.6. Preparation of
[Ru(CO)(CPhꢁCHPh)(S2CCꢀCPh)(PPh3)2] (3b)
A red solution of Li[S2CCꢀCPh] (2.64 mmol in 20 ml
of THF) was prepared as described in Section 4.3, and
8.72 ml of this solution was added to a suspension of
[Ru(Cl)(CO)(CPhꢁCHPh)(PPh3)2] (1 g, 1.153 mmol) in

H. Adams et al. / Journal of Organometallic Chemistry 619 (2001) 209–217
215
THF (50ml). The solid dissolved and a red–green solu-
tion was obtained after overnight stirring. After absorp-
tion onto a small amount of silica, the residue was
chromatographed. Elution with light petroleum–
dichloromethane (3:2) afforded a large brown-green
solvent. Yield: 0.1009 g, 61%. M.p. 208–211°C (dec.).
IR (CH2Cl2): 2185 w (CꢀC), 2100 w (CꢀC), 1955 s (CO)
cm−1 1H-NMR: l 7.95–6.60 (m, Ph). 13C-NMR: l
.
217.0 (t, J=5 Hz, S2C), 203.7 (t, J=13 Hz, CO),
134.8–128.0 (m, Ph), 124.7, 122.0 (both s, Cipso of
CꢀCPh), 118.5 (s, CꢀC of acetylide), 110.5 (t, J=19
Hz, Ru–CꢀC of acetylide), 96.9, 92.5 (both s, CꢀC).
31P-NMR: l 38.8. Anal. Found: C, 64.71; H, 4.31; S,
7.36. Calc. for C54H40OP2RuS2·CH2Cl2: C, 64.96; H,
4.13; S, 6.29%. Mass spectrum (electrospray): m/z 830
(M–C2Ph)+.
band, which yielded
a
dark green powder of
[Ru(CO)(CPhꢁCHPh)(S2CCꢀCPh)(PPh3)2] on removal
of the solvent. Yield 0.8357 g, 72%. M.p. 194–196°C.
1
IR (CH2Cl2): 2184 w (CꢀC), 1931 s (CO) cm−1. H-
NMR: l 7.45–6.76 (m, H, Ph), 6.36 (br s, Ph), 5.85 (br
s, CH). 13C-NMR: l 215.0 (t, J=5 Hz, S2C), 205.7 (t,
J=16 Hz, CO), 166.3 (s, CPh of vinyl), 140.8 (s, CHPh
of vinyl), 135.0–123.1 (m, Ph), 121.6 (s, Cipso of Ph),
96.1, 92.0 (both s, CꢀC). 31P-NMR: l 37.3. Anal.
Found: C, 69.29; H, 4.70; S, 6.69. Calc. for
C60H46OP2RuS2·0.5CH2Cl2: C, 69.04; H, 4.47; S, 6.09%.
Mass spectrum: m/z 1011 (M+), 983 (M–CO+), 831,
803.
4.9. Preparation of
[Ru(CO)(CꢀCMes)(S2CCꢀCPh)(PPh3)2] (5)
In the same manner, [Ru(CO)(CPhꢁCHPh)-
(S2CCꢀCPh)(PPh3)2] (0.5 g, 0.496 mmol) in THF (50
ml) reacted with mesityl acetylene (0.2 ml, 0.256 g, 1.78
mmol) to give a red solution after stirring for 4 days.
The solvent was removed and the remaining solid was
absorbed onto silica and chromatograped as above.
Elution with light petroleum–dichloromethane (3:2) af-
forded a large red band, which yielded a dark red
powder of [Ru(CO)(CꢀCMes)(S2CCꢀCPh)(PPh3)2] on
removal of solvent. Yield 0.1977 g, 41%. M.p. 194–
198°C. IR (CH2Cl2): 2184 w (CꢀC), 2086 w (CꢀC), 1951
4.7. Preparation of
[Ru(CO)(CPhꢁCHPh)(S2CCꢀCBut)(PPh3)2] (3c)
A dark orange solution of Li[S2CCꢀCBut] (2.5 mmol
in 20 ml of THF) was prepared as described in Section
4.4, and 4.61 ml of this solution was added to a
suspension of [Ru(Cl)(CO)(CPhꢁCHPh)(PPh3)2] (0.5 g,
0.576 mmol) in THF (50 ml). A dark red solution was
obtained after stirring overnight. Chromatography as
above, eluting with light petroleum–dichloromethane
(3:2) afforded a large brown–green band, which yielded
1
s (CO) cm−1. H-NMR: l 7.96–6.68 (m, 17H, Ph+
Mes), 2.20 (s, 3 H, Me), 2.18 (s, 6 H, 2 Me). 13C-NMR:
l 215.7 (t, J=5 Hz, S2C), 203.5 (t, J=13 Hz, CO),
140.4–121.1 (m, Ph+Mes), 115.3 (s, CꢀC of acetylide),
113.8 (t, J=19 Hz, Ru–CꢀC of acetylide), 96.3 (t,
J=3 Hz, CꢀC), 91.9 (s, CꢀC), 20.7 (s, 2 Me), 14.9 (s,
Me). 31P-NMR: l 37.1. Anal. Found: C, 68.44; H, 4.81;
S, 6.87. Calc. for C57H46OP2RuS2·0.5CH2Cl2: C, 67.95;
H, 4.53; S, 6.30%. Mass spectrum: m/z 975 (M+), 947,
831, 684.
a
dark brown powder of [Ru(CO)(CPhꢁCHPh)-
(S2CCꢀCBut)(PPh3)2] on removal of the solvent. Yield
0.1446 g, 25%. M.p. 194–197°C. IR(CH2Cl2): 2200 w
(CꢀC), 1930 s (CO) cm−1. H-NMR: l 7.45–6.78 (m,
1
Ph), 6.35 (br s, Ph), 5.78 (br s, 1 H, CH of vinyl), 1.05
(s, 9 H, Me). 13C-NMR: l 217.6 (t, J=5 Hz, S2C),
205.8 (t, J=16 Hz, CO), 166.7 (br s, CPh), 140.9 (s,
CHPh), 134.8–123.0 (m, Ph), 102.6, 87.8 (both s, CꢀC),
29.9 (s, Me), 27.9 (s, CMe3). 31P-NMR: 37.8. Anal.
Found: C, 68.45; H, 5.02; S, 7.07. Calc. for
C58H50OP2RuS2·0.5CH2Cl2: C, 68.05; H, 4.94; S, 6.20%.
Mass spectrum: m/z 991 (M+H+).
4.10. Crystal structure determinations of 2b, 3b and 5
Details of the crystal structure determinations are
given in Table 3. Data collected were measured on a
Bruker SMART CCD area detector with Oxford
Cryosystems low temperature system. Reflections were
measured from a hemisphere of data collected of frames
each covering 0.3° in omega. Of the reflections mea-
sured, all of which were corrected for Lorentz and
polarisation effects and for absorption by semi empiri-
cal methods based on symmetry-equivalent and re-
peated reflections, those independent reflections which
exceeded the significance level ꢀFꢀ/|(ꢀFꢀ)\4.0 were used
in refinement. The structure was solved by direct meth-
ods and refined by full-matrix least-squares methods on
F2. Hydrogen atoms were placed geometrically and
refined with a riding model (including torsional free-
dom for methyl groups) and with Uiso constrained to be
1.2 (1.5 for methyl groups) times Ueq of the carrier
4.8. Preparation of
[Ru(CO)(CꢀCPh)(S2CCꢀCPh)(PPh3)2] (4)
A
suspension of [Ru(CO)(CPhꢁCHPh)(S2CCꢀ
CPh)(PPh3)2] (0.18 g, 0.178 mmol) in THF (50 ml) was
treated with an excess of phenylacetylene (0.1 ml, 0.093
g, 0.91mmol). The green–red solution had turned red
after stirring for 4 days. The solvent was removed and
the remaining solid was absorbed onto silica and
loaded onto a chromatography column. Elution with
light petroleum–dichloromethane (3:2) afforded a large
red band, which yielded a bright red powder of
[Ru(CO)(CꢀCPh)(S2CCꢀCPh)(PPh3)2] on removal of

216
H. Adams et al. / Journal of Organometallic Chemistry 619 (2001) 209–217
Table 3
Summary of crystallographic data for complexes 2b·2CH2Cl2, 3b and 5
2b·2CH2Cl2
3b
5
Identification code
Empirical formula
Formula weight
Temperature (K)
ims10m
C48H39Cl4OP2RuS2
1000.72
ims17a
C60H46OP2RuS2
1010.10
ims20m
C57H46OP2RuS2
974.07
150(2)
150(2)
150(2)
,
Wavelength (A)
0.71073
Monoclinic
P2(1)/n
0.71073
Triclinic
0.71073
Triclinic
Crystal system
Space group
(
(
P1
P1
Unit cell dimensions
,
a (A)
11.451(3)
33.727(10)
11.879(4)
90
100.372(6)
90
4512(2)
4
12.270(4)
14.297(4)
16.115(5)
86.004(6)
69.513(5)
64.738(5)
2384.2(12)
2
1.407
0.526
11.3531(12)
11.8388(12)
18.3351(18)
72.229(2)
85.892(2)
79.352(2)
2306.1(4)
2
1.403
0.541
,
b (A)
,
c (A)
h (°)
i (°)
k (°)
3
,
Volume (A )
Z
Dcalc (Mg m−3
)
1.473
0.784
2036
Absorption coefficient (mm−1
F(000)
)
1040
1004
Crystal size (mm)
q Range for data collection (°)
Index ranges
0.25×0.10×0.10
1.21–28.34
−155h59, −445k544,
−155l515
29 075
0.19×0.08×0.03
1.35–28.34
−165h510, −185k519,
−205l519
14 820
0.24×0.20×0.18
1.83–28.30
−155h510, −145k515,
−215l524
14 063
Reflections collected
Independent reflections
Completeness to q (%)
Absorption correction
Max. and min. transmission
Refinement method
10 700 [Rint=0.1530]
95.1
Semi-empirical
0.9257 and 0.8281
10 872 [Rint=0.0911]
91.4
Semi-empirical from equivalents None
0.9844 and 0.9066 0.9089 and 0.8811
10364 [Rint=0.1066]
90.3
Full-matrix least-squares on F2 Full-matrix least-squares on F2 Full-matrix least-squares on F2
Data/restraints/parameters
Goodness-of-fit on F2
Final R indices [I\2|(I)]
R indices (all data)
10 700/9/522
1.096
R1=0.0733, wR2=0.1910
R1=0.0850, wR2=0.1995
10 872/0/590
0.910
R1=0.0578, wR2=0.1391
R1=0.1199, wR2=0.1921
0.868 and −0.979
10 364/0/568
0.902
R1=0.0698, wR2=0.1550
R1=0.1199, wR2=0.1764
1.053 and −2.296
Largest difference peak and hole (e 1.643 and −1.563
−3
,
A
)
atom. Refinement converged at the final R values
shown with allowance for the thermal anisotropy of all
non-hydrogen atoms. Weighting schemes w=1/
[|2(Fo2)+(0.0939P)2+12.70P] (for 2b), w=1/[|2(F2o)+
(0.1019P)2+0.00P] (for 3b) and w=1/[|2(F2o)+
(0.0850P)2+0.00P] (for 5) where P=(Fo2 +2F2c)/3 were
used in the latter stages of refinement. Complex scatter-
ing factors were taken from the program package
SHELXTL [17] as implemented on the Viglen Pentium
computer.
Cambridge, CB2 1EZ, UK (fax: +44-1223-336033;
e-mail: deposit@ccdc.cam.ac.uk or http://www.ccdc.
cam.ac.uk).
Acknowledgements
We thank the Nuffield Foundation for support of the
initial stages of this work through a Student Bursary
for P.E. McH., and the many past undergraduate stu-
dents who prepared the samples of [Ru(H)(Cl)(CO)-
(PPh3)3] and [RuCl(CO)(CPhꢁCHPh)(PPh3)2] as part of
their laboratory course.
5. Supplementary material
Crystallographic data for the structures reported in
this paper have been deposited with the Cambridge
Crystallographic Data Centre, CCDC nos. 147705,
147706 and 147707 for complexes 2b, 3b and 5, respec-
tively. Copies of this information may be obtained free
of charge from the Director, CCDC, 12 Union Road,
References
[1] (a) D. Coucouvanis, Prog. Inorg. Chem. 11 (1970) 233. (b) D.
Coucouvanis, Prog. Inorg. Chem. 26 (1979) 301.

H. Adams et al. / Journal of Organometallic Chemistry 619 (2001) 209–217
217
[2] J. Meijer, P. Vermeer, L. Brandsma, Recl. Trav. Chim. Pays-Bas
92 (1973) 601.
[3] (a) K. Hartke, H.-D. Gerber, U. Roesrath, Annalen (1991) 903.
(b) K. Hartke, H.-D. Gerber and U. Roesrath, Tetrahedron
Lett. 30 (1989) 1073.
[10] R.B. Bedford, C.S.J. Cazin, J. Organomet. Chem. 598 (2000) 20.
[11] M. El Guaouzi, J. Ros, X. Solans, M. Font-Bardia, Inorg. Chim.
Acta 231 (1995) 181.
[12] H. Adams, L.J. Gill, M.J. Morris, Organometallics 15 (1996)
464.
[4] M.I. Bruce, M.J. Liddell, M.R. Snow, E.R.T. Tiekink, J.
Organomet. Chem. 352 (1988) 199.
[13] H. Adams, N.A. Bailey, L.J. Gill, M.J. Morris, F.A. Wildgoose,
J. Chem. Soc., Dalton Trans. (1996) 1437.
[5] P.B. Critchlow and S.D. Robinson, J. Chem. Soc., Dalton Trans.
(1975) 1367.
[6] M. El Guaouzi, I. Moldes, J. Ros, A. Alvarez-Larena, J.F.
Piniella, Inorg. Chem. Commun. 1 (1998) 335.
[7] M.R. Torres, A. Vegas, A. Santos, J. Organomet. Chem. 309
(1986) 169.
[8] H. Loumrhari, J. Ros, M.R. Torres, Polyhedron 10 (1991) 421.
[9] M. El Guaouzi, R. Yanez, J. Ros, A. Alvarez-Lerena, J.P.
Piniella, Inorg. Chem. Commun. 2 (1999) 288.
[14] (a) K. Yates, G. Mandrapilias, J. Org. Chem. 45 (1980) 3892,
3902. (b) A.H.A. Tinnemans, W. Laarhoven, Tetrahedron 35
(1979) 1540.
[15] N. Ahmad, J.J. Levison, S.D. Robinson, M.F. Uttley, Inorg.
Synth. 15 (1974) 44.
[16] H. Adams, M.J. Morris, P.J. Wright (in preparation).
[17] G.M. Sheldrick, SHELXL Version, An Integrated System for
Solving and Refining Crystal Structures from Diffraction Data
(Revision 5.1), Bruker AXS Ltd.
.