Dppm-substituted ruthenium clusters with capping sulfido and selenido ligands derived from thiourea, tetramethylthiourea and elemental selenium

Article abstract of DOI:10.1016/j.jorganchem.2005.08.017

Treatment of [Ru₃(CO)₁₀(μ-dppm)] (4) [dppm = bis(diphenylphosphido)methane] with tetramethylthiourea at 66 °C gave the previously reported dihydrido triruthenium cluster [Ru₃(μ-H) ₂(μ₃-S)(CO)₇(μ-dppm)] (5) and the new compounds [Ru₃(μ₃-S)₂(CO) ₇(μ-dppm)] (6), [Ru₃(μ₃-S)(CO) ₇(μ₃-CO)(μ-dppm)] (7) and [Ru₃(μ ₃-S){η¹-C(NMe₂)₂}(CO) ₆(μ₃-CO)(μ-dppm)] (8) in 6%, 10%, 32% and 9% yields, respectively. Treatment of 4 with thiourea at the same temperature gave 5 and 7 in 30% and 10% yields, respectively. Compound 7 reacts further with tetramethylthiourea at 66 °C to yield 6 (30%) and a new compound [Ru ₃(μ₃-S)₂{η¹-C(NMe ₂)₂}(CO)₆(μ-dppm)] (9) (8%). Thermolysis of 8 in refluxing THF yields 7 in 55% yield. The reaction of 4 with selenium at 66 °C yields the new compounds [Ru₃(μ₃-Se)(CO) ₇(μ₃-CO)(μ-dppm)] (10) and [Ru₃(μ ₃-Se)(μ₃-η³-PhPCH₂PPh(C ₆H₄)}(CO)₆(μ-CO)] (11) and the known compounds [Ru₃(μ-H)₂(μ₃-Se)(CO) ₇(μ-dppm)] (12) and [Ru₄(μ₃-Se) ₄(CO)₁₀(μ-dppm)] (13) in 29%, 5%, 2% and 5% yields, respectively. Treatment of 10 with tetramethylthiourea at 66 °C gives the mixed sulfur-selenium compounds [Ru₃(μ₃-S) (μ₃-Se)(CO)₇(μ-dppm)] (14) and [Ru ₃(μ₃-S)(μ₃-Se){η¹- C(NMe₂)₂}(CO)₆(μ-dppm)] (15) in 38% and 10% yields, respectively. The single-crystal XRD structures of 6, 7, 8, 10, 14 and 15 are reported.

Full text of DOI:10.1016/j.jorganchem.2005.08.017

Journal of Organometallic Chemistry 691 (2006) 309–322
www.elsevier.com/locate/jorganchem
Dppm-substituted ruthenium clusters with capping sulfido and
selenido ligands derived from thiourea, tetramethylthiourea
and elemental selenium
Syed J. Ahmed , Md. Iqbal Hyder , Shariff E. Kabir ,a, Md. Arzu Miah ,
a
a
a
*
b,
,c
*
Antony J. Deeming *, Ebbe Nordlander
a
Department of Chemistry, Jahangirnagar University, Savar, Dhaka 1342, Bangladesh
Department of Chemistry, University College London, 20 Gordon Street, London WC 1H OAJ, UK
Inorganic Chemistry, Center for Chemistry and Chemical Engineering, Lund University, P.O. Box 124, S-22100 Lund, Sweden
b
c
Received 9 August 2005; accepted 12 August 2005
Available online 20 October 2005
Abstract
Treatment of [Ru3(CO)10(l-dppm)] (4) [dppm = bis(diphenylphosphido)methane] with tetramethylthiourea at 66 ꢀC gave the previ-
ously reported dihydrido triruthenium cluster [Ru3(l-H)2(l3-S)(CO)7(l-dppm)] (5) and the new compounds [Ru3(l3-S)2(CO)7(l-dppm)]
(6), [Ru3(l3-S)(CO)7(l3-CO)(l-dppm)] (7) and [Ru3(l3-S){g1-C(NMe2)2}(CO)6(l3-CO)(l-dppm)] (8) in 6%, 10%, 32% and 9% yields,
respectively. Treatment of 4 with thiourea at the same temperature gave 5 and 7 in 30% and 10% yields, respectively. Compound 7 reacts
further with tetramethylthiourea at 66 ꢀC to yield 6 (30%) and a new compound [Ru3(l3-S)2{g1-C(NMe2)2}(CO)6(l-dppm)] (9) (8%).
Thermolysis of 8 in refluxing THF yields 7 in 55% yield. The reaction of 4 with selenium at 66 ꢀC yields the new compounds
[Ru3(l3-Se)(CO)7(l3-CO)(l-dppm)] (10) and [Ru3(l3-Se)(l3-g3-PhPCH2PPh(C6H4)}(CO)6(l-CO)] (11) and the known compounds
[Ru3(l-H)2(l3-Se)(CO)7(l-dppm)] (12) and [Ru4(l3-Se)4(CO)10(l-dppm)] (13) in 29%, 5%, 2% and 5% yields, respectively. Treatment
of 10 with tetramethylthiourea at 66 ꢀC gives the mixed sulfur-selenium compounds [Ru3(l3-S)(l3-Se)(CO)7(l-dppm)] (14) and
[Ru3(l3-S)(l3-Se){g1-C(NMe2)2}(CO)6(l-dppm)] (15) in 38% and 10% yields, respectively. The single-crystal XRD structures of 6, 7,
8, 10, 14 and 15 are reported.
ꢁ 2005 Elsevier B.V. All rights reserved.
Keywords: Triruthenium clusters; Tetramethylthiourea; Sulfur; Selenium; Carbene; Alkylidene; X-ray structures
1. Introduction
(CO)9] (Scheme 1), containing triply-bridging thioureato li-
gands by N–H bond cleavage [1].
Reactions between thioureas and transition metal car-
bonyl clusters of ruthenium [1–9] and osmium [10–12] have
been extensively studied, initially by the Suss-Fink group
¨
[1–9]. These reactions are generally accompanied by cleav-
age of N–H, C–N, C@S and C–H bonds depending upon
the substituted thiourea and reaction conditions. For
example, thiourea, dimethylthiourea and diphenylthiourea
with [Ru3(CO)12] lead to [Ru3(l-H)(l3-g2-RNCSNRH)-
In contrast, diisopropylthiourea and diethylthiourea re-
act with [Ru3(CO)12] under more forcing conditions to give
tetraruthenium clusters, containing sulfido and diamino-
carbene ligands (Scheme 2) by cleavage of the C@S bond
[3].
Further variations are found in the treatment of di-tert-
butylthiourea with [Ru3(CO)12] at room temperature to
give [Ru3(l-H)(l3-S)(g2-CH2CMe2NHCNHBut)(CO)8] and
[Ru3(l-H){l3-SRu(CO)3}(g2-CH2CMe2NHCNHBut)(CO)9]
in which both C@S and C–H bonds are cleaved, leaving
coordinated S and carbene ligands [6]. On the other hand,
*
Corresponding author.
E-mail address: a.j.deeming@ucl.ac.uk (A.J. Deeming).
0022-328X/$ - see front matter ꢁ 2005 Elsevier B.V. All rights reserved.
doi:10.1016/j.jorganchem.2005.08.017

310
S.J. Ahmed et al. / Journal of Organometallic Chemistry 691 (2006) 309–322
H
(l-dppm)] (1) and obtained only [Os3(l3-S)2(CO)7(l-
dppm)] as two separable isomers [14] (Scheme 3).
R
N
C
R
These compounds are potential building blocks for
higher nuclearity clusters [15]. Naturally, we wished to
compare such reactivity patterns for osmium with that of
the ruthenium analogue 4, which has also attracted atten-
tion for its reactivity with various small organics and for
the role of dppm in stabilizing the cluster [16–27]. In this
context, we describe in this paper the reactions of 4 with
tetramethylthiourea, thiourea and elemental selenium.
N
S
NHR
NHR
25 oC
[Ru3(CO)12
]
+ S
C
(CO)
3 Ru
Ru (CO)3
H
Ru
(CO)3
(R = H, Me or Ph)
Scheme 1.
tetramethylthiourea reacts with [Ru3(CO)12] at 66 ꢀC to
give two isomers of [Ru3(l-H)(l3-S)(CH2NMeCNMe2)-
(CO)8] with the organic group either bridging or chelating,
as well as corresponding tetranuclear clusters [3].
2. Results and discussion
2.1. Synthesis
Lewis et al. [10] and we [11,12] have investigated reac-
tions of the reactive triosmium cluster [Os3(CO)10-
(MeCN)2] with thiourea, phenylthiourea and diphenyl-
thiourea and obtained triosmium clusters of the type
[Os3(l-H)(l-g2-RNCSNHR)(CO)10] and [Os3(l-H)(l3-g2-
RNCSNHR)(CO)9] containing edge- and triply-bridging
thioureato ligands, respectively. In contrast, tetramethyl-
thiourea reacts with [Os3(CO)12] in the presence of Me3NO Æ
2H2O giving [Os3(CO)11{g1-SC(NMe2)2}], [Os3(l-OH)(l-
MeOCO){g1-SC(NMe2)2}(CO)9] and [Os3(l-H)(l3-S)(l-
MeOCO){g1-SC(NMe2)2}(CO)8] containing S-coordinated
tetramethylthiourea ligands [12]. We recently began sys-
tematic investigations of tetramethylthiourea reactivity
with unsaturated triosmium clusters for which a variety
of ligand coordination modes and transformations have
been demonstrated including g1-S-coordination, the latter
being useful for further transformation [13]. Most recently
we have investigated the reaction of tetramethylthiourea
with the dppm-bridging triosmium cluster [Os3(CO)10-
Cluster 4 reacts with tetramethylthiourea in refluxing
THF to give, after chromatography, four triruthenium
clusters: the known compound [Ru3(l-H)2(l3-S)(CO)7-
(l-dppm)] (5) (6%), and the new compounds [Ru3(l3-
S)2(CO)7(l-dppm)] (6), [Ru3(l3-S)(CO)7(l3-CO)(l-dppm)]
(7) and [Ru3(l3-S){g1-C(NMe2)2}(CO)6(l3-CO)(l-dppm)]
(8) in 10%, 32% and 9% yields, respectively (see Scheme
4). We recently reported 5 from the treatment of 4 with
H2S and it was characterized by single-crystal XRD [28].
Treatment of 4 with thiourea in refluxing THF gives 5
and 7 in 30% and 10% yields, respectively. This observation
is similar to that reported for the corresponding osmium
analogue [Os3(CO)10(l-dppm)] which afforded [Os3(l-
H)2(l3-S)(CO)7(l-dppm)] and [Os3(l3-S)(l3-CO)(CO)7(l-
dppm)] when treated with thiourea at 110 ꢀC [14].
Treatment of 7 with tetramethylthiourea in refluxing
THF gives the new cluster [Ru3(l3-S)2{g1-C(NMe2)2}-
(CO)6(l-dppm)] (9) together with compound 6 (Scheme
5) in 8% and 30% yields, respectively.
NHR
NHR
C
RHN
C
NHR
S
S
NHR
(CO)
OC
Ru
Ru
(CO)
CO
Ru
[Ru3(CO)12] + S
C
NHR
Ru
(CO)2
(CO)2
(R = Et or iPr)
Scheme 2.
(CO)3
P
(CO)4
Os
Os
(CO)2
Os
S
S
S
S
P
NMe2
(CO)
Os
P
Os
P
(CO)2
2
Os
P
(CO)3
+
+
(CO)
Os
P
S
C
3
(CO)3 Os
Os
(CO)2
NMe2
1
3
2
(diphosphine = dppm)
Scheme 3.

S.J. Ahmed et al. / Journal of Organometallic Chemistry 691 (2006) 309–322
311
(CO)3
Ru
(CO)3
Ru
(CO)4
Ru
H
S
S
S
H
NMe2
NMe2
(CO)
Ru
P
Ru
(CO)2
(CO)
THF
66 oC
Ru
P
(CO)2
2
Ru
P
2
Ru
P
(CO)3
+
(CO)
Ru
P
S
C
3
P
6
4
5
NMe2
C
NMe2
(CO)3
Ru
(CO)2
Ru
S
S
OC
OC
(CO)
Ru
P
Ru
P
(CO)2
(CO)
Ru
P
Ru
2
(CO)2
2
P
7
8
Scheme 4.
(CO)3
Ru
P
(CO)3
Ru
(CO)2
Ru
S
S
S
OC
S
S
P
NMe2
THF
+
(CO)
2
Ru
P
Ru
P
(CO)
(CO)2
Ru
P
Ru
P
(CO)2
+
S
2
C
66 oC
(CO)2 Ru
Ru
(CO)2
NMe2
C
NMe2
NMe2
9
6
7
Scheme 5.
˚
Treatment of 4 with elemental Se in refluxing THF at
66 ꢀC produces two new clusters: [Ru3(l3-Se)(CO)7-
(l3-CO)(l-dppm)] (10) and [Ru3(l3-Se)(CO)6(l-CO){l3-
g3-PPhCH2PPh(C6H4)}] (11) in 29% and 5% yields,
respectively and two known compounds [Ru3(l-H)2(l3-
Se)(CO)7(l-dppm)] (12) and [Ru4(l3-Se)(CO)10(l-dppm)]
(13) in 2% and 5% yields, respectively (see Scheme 6). We
[38] have recently reported 12 from hydrogenation of 10
while Predieri et al. [32] reported 13 from the reaction of
[Ru3(CO)12] with dppmSe2.
The reaction of 10 with tetramethylthiourea at 66 ꢀC
yields two triruthenium mixed sulfur-selenium compounds
[Ru3(l3-S)(l3-Se)(CO)7(l-dppm)] (14) and [Ru3(l3-S)(l3-
Se){g1-C(NMe2)2}(CO)6(l-dppm)] (15) in 38% and 10%
yields, respectively (see Scheme 7). The new compounds
were characterized by elemental analysis, infrared, 1H
NMR, 31P{1H} NMR spectroscopy and MS data together
with single-crystal XRD studies for 6–8, 10, 14, and 15.
two metal–metal bonds [Ru(1)–Ru(2) = 2.8150(9) A,
˚
Ru(1)–Ru(3) = 2.8217(9) A for
6 and Ru(1)–Ru(2) =
2.8444(8) A and Ru(1)–Ru(3) = 2.8373(8) A for 14], a non-
˚
˚
˚
˚
bonded separation of 3.5802 A for 6 and 3.626 A for 14
along the Ru(2)–Ru(3) edge, seven terminal carbonyl
groups, a l2-dppm and two l3-S for 6 and a l3-Se and a
l3 S ligands for 14. The metal–metal bond lengths are
similar but very slightly shorter that those in [Ru3(CO)12]
[average 2.854(4) A] [29] but are comparable to the
Ru–Ru distances in [Ru3(l3-Se)2(CO)7(l-dppa)] [2.831(1)
and 2.842(1) A] [30] and [Ru3(l3-Se)2(CO)7(l-dppe)]
[2.796(2) and 2.828(2) A] [31]. The seven carbonyl groups
˚
˚
˚
are distributed so that two are attached to each Ru(2)
and Ru(3) and three to Ru(1). The diaxially coordinated
dppm ligand spans the nonbonded Ru–Ru edge. The
˚
Ru–P distances [Ru(2)–P(1) = 2.3040(17) A and Ru(3)–
˚
˚
P(2) = 2.3046(16) A for 6 and Ru(3)–P(1) = 2.3014(18) A,
˚
Ru(2)–P(2) = 2.2956(17) A for 14] are slightly shorter than
those found in 4 [35]. The nonbonding Ru(2)ꢀ ꢀ ꢀRu(3)
˚
˚
2.2. XRD and spectroscopic studies
separations [3.5802 A for 6 and 3.626 A for 14] are signifi-
cantly shorter than the corresponding nonbonding separa-
˚
The structures of 6 (Fig. 1 and Table 1) and 14 (Fig. 2
and Table 2) consist of an ꢀopenꢁ trinuclear clusters with
tion in [Ru3(l3-Se)2(CO)7(l-dppe)] (3.75 A) [31] and
˚
[Ru3(l3-Se)2(CO)7(l-dppf)] (3.87 A) [31]. In 7, the Ru–S

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S.J. Ahmed et al. / Journal of Organometallic Chemistry 691 (2006) 309–322
(CO)3
Ru
(CO)3
Ru
(CO)4
Ru
H
Se
OC
Se
H
(CO)
Ru
(CO)2
Ru
P
THF
2
(CO)2 Ru
Ru(CO)2
P
Ru
P
(CO)3
+
(CO)
Ru
P
Se
3
66 oC
P
P
12
10
Ph
P
P
(CO)2
Ru
P
Se
Se
(CO)
Ru
(CO)
2 Ru
2
Se
Ru
(CO)3
PPh
(CO)
2 Ru
(CO)
Ru
2
Se
Se
C
O
Ru
(CO)3
11
13
Scheme 6.
P
(CO)3
Ru
(CO)2
(CO)3
Ru
Ru
Se
S
Se
Se
S
OC
P
NMe2
NMe2
THF
66 oC
Ru
P
Ru (CO)2
(CO)2
(CO)2 Ru
Ru
(CO)2
(CO)
Ru
P
Ru
P
+
(CO)2
+
S
2
C
C
P
NMe2
15
NMe2
10
14
Scheme 7.
distances to the central 7-coordinate ruthenium atom Ru(1)
single isomer with dppa bridging the open Ru–Ru edge,
but quite different from those of [Ru3(l3-Se)2(CO)7(l-
dppm)] (2066vs, 2052m, 2007w, 1956w cmꢁ1), a 1:2 mixture
of isomers in solution differing in the relative disposition of
the diphosphine ligand [32]. In the major isomer dppm
bridges a bonded Ru–Ru edge and in the minor isomer
two nonbonded Ru atoms.
The mass spectrum of 14 shows the expected parent ion
at m/z 995, confirming that it is [Ru3(l3-S)(l3-Se)(CO)7-
(l-dppm)] and is not a mixture containing [Ru3(l3-Se)2-
(CO)7(l-dppm)] and [Ru3(l3-S)2(CO)7(l-dppm)]. The
31P{1H} NMR spectrum shows the presence of two insep-
arable isomers differing in the distribution of the Ru–Ru
bonds. The major isomer 14a (90%) has the dppm bridging
two Ru atoms not connected by a Ru–Ru bond and gives a
singlet (d 63.9) while the minor isomer 14b (10%) gives two
doublets (d 24.8 and 15.9, J = 94.0 Hz) since the dppm is
across a bonded Ru–Ru edge. We have not confirmed
experimentally that these isomers are in equilibrium but
in the light of earlier results on [Ru3(l3-Se)2(CO)7-
(l-dppm)] [32] they are probably are (see Scheme 8). The
˚
˚
[Ru(1)–S(1) = 2.4059(17) A, Ru(1)–S(2) = 2.4244(17) A] are
longer than those to the external 6-coordinate ruthenium
˚
atoms [2.3729(18)–2.3924(18) A]. In 14, there is some disor-
der between the S and Se atoms with one site occupied by
0.83 Se and 0.17 S with the reverse in the other site. Fig. 2
shows the major occupancy labelled as Se(1) and S(1) and
the minor as Se(10) and S(10). Although the l3-selenido
triruthenium complexes [Ru3(l3-Se)2(CO)7(l-PP)] (PP =
dppm [32,33], dppf [31], dppe [31], dppa [30] have been
reported, compounds 6 and 14 provide the first S mixed
S, Se analogues.
The spectroscopic data of 6 are consistent with the solid-
state structure. The MS shows the molecular ion (m/z 949)
1
and the loss of seven carbonyl groups. The H NMR spec-
trum contains a triplet at d 3.14 (J = 10.0 Hz) for the dppm
methylene. The 31P{1H} NMR spectrum exhibits a singlet
at d 61.2 implying one isomer with equivalent P nuclei.
The m(CO) values for 6 (2054s, 2016s, 1984m, 1971m
cmꢁ1) are very similar to those of [Ru3(l3-Se)2(CO)7(l-
dppa)] (2057vs, 2022m, 1988w, 1971w cmꢁ1) [30], also a

S.J. Ahmed et al. / Journal of Organometallic Chemistry 691 (2006) 309–322
313
Fig. 1. Molecular structure of [Ru3(l3-S)2(CO)7(l-dppm)] (6).
IR spectrum is similar to that of [Ru3(l3-Se)2(CO)7-
(l-dppm)], supporting the presence of two isomers in
solution.
Chalcogenido compounds [Ru3(l3-E)(CO)7(l3-CO)(l-PP)]
(PP = dppm, dppe, dppa, dppf; E = S, Se, Te) have not
previously been reported.
The molecular structures of 7 and 10 are in Figs. 3 and
4, respectively, with data in Tables 3 and 4, respectively.
There are two crystallographically independent but chemi-
cally equivalent molecules of 7. The structures of 7 and 10
contain one l3-E, a l-dppm, seven terminal carbonyl
groups and a l3-carbonyl group, being formally derived
from that of [Ru3(l3-E)(CO)9(l3-CO)] [34] by replacement
of an equatorial carbonyl group on each of the two
Ru atoms by the dppm ligand. The complexes display
tetrahedral Ru3E cores with almost equilatorial Ru3 trian-
The mass spectra of 7 and 10 show the molecular ion
peaks (m/z 945 for 7 and 991 for 10) with successive loss
of seven carbonyl groups, while IR and NMR spectra of
7 and 10 show the solid-state structures persist in solution.
The IR carbonyl absorptions show a pattern similar to that
reported for the corresponding osmium analogues [Os3-
(l3-S)(CO)7(l3-CO)(l-dppm)] [14] and [Os3(l3-Se)(CO)7-
(l3-CO)(l-dppm)] [38]. The presence of l3 carbonyl groups
in 7 and 10 are apparent from the m(CO) bands at
1736 cmꢁ1 for 7 and 1655 cmꢁ1 for 10. The 31P{1H}
NMR spectra contain a singlet at d 25.6 for 7 and 25.9
for 10 indicating equivalent 31P nuclei.
˚
gles [Ru(1)–Ru(3) = 2.8103(13) A, Ru(2)–Ru(3) = 2.8122
˚
˚
(15) A and Ru(1)–Ru(2) = 2.7976(14) A for 7 and Ru(2)–
˚
˚
Ru(3) = 2.7964(3) A, Ru(1)–Ru(3) = 2.8071(3) A and
Ru(1)–Ru(2) = 2.8184(3) A for 10] symmetrically capped
by chalcogenido ligands [Ru(1)–S(1) = 2.362(3) A, Ru(2)–
S(1) = 2.369(3) A and Ru(3)–S(1) = 2.368(3) A for 7 and
The molecular structure of 8 (Fig. 5 and Table 5)
consists of a Ru3 triangle with three metal–metal bonds
˚
˚
˚
˚
[Ru(1)–Ru(2) = 2.7874(4) A, Ru(1)–Ru(3) = 2.8151(4) A
˚
˚
˚
and Ru(2)–Ru(3) = 2.8231(4) A]. It is a structurally unique
˚
˚
Ru(1)–Se(1) = 2.4844(4) A,
Ru(3)–Se(1) = 2.4901(4) A
compound with seven terminal carbonyls and one triply
bridging carbonyl, a capping S, and a tetramethyldiamino-
carbene ligand. The structure of this molecule relates to
that of 7 except for tetramethyldiaminocarbene ligand.
The Me2NCNMe2 ligand formed by C@S bond cleavage
of the tetramethylthiourea is coordinated equatorially at
˚
and Ru(2)–Se(1) = 2.4935(4) A for 10]. Three of seven ter-
minal carbonyl groups are bound to the Ru(1) atom and
two to each of the other two Ru atoms. The triply-bridging
carbonyl groups are asymmetrically attached [Ru(2)–
C(1) = 2.105(11) A, Ru(1)–C(1) = 2.273(10) A and Ru(3)–
C(1) = 2.204(11) A for 7 and Ru(1)–C(8) = 2.242(3) A,
Ru(2)–C(8) = 2.157(3) A and Ru(3)–C(8) = 2.150(3) A for
10]. The Ru-P bond distances [Ru(2)–P(1) = 2.334(3) A
and Ru(3)–P(2) = 2.367(3) A for 7 and Ru(2)–P(1) =
2.3209(8) A and Ru(3)–P(2) = 2.3336(8) A for 10] are
˚
˚
˚
˚
˚
Ru(3). The Ru–carbene distance, Ru(3)–C(3) = 2.122(4) A,
˚
˚
is comparable to similar bonds in the tetraruthenium com-
˚
plexes [Ru4(l4-S)2(CO)7(l-CO)2{(C(NMe2)2}2] [2.053(9)
˚
˚
and 2.085(9) A] [3] and [Ru4(l4-S)2(CO)8(l-CO)2{(C(N-
˚
˚
˚
Me2)2}] [2.086(4) A] [3] obtained by treating [Ru3(CO)12]
˚
comparable to those in 4 [2.322(2) and 2.334(2) A] [35].
with tetramethylthiourea. The carbene C–N distances,

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S.J. Ahmed et al. / Journal of Organometallic Chemistry 691 (2006) 309–322
Table 1
Table 2
˚
˚
Selected bond distances (A) and angles (ꢀ) for [Ru3(l3-S)2(CO)7(l-dppm)]
(6)
Selected bond distances (A) and angles (ꢀ) for [Ru3(l3-S)(l3-Se)(CO)7(l-
dppm)] (14)
Ru(1)–Ru(2)
Ru(1)–Ru(3)
Ru(2)–Ru(3)
Ru(1)–S(1)
Ru(1)–S(2)
Ru(2)–S(1)
Ru(2)–S(2)
Ru(3)–S(1)
Ru(3)–S(2)
Ru(2)–P(1)
Ru(3)–P(2)
P(1)–C(12)
P(2)–C(12)
2.8150(9)
2.8217(9)
3.5802(8)
2.4059(17)
2.4244(17)
2.3844(19)
2.3834(19)
2.3924(18)
2.3729(18)
2.3040(17)
2.3046(16)
1.866(7)
Ru(1)–Ru(3)
Ru(1)–Ru(2)
Ru(1)–Se(1)
Ru(2)–Se(1)
Ru(3)–Se(1)
Ru(3)–P(1)
Ru(2)–P(2)
Ru(3)–S(1)
Ru(2)–S(1)
Ru(1)–S(1)
2.8373(8)
2.8444 (8)
2.5240(9)
2.4760(10)
2.4756(10)
2.3014(18)
2.2956(17)
2.4182(16)
2.4262(15)
2.4328(13)
Ru(3)–Ru(1)–Ru(2)
S (1)–Ru(1)–Ru(2)
S(1)–Ru(1)–Ru(3)
S(1)–Ru(2)–Ru(1)
S(1)–Ru(3)–Ru(1)
Se(1)–Ru(1)–Ru(3)
Se(1)–Ru(1)–Ru(2)
Se(1)–Ru(2)–Ru(1)
Se(1)–Ru(3)–Ru(1)
Ru(2)–Se(1)–Ru(1)
Ru(3)–Se(1)–Ru(1)
Ru(3)–Se(1)–Ru(2)
Ru(3)–S(1)–Ru(2)
Ru(2)–S(1)–Ru(1)
Ru(3)–S(1)–Ru(1)
P(1)–C(8)–P(2)
79.31(2)
54.06(4)
53.97(4)
54.28(3)
54.45(3)
54.62(2)
54.54(2)
56.13(2)
56.23(2)
69.34(3)
69.14(3)
94.15(3)
96.91(5)
71.66(4)
71.59(4)
121.2(3)
1.846(6)
Ru(2)–Ru(1)–Ru(3)
Ru(2)–S(1)–Ru(1)
Ru(3)–S(2)–Ru(2)
Ru(2)–S(2)–Ru(1)
Ru(2)–S(1)–Ru(3)
Ru(1)–S(1)–Ru(3)
Ru(1)–S(2)–Ru(3)
S(1)–Ru(1)–Ru(3)
S(1)–Ru(1)–Ru(2)
S(1)–Ru(2)–Ru(1)
S(1)–Ru(3)–Ru(1)
S(2)–Ru(1)–Ru(2)
S(2)–Ru(1)–Ru(3)
S(2)–Ru(2)–Ru(1)
S(2)-Ru (3)–Ru(1)
S(1)–Ru(1)–S(2)
S(1)–Ru(2)–S(2)
S(1)–Ru(3)–S(2)
P(1)–Ru(2)–S(2)
P(2)–Ru(3)–S(1)
P(1)–Ru(2)–Ru(1)
P(2)–Ru(3)–Ru(1)
78.86(3)
71.98(5)
97.65(6)
71.67(5)
97.09(6)
72.04(5)
72.05(5)
53.76(4)
53.66(4)
54.36(4)
54.20(4)
53.49(4)
53.13(4)
54.84(4)
54.82(4)
79.30(6)
80.55(6)
80.60(6)
96.25(6)
92.03(6)
137.02(5)
135.34(5)
˚
˚
C(33)–N(1) = 1.355(5) A and C(33)–N(2) = 1.345(5) A, are
characteristic of terminally coordinated aminocarbenes
[36,37]. The l3-S ligand symmetrically caps the Ru3 triangle
with Ru–S distances in the narrow range 2.3744(9)–
2.3821(10) A. The l3-CO group is also bonded symmetri-
cally. The higher electron density at Ru(3) caused by the
˚
Fig. 2. Molecular structure of [Ru3(l3-S)(l3-Se)(CO)7(l-dppm)] (14).

S.J. Ahmed et al. / Journal of Organometallic Chemistry 691 (2006) 309–322
315
(CO)3
Ru
carbene ligand is most probably distributed over the whole
ruthenium framework to result in nearly symmetrical car-
bonyl and S bridges in contrast to 7 where these bridges
are unsymmetrical. The Ru–P distances in 8 [Ru(1)–
(CO)3
Ru
Se
(CO)
Se
S
S
Ru
P
Ru
(CO)2
Ru
P
2
Ru (CO)2
(CO)2
˚
˚
P(1) = 2.3419(11) A, Ru(2)–P(2) = 2.3211(11) A] are com-
parable to those in 4 [35].
P
P
The IR spectrum of 8 shows a band at 1642 cmꢁ1 for the
l3-carbonyl ligand while the mass spectrum shows the
molecular ion at m/z 1017 which loses seven carbonyl
groups sequentially. The 1H NMR spectrum contains three
14b
14a
Scheme 8.
Fig. 3. Molecular structure of [Ru3(l3-S)(CO)7(l3-CO)(l-dppm)] (7).
Fig. 4. Molecular structure of [Ru3(l3-Se)(CO)7(l3-CO)(l-dppm)] (10).

316
S.J. Ahmed et al. / Journal of Organometallic Chemistry 691 (2006) 309–322
Table 3
Table 4
˚
˚
Selected bond distances (A) and angles (ꢀ) for [Ru3(l3-S)(CO)7(l3-CO)(l-
dppm)] (7)
Selected bond distances (A) and angles (ꢀ) for [Ru3(l3-Se)(CO)7(l3-CO)(l-
dppm)] (10)
Molecule 1
Molecule 2
Ru(1)–Ru(2)
Ru(1)–Ru(3)
Ru(2)–Ru(3)
Ru(1)–Se(1)
Ru(3)–Se(1)
Ru(2)–Se(1)
Ru(1)–C(8)
Ru(3)–C(8)
Ru(2)–C(8)
Ru(2)–P(1)
Ru(3)–P(2)
P(1)–C(9)
2.8184(3)
2.8071(3)
2.7964(3)
2.4844(4)
2.4901(4)
2.4935(4)
2.242(3)
2.150(3)
2.157(3)
2.3209(8)
2.3336(8)
1.844(3)
1.846(3)
Ru(1)–Ru(2)
Ru(1)–Ru(3)
Ru(2)–Ru(3)
Ru(1)–S(1)
Ru(2)–S(1)
Ru(3)–S(1)
Ru(1)–C(1)
Ru(2)–C(1)
Ru(3)–C(1)
Ru(2)–P(1)
Ru(3)–P(2)
2.7976(14)
2.8103(13)
2.8122(15)
2.362(3)
2.369(3)
2.368(3)
2.273(10)
2.105(11)
2.204(11)
2.334(3)
2.8129(14)
2.8021(13)
2.8080(14)
2.365(3)
2.372(3)
2.367(3)
2.272(9)
2.155(10)
2.154(10)
2.344(3)
2.367(3)
2.335(3)
P(2)–C(9)
S(1)–Ru(1)–Ru(2)
S(1)–Ru(2)–Ru(3)
S(1)–Ru(1)–Ru(3)
S(1)–Ru(3)–Ru(2)
S(1)–Ru(3)–Ru(1)
C(1)–Ru(1)–Ru(3)
C(1)–Ru(2)–Ru(3)
C(1)–Ru(3)–Ru(2)
C(1)–Ru(3)–Ru(1)
P(1)–Ru(2)–Ru(3)
P(2)–Ru(3)–Ru(2)
53.87(7)
53.57(7)
53.65(7)
53.60(7)
53.44(7)
50.0(3)
50.8(3)
47.7(3)
52.2(3)
92.08(8)
93.82(8)
53.68(7)
53.59(7)
53.72(7)
53.74(7)
53.67(7)
48.9(3)
49.3(3)
49.4(3)
52.6(3)
94.54(7)
92.92(7)
Ru(3)–Ru(2)–Ru(1)
Ru(3)–Ru(1)–Ru(2)
Ru(2)–Ru(3)–Ru(1)
Se(1)–Ru(2)–Ru(1)
Se(1)–Ru(2)–Ru(2)
Se(1)–Ru(3)–Ru(2)
Se(1)–Ru(1)–Ru(3)
Se(1)–Ru(3)–Ru(1)
Se(1)–Ru(2)–Ru(3)
C(8)–Ru(1)–Ru(3)
C(8)–Ru(1)–Ru(2)
C(8)–Ru(3)–Ru(2)
C(8)–Ru(2)-Ru (3)
C(8)–Ru(2)–Ru(1)
Ru(1)–Se(1)–Ru(3)
Ru(3)–Se(1)–Ru(2)
Ru(1)–Se(1)–Ru(2)
Ru(2)–C(8)–Ru(1)
Ru(3)–C(8)–Ru(2)
Ru(3)–C(8)–Ru(1)
P(2)–Ru(3)–Ru(2)
P(1)–Ru(2)–Ru(3)
P(1)–C(9)–P(2)
59.991(8)
59.616(8)
60.393(8)
55.364(10)
55.669(9)
55.925(9)
55.742(9)
55.551(10)
55.808(9)
48.86(8)
48.83(8)
49.61(8)
49.42(8)
51.49(8)
68.707(11)
68.267(10)
68.968(11)
79.68(10)
80.97(11)
79.42(10)
96.688(19)
89.53(2)
multiplets at d 7.32, 3.88, 3.44 and a singlet at d 3.26 in a
relative intensity of 20:1:1:12 corresponding, respectively,
to Ph, the non-equivalent CH2 protons of dppm, and the
Me of the carbene ligand. The 31P{1H} NMR spectrum
contains a singlet at d 28.5 indicating that the 31P nuclei
are equivalent. These solution data fit a structure like that
found in the crystal.
Crystals of 9 suitable for XRD studies were unobtainable
and spectroscopic data do not provide a unique structure.
113.55(16)
Fig. 5. Molecular structure of [Ru3(l3-S)(CO)6(l3-CO){g1-C(NMe2)2}(l-dppm)] (8).

S.J. Ahmed et al. / Journal of Organometallic Chemistry 691 (2006) 309–322
317
Table 5
chemical shifts are close to those reported for structurally
characterized orthometallated compound [Ru3{l3-g3-
PhPCH2PPh(C6H4)}(CO)9] [d 2.9 (d), 117.3 (d), J =
1
˚
Selected bond distances (A) and angles (ꢀ) for [Ru3(l3-S){g -C(NMe2)2}-
(CO)6(l3-CO)(l-dppm)] (8)
85.0 Hz)], [9] suggesting the presence of
a
l3-g3-
Ru(1)–Ru(2)
Ru(1)–Ru(3)
Ru(2)–Ru(3)
Ru(1)–S(1)
Ru(2)–S(1)
Ru(3)–S(1)
Ru(1)–C(7)
Ru(2)–C(7)
Ru(3)–C(7)
O(1)–C(1)
N(1)–C(33)
N(2)–C(33)
N(1)–C(35)
N(1)–C(34)
Ru(1)–P(1)
Ru(2)–P(2)
P(1)–C(20)
P(2)–C(20)
2.7874(4)
2.8151(4)
2.8231(4)
2.3744(9)
2.3821(10)
2.3795(11)
2.197(4)
2.180(4)
2.154(4)
1.150(5)
1.355(5)
1.345(5)
1.464(6)
1.461(6)
2.3419(11)
2.3211(11)
1.842(4)
1.831(4)
PhPCH2PPh(C6H4) ligand in 11. The mass spectrum shows
the parent at m/z 885 and fragments ions formed by the
sequential loss of one Ph and seven carbonyl groups. Most
probably 11 is formed by the reaction of the orthometal-
lated compound [Ru3{l3-g3-PhPCH2PPh(C6H4)}(CO)9],
formed in situ from the thermolysis of 4, with selenium
but we have not demonstrated this.
The solid-state molecular structure of 15 (Fig. 6 and Ta-
ble 6) consists of an open Ru3 triangle with six terminal
carbonyl groups, a triply-bridging S, a triply-bridging Se,
a bridging dppm and a tetramethyldiaminocarbene ligand.
As with 8, the tetramethyldiaminocarbene ligand is derived
from C@S cleavage in the tetramethylthiourea ligand.
Compound 15 is simply a tetramethyldiaminocarbene-
substitution product of 14 but the replacement of CO by
the carbene has significantly affected the geometry. There
appears to be complete disorder between S and Se in com-
pound 15 and the model was refined with 50% of each atom
with identical coordinates in each site. The dppm coordina-
tion has shifted from the open metal–metal edge to the
bonded Ru(1)–Ru(2) edge with Ru–P distances [Ru(1)–
Ru(1)–Ru(3)–Ru(2)
Ru(2)–Ru(1)–Ru(3)
Ru(1)–Ru(2)–Ru(3)
Ru(1)–S(1)–Ru(3)
Ru(3)–S(1)–Ru(2)
Ru(1)–S(1)–Ru(2)
Ru(3)–C(7)–Ru(1)
Ru(2)–C(7)–Ru(1)
C(7)–Ru(3)–Ru(1)
C(7)–Ru(3)–Ru(2)
C(7)–Ru(1)–Ru(2)
S(1)–Ru(3)–Ru(2)
S(1)–Ru(1)–Ru(2)
S(1)–Ru(3)–Ru(1)
S(1)–Ru(2)–Ru(1)
S(1)–Ru(2)–Ru(3)
S(1)–Ru(1)–Ru(3)
P(2)–Ru(2)–Ru(1)
P(1)–Ru(1)–Ru(2)
P(2)–C(20)–P(1)
59.258(10)
60.515(10)
60.227(10)
72.62(3)
72.72(3)
71.75(3)
80.62(14)
79.10(14)
50.36(11)
49.76(11)
50.18(10)
53.68(2)
54.25(2)
53.61(2)
54.00(2)
53.60(3)
53.77(3)
90.00(3)
94.95(3)
111.7(2)
122.5(3)
113.4(3)
˚
˚
P(2) = 2.329(2) A and Ru(2)–P(1) = 2.318(2) A] similar to
those in 4. The dppm-bridged Ru(1)–Ru(2) distance of
˚
2.7801(16) A is significantly shorter than the nonbridged
˚
Ru(2)–Ru(3) distance of 2.8313(15) A. The diaminocar-
bene ligand is coordinated equatorially to Ru(3) and the
˚
Ru(3)–C(1) distance of 2.078(7) A is shorter than the corre-
sponding distance in 8 but very similar to the osmium–
carbene distance in [Os3(l-H)(CO)8{l-g3-CN(Me)-
˚
C(Et)C(Ph)C(Ph)}] [2.07(1) A] [36]. The carbene C–N bond
lengths are similar to those in 8. The l3-S ligand is bonded
N(1)–C(33)–Ru(3)
N(2)–C(33)–N(1)
symmetrically with the three Ru–S distances in the
˚
range 2.4904(8)–2.5083(7) A, whereas l3-Se ligand caps the
Ru3 core asymmetrically with the three Ru–Se distances
˚
The structure of 9 is therefore based on comparison of spec-
tra with those of the corresponding mixed S–Se analogue
15, the XRD structure of which we report in this paper.
The IR spectra of 9 and 15 are very similar, indicating that
they are isostructural. The FAB MS shows the molecular
ion (m/z 1021) and the stepwise loss of up to six carbonyl
ranging from 2.4648(15) to 2.5242(16) A.
The IR spectrum of 15 shows only terminal carbonyl
groups. The 31P{1H} NMR spectrum contains two dou-
blets at d 23.6 and 14.2, indicating non-equivalent 31P nu-
clei. The mass spectrum shows the parent at m/z 1068.
Compound 15 provides the first example of a structurally
characterized 50-electron triruthenium cluster containing
capping S/Se and a diphosphine bridging a bonded pair
of Ru atoms. The coordination of the dppm ligand is struc-
turally similar to that which has recently been reported for
the 50-electron compound [Os3(l3-Se)2(CO)7(l-dppm)]
[38].
1
groups. The H NMR spectrum shows three multiplets at
d 7.48, 4.33, 3.83 and a singlet at d 3.38 in a 20:1:1:12 inten-
sity ratio assigned, respectively, to Ph, non-equivalent CH2
protons of dppm and Me of (Me2N)2C.
The IR spectrum for 11 exhibits a bridging carbonyl
1
band at 1740 cmꢁ1 and the H NMR spectrum in the aro-
matic region is characteristic of an orthometallated phenyl
ring. The 31P{1H} NMR spectrum contains two doublets
(J = 102.0 Hz) of equal intensity at d 22.6 and 138.3 due
to the magnetically non-equivalent 31P nuclei of the ligand.
The signal at d 22.6 is due to the terminal phosphorus atom
while the low field signal at d 138.3 is characteristic of a
phosphorus atom bridging a metal–metal bond. The 31P
3. Conclusions
Our results on the treatment of 4 with tetramethylthiou-
rea are summarised in Scheme 4 while those with elemental
Se are in Scheme 6. Compounds 6 and 14 have bicapped
open triangular structures with nido Ru3EE0 cores (6,

318
S.J. Ahmed et al. / Journal of Organometallic Chemistry 691 (2006) 309–322
Fig. 6. Molecular structure of [Ru3(l3-S)(l3-Se){g1-C(NMe2)2}(CO)6(l-dppm)] (15).
E = E0 = S; 14, E = S, E0 = Se). A dppm spans the non-
Table 6
1
˚
Selected bond distances (A) and angles (ꢀ) for [Ru3(l3-S)(l3-Se){g -
C(NMe2)2}(CO)6(l-dppm)] (15)
bonded metal–metal edge. The structures could be de-
scribed as a square pyramid with two Ru and two S/Se
alternating in the basal plane with the third Ru atom at
the apex. In sharp contrast to the reaction of 1 with tetram-
ethylthiourea which affords two isomeric forms of the nido
cluster [Os3(l-S)2(CO)7(l-dppm)], the reaction of 4 with
tetramethylthiourea gives four triruthenium clusters 5 to
8 containing bridging dppm and capping S ligands, the lat-
ter from C@S bond cleavage. Compounds 7 and 10 contain
l3-CO on one face and a l3-S or Se on the opposite face
and a bridging dppm. They both display tetrahedral
Ru3E (E = S or Se) cores. Compound 8 represents an unu-
sual example of a S-capped Ru3 cluster containing a diami-
nocarbene ligand. Cluster 7 can formally be derived from 8
by replacement of the diaminocarbene ligand by CO.
In contrast to the reaction of elemental Se with 1 which
gave intractible materials, it reacts with 4 to give three new
Ru3 selenido clusters 10–12 and the previously reported cu-
bane cluster 13. Further reaction of 10 with elemental Se
does not produce [Ru3(l3-Se)2(CO)7(l-dppm)] whereas
with tetramethylthiourea the mixed S/Se compound 14 is
formed.
Ru(1)–Ru(2)
Ru(2)–Ru(3)
Ru(1)–S(1)/Se(1)
Ru(1)–S(2)/Se(2)
Ru(2)–S(1)/Se(1)
Ru(2)–S(2)/Se(2)
Ru(3)–S(2)/Se(2)
Ru(3)–S(1)/Se(1)
Ru(1)–P(2)
Ru(2)–P(1)
Ru(3)–C(1)
N(1)–C(3)
N(2)–C(1)
2.7808(16)
2. 8313(15)
2.4904(18)
2.4648(15)
2.5083 (17)
2.5242(16)
2.4803(17)
2.5028(17)
2.329(2)
2.318 (2)
2.078(7)
1.479(10)
1.348(10)
1.486(10)
1.443(12)
1.367(10)
1.461(11)
N(2)–C(5)
N(2)–C(4)
N(1)–C(1)
N(1)–C(2)
Ru(1)–S(2)/Se(2)–Ru(2)
Ru(1)–S(1)/Se(1)–Ru(2)
Ru(1)–S(2)/Se(2)–Ru(3)
Ru(3)–S(2)/Se(2)-Ru (2)
S(2)/Se(2)–Ru(1)–Ru(2)
S(1)/Se(1)–Ru(1)–Ru(2)
S(1)/Se(1)–Ru(2)–Ru(1)
S(2)/Se(2)–Ru(2)–Ru(3)
S(2)/Se(2)–Ru(3)–Ru(2)
S(1)/Se(1)–Ru(2)–Ru(3)
P(2)–Ru(1)–Ru(2)
P(1)–Ru(2)–Ru(1)
Ru(1)–Ru(2)–Ru(3)
C(1)–Ru(3)–Ru(2)
N(2)–C(1)–N(1)
S(2)/Se(2)–Ru(2)–Ru(1)
Ru(3)–S(1)/Se(1)–Ru(2)
Ru(1)–S(1)/Se(1)–Ru(3)
S(1)/Se(1)–Ru(3)–Ru(2)
67.72(5)
67.58(4)
98.36(6)
68.90(4)
57.16(3)
56.52(4)
55.90(5)
54.82(3)
56.28 (4)
55.51(4)
99.23(5)
87.16(6)
83.56(5)
144.65(19)
114.1(7)
55.12(4)
68.80(5)
97.09(7)
55.69(4)
4. Experimental
Although the products are air-stable, all reactions were
performed under an atmosphere of nitrogen. THF, tolu-
ene, heptane and hexane were dried over sodium and dis-
tilled from sodium benzophenone ketyl under nitrogen
immediately prior to use. Methylene chloride was freshly
distilled from calcium hydride before use. IR spectra were
recorded on a Shimadzu FTIR 1401 spectrometer, NMR
spectra on a Bruker 400 or AM-300 or Varian Unity Plus

S.J. Ahmed et al. / Journal of Organometallic Chemistry 691 (2006) 309–322
319
400 spectrometers. 31P NMR chemical shifts are relative to
85% H3PO4 (external reference) and 1H chemical shifts are
referenced against residual protonated solvent. Fast atom
bombardment mass spectra were obtained on a JEOL
SX-102 spectrometer using 3-nitrobenzyl alcohol as matrix
and CsI as calibrant. The cluster [Ru3(CO)10(l-dppm)] (4)
was prepared by a published procedure [39].
(0.009 g, 8%) (Anal. Calc. for C36H34N2O6P2Ru3S2: C,
42.39; H, 3.36; N, 2.75. Found: C, 42.45; H, 3.65; N,
2.84%), IR (mCO, CH2Cl2): 2012s, 1987vs, 1973s, 1939s
1
cmꢁ1; H NMR (CDCl3): d 7.48 (m, 20H), 4.33(m, 1H),
3.83 (m, 1H) 3.38 (s, 12H). 31P{1H} NMR (CDCl3): d
28.1 (d, J = 51.5 Hz), 18.5 (d, J = 51.5 Hz). FAB MS:
m/z 1021(M+).
4.1. Reaction of [Ru3(CO)10(l-dppm)] (4) with
tetramethylthiourea
4.4. Thermolysis of 8
A THF solution (15 ml) of 8 (0.020 g, 0.019 mmol) was
refluxed for 5 h. The solvent was pumped off and the resi-
due chromatographed as above to give 7 (0.011 g, 55%).
A THF solution (35 ml) of 4 (0.300 g, 0.31 mmol) and
tetramethylthiourea (0.161 g, 1.22 mmol) was refluxed for
6 h. The solvent was pumped off and the residue chromato-
graphed (TLC on silica gel). Elution with cyclohexane/
CH2Cl2 (7:3, v/v) developed four bands. The first band
afforded [Ru3(l-H)2(l3-S)(CO)7(l-dppm)] (5) (0.017 g,
6%) as red crystals from CH2Cl2/hexane at room tempera-
ture. The second band yielded [Ru3(l3-S)2(CO)7(l-dppm)]
(6) (0.030 g, 10%) as red crystals from hexane/CH2Cl2 at
ꢁ20 ꢀC (Anal. Calc. for C32H22O7P2Ru3S2: C, 40.55; H,
2.34. Found: C, 40.65; H, 2.78%). IR (mCO, CH2Cl2):
4.5. Reaction of 4 with elemental selenium
A THF solution (35 ml) of 4 (0.200 g, 0.210 mmol) and
elemental Se (0.032 g, 0.417 mmol) was refluxed under N2
for 5 h. The solvent was pumped off and the residue
chromatographed (TLC on silica gel). Elution with cyclo-
hexane/CH2Cl2 (7:3, v/v) developed four bands. The first
band yielded [Ru3(l3-Se)(CO)7(l3-CO)(l-dppm)] (10)
(0.060 g, 29%) as orange crystals from hexane/CH2Cl2 at
5 ꢀC (Anal. Calc. for C33H22O8P2Ru3Se: C, 40.01; H,
2.24. Found: C, 40.23; H, 2.42%). IR (mCO, CH2Cl2):
1
2054s, 2016s, 1984m, 1971m cmꢁ1. H NMR (CDCl3): d
7.36 (m, 20H), 3.14 (t, J = 10.0 Hz). 31P{1H} NMR
(CDCl3): d 61.2 (s). FAB MS: m/z 949. The third band
yielded [Ru3(l3-S)(CO)7(l3-CO)(l-dppm)] (7) (0.095 g,
32%) as yellow crystals from hexane/CH2Cl2 at ꢁ20 ꢀC
(Anal. Calc. for C33H22O8P2Ru3S: C, 42.00; H, 2.35.
Found: C, 42.15; H, 2.49%). IR (mCO, hexane): 2072s,
1
2069s, 2023vs, 2000s, 1971m cmꢁ1. H NMR (CDCl3): d
7.34 (m, 20H), 4.23 (m, 1H), 3.61 (m, 1H). 31P{1H}
NMR (CDCl3): d 25.9 (s). Mass spectrum: m/z 991 (M+).
The second band gave [Ru3(l3-Se)(CO)6(l-CO){l3-g3-
P(C6H5)CH2P(C6H5)(C6H4)}] (11) (0.010 g, 5%) as yellow
needles from hexane/CH2Cl2 at 5 ꢀC (Anal. Calc. for
C26H16O7P2Ru3Se: C, 35.30; H, 1.82. Found: C, 35.52;
H, 2.02%). IR (mCO, CH2Cl2): 2079s, 2046vs, 2023vs,
1
2026vs, 2007s, 1980m, 1736br cmꢁ1. H NMR (CDCl3): d
7.34 (m, 20H), 3.92 (m, 1H), 3.57 (m, 1H). 31P{1H}
NMR (CDCl3): d 30.2 (s). FAB MS: m/z 945 (M+). The
fourth band gave [Ru3(l3-S){g1-C(NMe2)2}(CO)6(l3-
CO)(l-dppm)] (8) (0.028 g, 9%) as orange crystals from
hexane/CH2Cl2 at 4 ꢀC (Anal. Calc. for C37H34N2O7-
P2Ru3S: C, 43.74; H, 3.37; N, 2.76. Found: C, 43.98; H,
3.67; N, 2.82%). IR (mCO, CH2Cl2): 2021s, 1996vs,
1
2008w, 1992m cmꢁ1. H NMR (CDCl3): d 7.53 (m, 14H),
3.89 (m, 1H), 3.38 (m, 1 H). 31P{1H} NMR (CDCl3):
d 22.6 (d, J = 102.0 Hz), 138.3 (d, J = 102.0 Hz); FAB
MS: m/z 885. The third and the fourth bands gave the
known compounds [Ru3(l-H)2(l3-Se)(CO)7(l-dppm)] (12)
(0.004 g, 2%) and [Ru4(l3-Se)4(CO)10(l-dppm)] (13)
(0.003 g, 5%), respectively as yellow crystals from hexane/
CH2Cl2 at 5 ꢀC.
1
1985m, 1954s, 1942w cmꢁ1. H NMR (CD2Cl2): d 7.32
(m, 20H), 3.88 (m, 1H), 3.44 (m, 1H), 3.26 (s, 3H).
31P{1H} NMR (CD2Cl2): d 28.5 (s). FAB MS: m/z 1017.
4.2. Reaction of 4 with thiourea
4.6. Reaction of 10 with tetramethylthiourea
A mixture of 4 (0.100 g, 0.103 mmol) and thiourea
(0.015 g, 0.197 mmol) in THF (25 ml) was refluxed for
1 h. The solvent was pumped off and the residue chromato-
graphed (TLC on silica gel). Elution with cyclohexane/
CH2Cl2 (7:3, v/v) developed two bands affording 5
(0.029 g, 30%) and 7 (0.009 g, 10%).
A solution of 10 (0.100 g, 0.101 mmol) and tetrame-
thylthiourea (0.027 g, 0.204 mmol) in THF (30 ml) was re-
fluxed for 8 h. The solvent was pumped off and the residue
chromatographed (TLC on silica gel). Elution with cyclo-
hexane/CH2Cl2 (3:2, v/v) developed two bands. The major
band afforded [Ru3(l3-S)(l3-Se)(CO)7(l-dppm)] (14)
(0.038 g, 38%) as yellow crystals from CH2Cl2/hexane at
ꢁ15 ꢀC (Anal. Calc. for C32H22O7P2Ru3SSe: C, 38.64; H,
2.23. Found: C, 38.81; H, 2.34%). IR (mCO, CH2Cl2):
4.3. Reaction of 7 with tetramethylthiourea
A THF solution (25 ml) of 7 (0.100 g, 0.103 mmol) and
tetramethylthiourea (0.027 g, 0.204 mmol) was refluxed
for 4 h. Chromatographic separation as above afforded
unconsumed 7 (0.035 g), 6 (0.030 g, 30%), and a new
compound [Ru3(l3-S)2{g1-C(NMe2)2}(CO)6(l-dppm)] (9)
2067w, 2052vs, 2016vs, 1986m, 1956m cmꢁ1 1H NMR
.
(CDCl3): d 7.33 (m, 20H), 4.42 (m, 1H), 3.98 (m, 1H),
3.22 (t, 2H). 31P{1H} NMR (CDCl3): major isomer d
63.9 (s); minor isomer 24.8 (d, J = 94.0 Hz), 15.9 (d,

Table 7
Crystal data and structure refinement for 6, 7, 8, 10, 14 and 15
Compound
6
7
8 Æ CH2Cl2
10
14
15
Empirical formula
Formula weight
Temperature (K)
Crystal system
Space group
C
947.77
293(2)
Monoclinic
I2/a
22.270(6)
14.331(3)
23..681(5)
90
111.580(17)
90
32H22O7P2Ru3S2
C33H22O8P2Ru3S
943.72
150(2)
C38H36Cl2N2O7P2Ru3S
1100.80
150(2)
Monoclinic
P21/c
21.3770(3)
9.1714(2)
21.4585(4)
90
97.1196(11)
90
4174.65(13)
4
1.751
1.375
C33H22O8P2Ru3Se
990.62
150(2)
C32H22O7P2Ru3SSe
994.67
150(2)
Monoclinic
I2/a
22.1940(5)
14.0607(4)
23.6310(7)
90
111.6100(9)
90
6856.0(3)
8
1.927
2.566
C36H34N2O6P2Ru3SSe
1066.82
150(2)
Triclinic
Triclinic
Triclinic
ꢀ
ꢀ
ꢀ
P1
P1
P1
˚
a (A)
9.056(2)
9.16270(10)
10.12940(10)
18.8287(3)
96.9554(5)
101.4536(6)
94.5914(5)
1690.38(4)
2
9.013(6)
˚
b (A)
18.398(3)
22.148(5)
107.342(14)
97.740(7)
95.656(14)
3452.6(12)
4
1.816
1.497
1848
10.550(7)
21.627(14)
77.491(10)
79.943(11)
81.770(11)
1965(2)
˚
c (A)
a (ꢀ)
b (ꢀ)
c (ꢀ)
3
˚
V (A )
7028(3)
8
1.791
1.527
Z
2
Densitycalc (g cmꢁ3
)
1.946
2.544
960
1.803
2.245
1048
Absorption coefficient (mmꢁ1
F(000)
)
3712
2184
3856
Crystal size (mm)
h Range for data collection (ꢀ)
Limiting indices
0.35 · 0.25 · 0.12
1.97–25.03
ꢁ25 6 h 6 25
ꢁ16 6 k 6 13
ꢁ26 6 l 6 25
14159
0.20 · 0.08 · 0.06
1.75–25.01
ꢁ10 6 h 6 7
ꢁ20 6 k 6 20
ꢁ16 6 l 6 25
11643
0.28 · 0.22 · 0.20
2.93–26.37
ꢁ26 6 h 6 26
ꢁ10 6 k 6 11
ꢁ24 6 l 6 26
31985
0.18 · 0.08 · 0.07
3.03–27.47
ꢁ11 6 h 6 11
ꢁ13 6 k 6 13
ꢁ24 6 l 6 24
29637
0.25 · 0.10 · 0.05
3.09–27.51
ꢁ28 6 h 6 28
ꢁ17 6 k 6 17
ꢁ30 6 l 6 30
19084
0.57 · 0.15 · 0.08
1.99–28.33
ꢁ11 6 h 6 12
ꢁ13 6 k 6 13
ꢁ10 6 l 6 28
16287
Reflections collected
Independent reflections [Rint
Maximum and minimum
transmission
]
5337 [0.0641]
8415 [0.2359]
8506 [0.0834]
0.7705 and 0.6994
7652 [0.0411]
0.8420 and 0.6574
7751 [0.0416]
0.8824 and 0.5663
8800 [0.0549]
0.3611 and 0.8462
Data/restraints/parameters
Goodness-of-fit on F2
Final R indices [I > 2r(I)]
5337/30/367
1.010
8415/0/751
0.988
8506/0/500
0.975
7652/0/424
1.164
7751/30/415
1.010
8800/0/466
0.722
R1 = 0.0557,
wR2 = 0.1284
R1 = 0.0708,
wR2 = 0.1317
2.219 and ꢁ1.044
R1 = 0.0684,
wR2 = 0.1329
R1 = 0.1210,
wR2 = 0.1373
1.447 and ꢁ0.837
R1 = 0.0387,
wR2 = 0.0897
R1 = 0.0573,
wR2 = 0.1048
0.781 and ꢁ1.133
R1 = 0.0266,
wR2 = 0.0698
R1 = 0.0326,
wR2 = 0.0879
0.732 and ꢁ1.648
R1 = 0.0656,
wR2 = 0.1744
R1 = 0.0859,
wR2 = 0.1819
6.199 and ꢁ1.142
R1 = 0.0612,
wR2 = 0.1618
R1 = 0.0839,
wR2 = 0.1849
3.466 and ꢁ1.1807
R indices (all data)
Largest difference peak
ꢁ3
˚
and hole (e A
)

S.J. Ahmed et al. / Journal of Organometallic Chemistry 691 (2006) 309–322
321
J = 94.0 Hz); FAB MS: m/z 995. The minor band gave
[Ru3(l3-S)(l3-Se){g1-SC(NMe2)2}(CO)6(l-dppm)]
(15)
posit@ccdc.cam.ac.uk or on the web www: http://
www.ccdc.ac.uk.
(0.011 g, 10%) as yellow crystals from hexane/CH2Cl2 at
5 ꢀC. (Anal. Calc. for C36H34N2O6P2Ru3SSe: C, 40.53; H,
3.21; N, 2.63. Found: C, 40.72; H, 3.34; N, 2.78%). IR
Acknowledgements
(mCO, CH2Cl2): 2010s, 1987vs, 1970s, 1935s cmꢁ1 1H
;
We thank Dr. K.M. Abdul Malik (Department of
Chemistry, University of Cardiff) for obtaining X-ray data
on compounds 6–14. The Royal Society (London) and the
Swedish Academy of Sciences are thanked for supporting
the collaboration between AJD and EN and the Wenner-
Gren Foundation (Stockholm) for a fellowship to A.J.D.
to work at Lund University. SEK acknowledges support
from the Royal Society (London), the Swedish Interna-
tional Development Agency and the Swedish Science Re-
search Council.
NMR (CDCl3): d 7.25 (m, 20H), 4.18(m, 1H), 3.97 (m,
1H) 3.33 (s, 12H). 31P{1H} NMR (CDCl3): d 23.6 (d,
J = 35.5 Hz), 14.2 (d, J = 35.5 Hz); FAB MS: m/z 1068
(M+).
4.7. X-ray crystallography
Intensity data for 6 and 7 were obtained using a Delft
Instruments FAST TV area detector diffractometer using
˚
Mo Ka radiation (k = 0.71073 A) as described previously
[40]. Data sets were corrected for absorption using DIFABS
[41]. Crystal quality for 6 and 7 was poor, but their struc-
tures were satisfactory. Data for complexes 8–14 were ob-
tained using a Bruker Nonius Kappa CCD diffractometer
using Mo Ka radiation. Data collection and processing
were carried out by using the programs COLLECT [42] and
DENZO [43]. The data were corrected for absorption effects
by comparing the symmetry related data using SORTAV
[44]. Intensity data for 15 were obtained on a Bruker
SMART APEX CCD diffractometer using Mo Ka radia-
tion at 150(2) K. Data reduction and integration was car-
ried out with SAINT+ and absorption corrections using
SADABS [45,46].
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