Reactions of trans-[RuCl2(CO)2(PEt3) 2] with 1,1-dithiolates: Stepwise formation of cis-[Ru(CO)(PEt 3)(S2X)] (X = CNMe2, CNEt2, COEt, P(OEt)2, PPh2)

Article abstract of DOI:10.1016/j.jorganchem.2005.08.051

Trans-[RuCl₂(CO)₂(PEt₃)₂] reacts with two equivalents of a series of 1,1-dithiolate ligands to form the bis(dithiolate) complexes, cis-[Ru(CO)(PEt₃)(S₂X) ₂] (X = CNMe₂, CNEt₂, COEt, P(OEt)₂, PPh₂). Two intermediates have been isolated; trans-[Ru(PEt ₃)₂Cl(CO){S₂P(OEt)₂}] and trans-[Ru(PEt₃)₂(CO)(η¹-S ₂COEt)(η²-S₂COEt)], allowing a simple reaction scheme to be postulated involving three steps; (i) initial replacement of cis carbonyl and chloride ligands, (ii) substitution of the second chloride, (iii) loss of a phosphine. Thermolysis of cis-[Ru(CO)(PEt₃)(S ₂CNMe₂)₂] with Ru₃(CO)₁₂ in xylene affords trinuclear [Ru₃(μ₃-S) ₂(PEt₃)(CO)₈] as a result of dithiocarbamate degradation. Crystal structures of cis-[Ru(CO)(PEt₃)(S ₂X)₂] (X = NMe₂, COEt), trans-[Ru(PEt ₃)₂Cl(CO){S₂P(OEt)₂}], trans-[Ru(PEt₃)₂(CO)(η¹-S ₂COEt)(η²-S₂COEt)] and [Ru ₃(μ₃-S)₂(PEt₃)(CO)₈] are reported.

Full text of DOI:10.1016/j.jorganchem.2005.08.051

Journal of Organometallic Chemistry 691 (2006) 79–85
www.elsevier.com/locate/jorganchem
Reactions of trans-[RuCl2(CO)2(PEt3)2] with 1,1-dithiolates:
Stepwise formation of cis-[Ru(CO)(PEt3)(S2X)] (X = CNMe2,
CNEt2, COEt, P(OEt)2, PPh2)
*
Anthony J. Deeming, Caroline Forth, Graeme Hogarth
Department of Chemistry, University College London, 20 Gordon Street, London WC1H 0AJ, UK
Received 22 July 2005; received in revised form 23 August 2005; accepted 23 August 2005
Available online 11 October 2005
Abstract
Trans-[RuCl2(CO)2(PEt3)2] reacts with two equivalents of a series of 1,1-dithiolate ligands to form the bis(dithiolate) complexes,
cis-[Ru(CO)(PEt3)(S2X)2] (X = CNMe2, CNEt2, COEt, P(OEt)2, PPh2). Two intermediates have been isolated; trans-[Ru(PEt3)2Cl-
(CO){S2P(OEt)2}] and trans-[Ru(PEt3)2(CO)(g1-S2COEt)(g2-S2COEt)], allowing a simple reaction scheme to be postulated involving
three steps; (i) initial replacement of cis carbonyl and chloride ligands, (ii) substitution of the second chloride, (iii) loss of a phosphine.
Thermolysis of cis-[Ru(CO)(PEt3)(S2CNMe2)2] with Ru3(CO)12 in xylene affords trinuclear [Ru3(l3-S)2(PEt3)(CO)8] as a result of dithio-
carbamate degradation. Crystal structures of cis-[Ru(CO)(PEt3)(S2X)2] (X = NMe2, COEt), trans-[Ru(PEt3)2Cl(CO){S2P(OEt)2}], trans-
[Ru(PEt3)2(CO)(g1-S2COEt)(g2-S2COEt)] and [Ru3(l3-S)2(PEt3)(CO)8] are reported.
ꢀ 2005 Elsevier B.V. All rights reserved.
Keywords: Dithiolate; Ruthenium; Dithiocarbamate; Phosphine; Carbonyl
1. Introduction
Thus, with cis-[Ru(CO)2(S2CNEt2)2], pentanuclear [Ru5-
(l4-S)2(l-CNEt2)2(CO)11] is the major product [3], while
with cis-[Ru(CO)2(S2CNMe2)2], octanuclear [Ru8(l4-S)3-
(l3-S)(l-CNMe2)2(CO)16] has been isolated and crystallo-
graphically characterized [4]. The mode of formation of
these clusters is unknown, but the likely initial process is
one of carbonyl loss from the bis(dithiocarbamate) com-
plexes to afford dimeric [Ru(CO)(S2CNR2)(l-S2CNR2)]2
(R = Me, Et), a process known to occur cleanly in the pres-
ence of trimethylamine N-oxide [5].
In order to explore further the potential of this method for
the formation of novel aminoalkylidyne clusters and to gain
more insight in to the processes involved, we sought to
prepare a range of phosphine-substituted derivatives, cis-
[Ru(CO)(PR3)(S2CNR2)2]. A number of potential routes
can be envisaged to such complexes. Unfortunately, car-
bonyl substitution in cis-[Ru(CO)2(S2CNR2)2] is a very
slow process and thus does not provide a viable method.
Critchlow and Robinson [6] have reported the preparation
of cis-[Ru(CO)(PPh3)(S2CNMe2)2] from the addition of
two equivalents of NaS2CNMe2 to [Ru(NO3)2(CO)(PPh3)2],
Dithiocarbamates are a versatile class of ligand with the
ability to stabilize transition metals in a wide range of
oxidation states [1] and while in the vast majority of cases
the ligands act in a simple spectator fashion, it is becoming
increasingly apparent that this is not always the case.
As early as 1973, Ricard and co-workers [2] reported that
the molybdenum(IV) dimer, [Mo(l-S)(S2CNPr2)(g2-
SCNPr2)]2, resulting from the cleavage of a carbon–sulfur
bond, generating sulfido and thiocarboxamide ligands,
was the product of the reaction of [Mo2(l-OAc)4] with four
equivalents of NaS2CNPr2. More recently, work in our
group has shown that heating the ruthenium(II) complexes
cis-[Ru(CO)2(S2CNR2)2] (R = Me, Et) with Ru3(CO)12 at
elevated temperatures leads to the formation of novel sul-
fido-capped aminoalkylidyne clusters resulting from a dou-
ble sulfur–carbon bond cleavage of the dithiocarbamates.
*
Corresponding author. Fax: +44 171 380 7463.
E-mail address: g.hogarth@ucl.ac.uk (G. Hogarth).
0022-328X/$ - see front matter ꢀ 2005 Elsevier B.V. All rights reserved.
doi:10.1016/j.jorganchem.2005.08.051

80
A.J. Deeming et al. / Journal of Organometallic Chemistry 691 (2006) 79–85
although it is noteworthy that a similar reaction of cis-
[RuCl2(CO)2 (PPh3)2] affords only the dicarbonyl, cis-[Ru-
(CO)2 (S2CNMe2)2] [7]. Formation of the latter results from
loss of two equivalents of phosphine and retention of both
carbonyls, which might be due to the steric bulk of the phos-
phine and their initial cis disposition. Trans-[RuCl2(CO)2-
(PEt3)2] is relatively easily prepared and has been widely
utilized as a starting material for a wide range of organome-
tallic chemistry [8]. This seemed an attractive starting mate-
rial for the synthesis of cis-[Ru(CO)(PEt3)(S2CNR2)2] since
the more basic and less sterically demanding triethylphos-
phine should be less readily lost, while the trans arrangement
of ligands and the preferred cis arrangement of dithiocarba-
mates at ruthenium(II) should facilitate the loss of one car-
bonyl and one phosphine. We herein report that this
is indeed the case, addition of two equivalents of dithiocar-
bamate salts to trans-[RuCl2(CO)2(PEt3)2] affording cis-
[Ru(CO)(PEt3)(S2CNR2)2] (R = Me, Et), together with
reactions with other 1,1-dithiolate anions, the latter leading
to elucidation of the reaction mechanism.
Fig. 1. Molecular structure of cis-[Ru(CO)(PEt3)(S2CNMe2)2] (1a) with
selected bond lengths (A) and angles (ꢁ). Ru(1)–P(1) 2.2980(9), Ru(1)–S(1)
2.4885(9), Ru(1)–S(2) 2.3937(9), Ru(1)–S(3) 2.3914(9), Ru(1)–S(4)
2.4767(9), Ru(1)–C(1) 1.835(4), C(1)–Ru(1)–P(1) 89.70(11), S(3)–Ru(1)–
S(2) 164.32(3), C(1)–Ru(1)–S(1) 169.38(12), P(1)–Ru(1)–S(4) 167.88(3),
S(2)–Ru(1)–S(1) 71.72(3), S(3)–Ru(1)–S(4) 72.02(3), S(1)–C(2)–S(2)
113.2(2), S(4)–C(5)–S(3) 113.2(2).
˚
2. Results and discussion
Heating trans-[RuCl2(CO)2(PEt3)2] and NaS2CNR2
(R = Me, Et) in ethanol for 4–7 h resulted in the clean
formation of bis(dithiocarbamate) complexes cis-[Ru(CO)-
(PEt3)(S2CNR2)2] (1a–b) as yellow crystalline solids. Char-
acterization was straightforward, each showing a single
strong carbonyl absorption in the IR spectrum and a sin-
glet in the 31P NMR spectrum, while in the 1H NMR spec-
trum of 1a, the appearance of four methyl signals
confirmed the cis disposition of carbonyl and phosphine li-
gands. In order to confirm these assignments a structural
study was carried out on 1a the results of which are sum-
marized in Fig. 1. The carbonyl and phosphine lie at right
angles [C(1)–Ru(1)–P(1) 89.70(11)ꢁ] at the octahedral
ruthenium(II) centre, the coordination sphere of which is
completed by a cis disposition of the two small bite angle
[S(2)–Ru(1)–S(1) 71.72(3), S(3)–Ru(1)–S(4) 72.02(3)ꢁ] dith-
iocarbamates. These are bound in a slightly asymmetric
manner [Ru(1)–S(1) 2.4885(9), Ru(1)–S(2) 2.3937(9),
better r-donor ability of the phosphine versus a carbonyl,
which results in an increase in electron-density at the metal
centre, thus disfavoring the thioureide resonance structure
which has carbon–nitrogen double bond character. On this
basis, it is also tempting to suggest that the lower of the two
values measured in 1a is associated with the dithiocarba-
mate lying trans to the phosphine, although we have been
1
unable substantiate this with a full assignment of the H
NMR spectrum.
Heating trans-[RuCl2(CO)2(PEt3)2] and KS2COEt in
ethanol for 6 h lead to the isolation after chromatography
of two products; a small amount (5%) of the expected
product, cis-[Ru(CO)(PEt3)(S2COEt)2] (3) together with
trans-[Ru(PEt3)2(CO)(g1-S2COEt)(g2-S2COEt)] (2) (20%).
From spectroscopic data it was clear that the latter con-
tained a carbonyl and two equivalents of phosphine and
xanthate; the phosphines occupying equivalent sites while
the xanthate ligands were inequivalent, suggesting mono-
and bidentate coordination. In order to confirm these
assignments a structural study was carried out on 2 the re-
sults of which are summarized in Fig. 2. The main struc-
tural feature is indeed the different coordination modes of
the xanthates, one binding in an approximately symmetri-
cal bidentate fashion [Ru(1)–S(1) 2.4164(8), Ru(1)–
˚
Ru(1)–S(3) 2.3914(9), Ru(1)–S(4) 2.4767(9) A], the longer
distances being those trans to the carbonyl and phosphine;
a similar trans-influence being exhibited by the two.
As detailed above, at room temperature all four methyl
groups in 1a are inequivalent, which is consistent with the
observed solid state structure, and is a consequence of the
restricted rotation about the central carbon–nitrogen bond.
In toluene these four signals are observed as two pairs at d
2.61 and 2.54 and d 2.53 and 2.49. Upon warming all sig-
nals broaden, the low field pair coalescing at 333 K, and
the high field pair at 338 K. From this data, free energies
of activation can be estimated as 71 1 and 74
1 kJ molÀ1, respectively. These values are slightly lower
than those of 78 1 and 77 1 kJ molÀ1 observed for
cis-[Ru(CO)2(S2CNMe2)2] and cis-[Fe(CO)2(S2CNMe2)2],
respectively [9]. The increased barrier may result from the
˚
S(2) 2.4782(8) A], while the second is monodentate
˚
[Ru(1)–S(3) 2.3915(8) A]. The different binding modes of
the two leads, as expected, to marked differences in the
carbon–sulfur bonds, being approximately equivalent in
˚
the bidentate [S(1)–C(2) 1.696(4), S(2)–C(2) 1.698(4) A]
but quite different in the monodentate [S(3)–C(3)

A.J. Deeming et al. / Journal of Organometallic Chemistry 691 (2006) 79–85
81
Fig. 2. Molecular structure of trans-[Ru(CO)(PEt3)2(g1-S2COEt)(g2-
˚
S2COEt)] (2) with selected bond lengths (A) and angles (ꢁ). Ru(1)–P(1)
2.3758(9), Ru(1)–P(2) 2.3679(10), Ru(1)–S(1) 2.4164(8), Ru(1)–S(2)
2.4782(8), Ru(1)–S(3) 2.3915(8), Ru(1)–C(1) 1.858(3), S(1)–C(2) 1.696(4),
S(2)–C(2) 1.698(4), S(3)–C(3) 1.700(4), S(4)–C(3) 1.666(4), P(2)–Ru(1)–
P(1) 176.99(3), S(3)–Ru(1)–S(1) 161.03(3), C(1)–Ru(1)–S(2) 170.71(10),
S(1)–Ru(1)–S(2) 71.51(3), S(1)–C(2)–S(2) 114.9(2), S(4)–C(3)–S(3)
120.6(2).
Fig. 3. Molecular structure of trans-[RuCl(CO)(PEt3)2{S2P(OEt)2}] (4)
˚
with selected bond lengths (A) and angles (ꢁ). Ru(1)–P(1) 2.3825(8),
Ru(1)–P(2) 2.3844(8), Ru(1)–S(1) 2.4879(8), Ru(1)–S(2) 2.4898(9), Ru(1)–
Cl(1) 2.3853(19), Ru(1)–C(2) 1.821(8), P(1)–Ru(1)–P(2) 175.07(2), C(2)–
Ru(1)–Cl(1) 93.35(18), S(1)–Ru(1)–S(2) 79.57(3), Cl(1)–Ru(1)–S(1)
172.48(4), C(2)–Ru(1)–S(2) 173.59(18), S(1)–P(3)–S(2) 106.38(4).
˚
1.700(4), S(4)–C(3) 1.666(4) A] ligand, while bond angles at
the central carbon also differ significantly [S(1)–C(2)–S(2)
114.9(2)ꢁ, S(4)–C(3)–S(3) 120.6(2)ꢁ].
Heating trans-[RuCl2(CO)2(PEt3)2] and either NH4S2P-
(OEt)2 or NaS2PPh2 in ethanol for 3 h also lead to the iso-
lation of two products. In both cases, the minor component
was the expected products cis-[Ru(CO)(PEt3){S2P(OEt)2}2]
(5) and cis-[Ru(CO)(PEt3)(S2PPh2)2] (7), while the major
components were the monosubstituted complexes trans-
[RuCl(CO)(PEt3)2{S2P(OEt)2}] (4) and trans-[RuCl(CO)-
(PEt3)2(S2PPh2)] (6). The latter were characterized by
spectroscopic and analytical data. The presence of two
equivalent phosphines and one new dithiolate ligand was
easily shown by 31P NMR spectroscopy; two singlets in a
2:1 ratio being observed in each case. In order to confirm
these assignments a structural study was carried out on 4
the results of which are summarized in Fig. 3. There are
two approximately equivalent independent molecules in
the unit cell and in both the carbonyl and chloride are
disordered over two sites. The dithiolate is bound approx-
imately symmetrically to the ruthenium(II) centre [Ru(1)–
Fig. 4. Molecular structure of cis-[Ru(CO)(PEt3){S2P(OEt)2}2] (5) with
selected bond lengths (A) and angles (ꢁ). Ru(1)–P(1) 2.3050(6), Ru(1)–S(1)
2.4264(6), Ru(1)–S(2) 2.5430(7), Ru(1)–S(3) 2.5111(7), Ru(1)–S(4)
2.4305(7), Ru(1)–C(1) 1.828(3), P(1)–Ru(1)–S(3) 175.42(2), S(1)–Ru(1)–
S(4) 167.32(2), C(1)–Ru(1)–S(2) 174.39(8), S(1)–Ru(1)–S(2) 80.55(2), S(4)–
Ru(1)–S(3) 80.34(2), S(1)–P(2)–S(2) 107.94(4), S(3)–P(3)–S(4) 106.39(4).
˚
˚
S(1) 2.4879(8), Ru(1)–S(2) 2.4898(9) A], which also
supports a trans arrangement of the two phosphines
[P(1)–Ru(1)–P(2) 175.07(2)ꢁ] and cis arrangement of car-
bonyl and chlorides [C(2)–Ru(1)–Cl(1) 93.35(18)ꢁ].
Structural characterization of 5 was also carried out in
order to compare the data with that from 1a and 4. The re-
sults of this are summarized in Fig. 4. The bite angle of the
dithiolate ligand in 4 [S(1)–Ru(1)–S(2) 79.57(3)ꢁ] is very
similar to those in 5 [S(1)–Ru(1)–S(2) 80.55(2)ꢁ, S(4)–
Ru(1)–S(3) 80.34(2)ꢁ], however, the ruthenium–sulfur dis-
tances differ appreciably. Thus in 4 the ligand is bound
approximately symmetrically, [Ru(1)–S(1) 2.4879(8),
˚
Ru(1)–S(2) 2.4898(9) A], while in 5 there is a pronounced
asymmetry [Ru(1)–S(1) 2.4264(6), Ru(1)–S(2) 2.5430(7),
˚
Ru(1)–S(3) 2.5111(7), Ru(1)–S(4) 2.4305(7) A]. As dis-
cussed above, the latter is similar to the situation found

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A.J. Deeming et al. / Journal of Organometallic Chemistry 691 (2006) 79–85
in structurally analogous 1a and relates to trans-influence
of the carbonyl and phosphine ligands.
unable to characterize all except one, namely triruthenium
[Ru3(l3-S)2(PEt3)(CO)8] (8) isolated as a yellow crystalline
solid in 10% yield (Scheme 2). In order to confirm this for-
mulation a crystallographic study was carried out, the
results of which are summarized in Fig. 5. The triruthe-
nium centre is characterized by two short [Ru(1)–Ru(2)
The isolation of trans-[Ru(PEt3)2(CO)(g1-S2COEt)-
(g2-S2COEt)] (2), trans-[RuCl(CO)(PEt3)2{S2P(OEt)2}] (4)
and trans-[RuCl(CO)(PEt3)2(S2PPh2)] (6) allows a full pic-
ture of the course of these reactions to be elucidated as
outlined in Scheme 1. Initial addition of the dithiolate
results in substitution of a chloride followed by carbonyl
loss to give trans-[RuCl(CO)(PEt3)2(dithiolate)]. Addition
of the second dithiolate results in substitution of the second
chloride to yield trans-[Ru(PEt3)2(CO)(g1-dithiolate)(g2-
dithiolate)], which can then eliminate either a phosphine
or the remaining carbonyl. The former occurs exclusively,
presumably since elimination of the carbonyl would lead
to the less favored trans-arrangement of dithiolate ligands.
As detailed in the introduction, one of our reasons for
preparing dithiocarbamate complexes 1a–b was in order
to attempt to use them as sources of aminoalkylidyne clus-
ters. Heating a xylene solution of 1a and Ru3(CO)12 for
2 h resulted in the consumption of the former and genera-
tion of a number of products. Unfortunately, we have been
˚
2.8157(3), Ru(1)–Ru(3) 2.7230(3) A] metal–metal interac-
tions being capped above and below by sulfido groups.
The phosphine lies in the plane of the three metal atoms,
occupying a position trans to a ruthenium–ruthenium vec-
tor, which results in a significant elongation of this bond.
This structural motif is very common for group 8 transition
metals and all show the same gross structural features [10].
Formation of 8 clearly results from cleavage of one or
both dithiocarbamate ligands, although disappointingly
the central aminoalkylidyne fragment has been lost. The
isolation of 8 does, however, shed some light onto the
relationship between penta- and octaruthenium clusters
[Ru5(l4-S)2(l-CNEt2)2CO11] [3] and [Ru8(l4-S)3(l3-S)-
(l-CNMe2)2(CO)16] [4] isolated upon thermolysis of cis-
[Ru(CO)2(S2CNR2)2] (R = Me, Et) with Ru3(CO)12. The
EtO
EtO
R2N
S
S
S
Ru
S
S
Et3P
S
S
PEt3
CO
CO
PEt3
S
S
CO
PEt3
Ru
Ru
S
S
S
EtO
R2N
OEt
3
1a R = Me
1b R = Et
2
Ph
Ph
OEt
P
OEt
P
Ph
S
Ru
S
P
EtO
EtO
EtO
Ph
S
Ru
S
S
Ru
Cl
6
P
S
Ru
Cl
S
S
CO
PEt3
S
S
CO
PEt3
S
Et3P
PEt3
CO
S
Et3P
PEt3
CO
P
Ph
P
Ph
OEt
7
4
5
S
X
Cl
Ru
Cl
2 [S2X]-
S
S
CO
PEt3
Et3P
OC
CO
PEt3
Ru
- 2 Cl-, - CO, - PEt3
X
S
- Cl-
[S2X]-
- PEt3
- CO
S
X
S
X
[S2X]-
- Cl-
S
Et3P
PEt3
CO
S
Et3P
PEt3
CO
Ru
Cl
Ru
S
S
X
Scheme 1.

A.J. Deeming et al. / Journal of Organometallic Chemistry 691 (2006) 79–85
83
Me2N
S
S
Ru(CO)3
∆, xylene
S
S
CO
PEt3
Ru
(OC)3Ru
Ru3(CO)12
Ru(CO)2(PEt3)
S
S
Me2N
1a
8
Scheme 2.
in ethanol (50 cm3) and heated under reflux for 7 h. The
solvent was removed by rotary evaporation resulting in a
yellow solid which was redissolved in dichloromethane
(20 cm3) and filtered to give a clear yellow solution. The
solvent was removed from the filtrate to give a yellow solid.
Crystallization from a dichloromethane–heptane solution
gave yellow crystals of cis-[Ru(CO)(PEt3)(S2CNMe2)2]
1
(1a) (0.1250 g, 59%). IR m(CO) (CH2Cl2): 1927s cmÀ1; H
NMR (CDCl3): d 3.26 (s, 3H, NMe), 3.24 (s, 3H, NMe),
3.20 (s, 3H, NMe), 3.19 (s, 3H, NMe), 1.83 (m, 6H,
PCH2), 1.05 (dt, J 15.0, 7.6, 9H, Me); 31P{1H} NMR
(CDCl3): d 20.8 (s); mass spectrum (FAB): m/z 488 (M+),
460 (M+ À CO); Anal. Calc. for RuPS4ON2C13H27: C,
32.02; H, 5.58; N, 5.74. Found: C, 31.61; H, 5.37; N, 5.76%.
Fig. 5. Molecular structure of [Ru3(l3-S)2(PEt3)(CO)8] (8) with selected
bond lengths (A) and angles (ꢁ). Ru(1)–Ru(2) 2.8157(3), Ru(1)–Ru(3)
2.7230(3), Ru(2)–P(1) 2.2956(7), Ru(1)–S(1) 2.4201(7), Ru(1)–S(2) 2.4137
(7), Ru(2)–S(1) 2.3720(7), Ru(2)–S(2) 2.4006(7), Ru(3)–S(1) 2.3824(7), Ru
(3)–S(2) 2.4075(7), Ru(3)–Ru(1)–Ru(2) 83.562(9), P(1)–Ru(2)–Ru(1)
147.49(2).
˚
3.2. Synthesis of cis-[Ru(CO)(PEt3)(S2CNEt2)2] (1b)
Trans-[RuCl2(PEt3)2(CO)2] (0.0993 g, 0.214 mmol) and
NaS2CNEt2Æ3H2O (0.2142 g, 1.28 mmol) were dissolved
in ethanol (50 cm3) and heated under reflux for 4 h. The
solvent was removed by rotary evaporation resulting in a
yellow solid which was redissolved in dichloromethane
(20 cm3) and filtered to give a clear yellow solution. The
solvent was removed from the filtrate to give a yellow solid.
Purification by TLC on silica using light petroleum and
dichloromethane (10:3 by volume) gave a single yellow
band characterized as cis-[Ru(CO)(PEt3)(S2CNEt2)2] (1b)
latter is formally related to the former by addition of an
‘‘Ru3(CO)5S2’’ fragment. The source of this may well be
the well known nonacarbonyl complex [Ru3(l3-S)2(CO)9]
[11] which Adams and co-workers have previously shown
is an excellent building block for cluster synthesis. This raises
the possibility that during thermolysis of cis-[Ru(CO)2-
(S2CNR2)2], the nonacarbonyl is produced but reacts further
and thus is not isolated. In contrast, phosphine adduct 8,
might be expected to be less reactive as a triruthenium source
since the ‘‘open’’ ruthenium sites are less available and also
the better r-donor ligand will lead to stronger binding of
the remaining carbonyls, thus hindering their loss.
In conclusion, we have shown that trans-[RuCl2(CO)2-
(PEt3)2] is a useful starting material for the synthesis of
bis(thiolate) complexes cis-[Ru(CO)(PEt3)(dithiolate)2],
the stepwise nature of the substitution process allowing a
full mechanistic scheme to be elucidated. Unfortunately,
complexes cis-[Ru(CO)(PEt3)(S2CNR2)2] do not seem to
be useful precursors to aminoalkylidyne clusters. This is
possibly due to the stronger donor ability of the phosphine
rendering carbonyl loss less favorable.
(0.0558 g, 48%). IR m(CO) (CH2Cl2): 1924s cmÀ1 1H
;
NMR (CDCl3): d 3.9–3.5 (m, 8H, NCH2), 1.84 (m, 6H,
PCH2), 1.24 (t, J 7.1, 3H, Me), 1.23 (t, J 7.1, 3H, Me),
1.21 (t, J 7.1, 3H, Me), 1.19 (t, J 7.1, 3H, Me), 1.07 (dt, J
14.9, 7.5, 9H, Me); 31P{1H} NMR (CDCl3): d 20.2 (s);
mass spectrum (FAB): m/z 544 (M+), 516 (M+) À CO;
Anal. Calc. for RuPS4ON2C17H35: C, 37.44; H, 6.49; N,
5.15. Found: C, 39.20; H, 6.27; N, 5.58%.
3.3. Reaction of trans-[RuCl2(PEt3)2(CO)2] and
KS2COEt
Trans-[RuCl2(PEt3)2(CO)2] (0.1038 g, 0.224 mmol) and
KS2COEt (0.2152 g, 1.34 mmol) were dissolved in ethanol
(50 cm3) and heated under reflux for 6 h. The solvent was
removed by rotary evaporation resulting in a yellow solid
which was dissolved in dichloromethane (20 cm3) and
filtered. The solvent was removed from the filtrate to give
a yellow solid. Purification by TLC on silica using light
petroleum spirit and dichloromethane (5:1 by volume)
gave three bands. The first green band band could not be
3. Experimental
3.1. Synthesis of cis-[Ru(CO)(PEt3)(S2CNMe2)2] (1a)
Trans-[RuCl2(PEt3)2(CO)2] (0.1032 g, 0.222 mmol) and
NaS2CNMe2 Æ 3H2O (0.2020 g, 1.41 mmol) were dissolved

84
A.J. Deeming et al. / Journal of Organometallic Chemistry 691 (2006) 79–85
characterized. The second and third bands were yellow and
shown to be cis-[Ru(CO)(PEt3)(S2COEt)2] (3) (0.0055 g,
5%) and trans-[Ru(CO)(PEt3)2(g1-S2COEt)(g2-S2COEt)]
(2) (0.0272 g, 20%), respectively. (2) IR m(CO) (CH2Cl2):
lid. This was dissolved in dichloromethane (20 cm3), fil-
tered and removal of volatiles gave a dark yellow solid.
Purification by TLC on silica using light petroleum and
dichloromethane (5:2 by volume) gave two bands. The first
was orange and was characterized as trans-[RuCl(CO)
(PEt3)2(S2PPh2)] (6) (0.0577 g, 49%). The second band
was yellow and shown to be cis-[Ru(CO)(PEt3)(S2PPh2)2]
(7) (0.0162 g, 12%). Both products were crystallized upon
slow diffusion of heptane in to concentrated dichlorometh-
ane solutions to afford yellow crystals. (6) IR m(CO)
1947s cmÀ1 1H NMR (CDCl3): d 4.61 (q, J 7.1, 2H,
;
OCH2), 4.48 (q, 2H, J 7.1, OCH2), 1.81 (m, 12H, PCH2),
1.40 (t, J 7.1, 3H, Me), 1.37 (t, J 7.1, 3H, Me), 1.05 (tt, J
12.4, 7.4, 18H, Me); 31P{1H} NMR (CDCl3): d 21.9 (s);
mass spectrum (FAB): m/z 608 (M+), 580 (M+ À CO).
1
(3) IR m(CO) (CH2Cl2): 1948s cmÀ1; H NMR (CDCl3): d
4.55 (q, J 7.1, 2H, OCH2), 4.52 (q, J 7.1, 2H, OCH2),
1.80 (m, 6H, PCH2), 1.41 (t, J 7.1, 3H, Me), 1.40 (t, J
7.1, 3H, Me), 1.05 (dt, J 15.3, 7.5, 9H, Me); 31P{1H}
NMR (CDCl3): d 0.1 (s); mass spectrum (FAB): m/z 490
(M+), 462 (M+ À CO); Anal. Calc. for RuP2S4O3C19H40:
C, 37.55; H, 6.63. Found: C, 37.35; H, 6.40%.
(CH2Cl2): 1940s cmÀ1 1H NMR (CDCl3): d 7.81–7.39
;
(m, 10H, Ph), 1.88 (m, 6H, PCH2), 1.77 (m, 6H, PCH2),
1.07 (tt, J 11.6, 7.4, 18H, Me); 31P{1H} NMR (CDCl3): d
69.2 (s, 1P, S2P), À1.99 (s, 1P, PEt3); mass spectrum
(FAB): m/z 650 (M+), 614 (M+ À Cl); Anal. Calc. for
RuClP3S2OC25H40: C, 46.18; H, 6.20. Found: C, 45.78;
H, 5.99%. (7) IR nu(CO) (CH2Cl2): 1934s cmÀ1 1H
;
3.4. Reaction of trans-[RuCl2(PEt3)2(CO)2] and
NH4S2P(OEt)2
NMR (CDCl3): d 7.83–7.39 (m, 20H, Ph), 1.82 (m, 6H,
PCH2), 1.05 (dt, J 15.1, 7.5, 9H, Me); 31P{1H} NMR
(CDCl3): d 74.6 (d, 1P, J 21.4, S2P), 69.0 (s, 1P, S2P),
24.0 (d, 1P, J 21.4, PEt3); mass spectrum (FAB): m/z 746
(M+), 718 (M+ À CO); Anal. Calc. for RuP3S4OC31H35:
C, 49.92; H, 4.73. Found: C, 49.94; H, 4.59%.
Trans-[RuCl2(PEt3)2(CO)2] (0.1092 g, 0.216 mmol) and
NH4S2P(OEt)2 (0.2304 g, 1.29 mmol) were dissolved in eth-
anol (50 cm3) and heated under reflux for 3 h. The solvent
was removed by rotary evaporation resulting in a yellow
solid. This was dissolved in dichloromethane (20 cm3), fil-
tered and the solvent removed to give a yellow solid. Puri-
fication by TLC on silica using light petroleum and
dichloromethane (5:2 by volume) gave two yellow bands.
Both products were crystallized upon slow diffusion of
heptane in to concentrated dichloromethane solutions to
afford yellow crystals which were characterized as trans-
[RuCl(CO)(PEt3)2{S2P(OEt)2}] (4) (0.0468 g, 34%) and
cis-[Ru(CO)(PEt3){S2P(OEt)2}2] (5) (0.0145 g, 10%),
3.6. Thermolysis of 1a and Ru3(CO)12
1a (0.0450 g, 0.092 mmol) and Ru3(CO)12 (0.0590 g,
0.092 mmol) were dissolved in xylene (20 cm3) and heated
under reflux for 2 h. The solvent was removed under re-
duced pressure resulting in a dark orange solid. Purifica-
tion by TLC on silica using light petroleum and
dichloromethane (2:1 by volume) gave three bands. The
first and third bands were orange and could not be charac-
terized due to low yields. The second yellow band was crys-
tallized from a dichloromethane–heptane solution to give
yellow crystals of [Ru3(l3-S)2(PEt3)(CO)8] (8) (0.0065 g,
10%). IR m(CO) (C6H12): 2079m, 2045vs, 2024m, 2007m,
respectively. (4) IR m(CO) (CH2Cl2): 1937s cmÀ1 1H
;
NMR (CDCl3): d 4.05 (dq, J 16.0, 8.0, 4H, OCH2), 2.06
(m, 6H, PCH2), 1.96 (m, 6H, PCH2), 1.36 (t, J 8.0, 12H,
Me), 1.61 (tt, J 12.0, 8.0, 18H, Me); 31P{1H} NMR
(CDCl3): d 99.9 (s, 1P, S2P), 15.2 (s, 1P, PEt3); mass spec-
trum (FAB): m/z 586 (M+), 550 (M+ À Cl); Anal. Calc. for
RuClP3S2O3C17H40: C, 34.84; H, 6.88. Found: C, 32.86; H,
1
1984w, 1972w cmÀ1; H NMR (CDCl3): d 2.16 (m, 6H,
PCH2), 1.22 (dt, J 17.9, 7.5, 9H, Me); 31P{1H} NMR
(CDCl3): d 41.3 (s); mass spectrum (FAB): m/z 710 (M+),
682 (M+ À CO), 654 (M+ À 2CO), 626 (M+ À 3CO), 598
(M+ À 4CO), 570 (M+ À 5CO), 542 (M+ À 5CO), 514
(M+ À 6CO), 486 (M+ À 7CO), 458 (M+ À 8CO).
6.37%. (5) IR m (CO) (CH2Cl2): 1943s cmÀ1 1H NMR
;
(CDCl3): d 4.26–4.07 (m, 8H, OCH2), 1.89 (m, 6H,
PCH2), 1.36 (t, J 7.1, 3H, Me), 1.31 (t, J 7.1, 3H, Me),
1.30 (t, J 7.1, 3H, Me), 1.29 (t, J 7.1, 3H, Me), 1.06 (dt,
J 15.4, 7.5, 9H, Me); 31P{1H} NMR (CDCl3): d 89.9 (d,
1P, J 10.7, S2P), 84.0 (s, 1P, S2P), 23.9 (d, 1P, J 10.7,
PEt3); mass spectrum (FAB): m/z 618 (M+), 590 (M+ À
CO); Anal. Calc. for RuP3S4O5C15H35: C, 29.17; H, 5.71.
Found: C, 29.08; H, 5.73%.
3.7. X-ray data collection and solution
Single crystals were mounted on glass fibres and all
geometric and intensity data were taken from these samples
using a Bruker SMART APEX CCD diffractometer using
graphite-monochromated Mo Ka radiation (k = 0.71073
˚
3.5. Reaction of trans-[RuCl2(PEt3)2(CO)2] and
NaS2PPh2
A) at 150 2 K. Data reduction was carried out with
SAINT PLUS and absorption correction applied using
the programme SADABS. Structures were solved by direct
methods and developed using alternating alternating cycles
of least-squares refinement and difference-Fourier synthe-
sis. All non-hydrogen atoms were refined anisotropically.
Hydrogens were generally placed in calculated positions
Trans-[RuCl2(PEt3)2(CO)2] (0.0841 g, 0.174 mmol) and
NaS2PPh2 (0.0680 g, 0.349 mmol) were dissolved in ethanol
(30 cm3) and heated under reflux for 3 h. The solvent was
removed by rotary evaporation resulting in an orange so-

A.J. Deeming et al. / Journal of Organometallic Chemistry 691 (2006) 79–85
85
(riding model). Structure solution used SHELXTL PLUS V6.10
program package.
Z = 4, F(000) 1272, dcalc = 1.553 g cmÀ3
,
l = 1.114
mmÀ1. 22856 reflections were collected, 6272 unique [Rint
= 0.0180] of which 5859 were observed [I > 2.0r(I)]. At
convergence, R1 = 0.0327, wR2 = 0.0798 [I > 2.0r(I)] and
R1 = 0.0350, wR2 = 0.0813 (all data), for 253 parameters.
Crystallographic data has been deposited with the
Cambridge Crystallographic Data Centre, CCDC No.
278449.
3.8. Crystallographic data for cis-[Ru(CO)(PEt3)-
(S2CNMe2)2] (1a)
Yellow block, dimensions 0.10 · 0.08 · 0.08 mm, mono-
clinic, space group C2/c, a = 33.510(3), b = 8.0715(8),
3
˚
˚
c = 14.8752(14) A, b = 93.047(2)ꢁ, V = 4017.7(7) A , Z =
8, F(000) 2000, dcalc = 1.612 g cmÀ3, l = 1.278 mmÀ1
.
3.12. Crystallographic data for [Ru3(l3-S)2(PEt3)(CO)8]
(8)
16870 reflections were collected, 4775 unique [Rint = 0.0370]
of which 4223 were observed [I > 2.0r(I)]. At convergence,
R1 = 0.0435, wR2 = 0.1000 [I > 2.0r(I)] and R1 = 0.0508,
wR2 = 0.1035 (all data), for 199 parameters. Crystallo-
graphic data hasbeendeposited withthe Cambridge Crystal-
lographic Data Centre, CCDC No. 278446.
Yellow block, dimensions 0.08 · 0.06 · 0.05 mm, mono-
˚
clinic, space group P21/n, a = 9.4328(5) A, b = 20.4730
˚
˚
(12) A, c = 11.4807(7) A, b = 98.8390(10)ꢁ, V = 2190.8(2)
A , Z = 4, F(000) 1368, dcalc = 2.151 g cmÀ3, l = 2.341
3
˚
mmÀ1. 19245 reflections were collected, 5259 unique
[Rint = 0.0286] of which 4655 were observed [I > 2.0r(I)].
At convergence, R1 = 0.0266, wR2 = 0.0538 [I > 2.0r(I)]
and R1 = 0.0328, wR2 = 0.0557 (all data), for 253 parame-
ters. Crystallographic data has been deposited with the
Cambridge Crystallographic Data Centre, CCDC No.
278450.
3.9. Crystallographic data for trans-[Ru(CO)(PEt3)2-
(g1-S2COEt)(g2-S2COEt)] (2)
Yellow block, dimensions 0.24 · 0.24 · 0.20 mm, mono-
clinic, space group P21/n, a = 9.8365(5), b = 18.4937(9),
3
˚
˚
c = 15.4517(7) A, b = 97.4950(10)ꢁ, V = 2786.9(2) A , Z =
4, F(000) 1264, dcalc = 1.449 g cmÀ3, l = 0.995 mmÀ1. 7518
reflections were collected, 2689 unique [Rint = 0.0356] of
which 2399 were observed [I > 2.0r(I)]. At convergence,
R1 = 0.0380, wR2 = 0.0924 [I > 2.0r(I)] and R1 = 0.0411,
wR2 = 0.0941 (all data), for 262 parameters. Crystallo-
graphic data hasbeendeposited withthe Cambridge Crystal-
lographic Data Centre, CCDC No. 278447.
Acknowledgement
We thank University College London for a Teaching
Assistantship to CF.
References
[1] G. Hogarth, Prog. Inorg. Chem. 53 (2005) 71.
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3.10. Crystallographic data for trans-[RuCl(CO)(PEt3)2-
{S2P(OEt)2}] (4)
[3] A.J. Deeming, R. Vaish, J. Organomet. Chem. 460 (1993) C8.
[4] A.J. Deeming, C.S. Forth and G. Hogarth, Can. J. Chem.
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[8] (a) J. Chatt, B.L. Shaw, A.E. Field, J. Chem. Soc., Sect. A (1968) 40;
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C43;
Yellow block, dimensions 0.14 · 0.14 · 0.12 mm, tri-
˚
˚
ꢀ
clinic, space group P1, a = 11.451(3) A, b = 11.717(3) A, c =
˚
20.143(6) A, a = 82.880(5)ꢁ, b = 89.830(5)ꢁ, c = 89.885(5)ꢁ,
3
˚
V = 2681.6(14) A , Z = 2, F(000) 1216, dcalc = 1.452
g cmÀ3, l = 1.034 mmÀ1. 23732 reflections were collected,
12343 unique [Rint = 0.0183] of which 11302 were ob-
served [I > 2.0r(I)]. At convergence, R1 = 0.0344, wR2 =
0.0778 [I > 2.0r(I)] and R1 = 0.0389, wR2 = 0.0799 (all
data), for 491 parameters. Crystallographic data has been
deposited with the Cambridge Crystallographic Data Cen-
tre, CCDC No. 278448.
(e) A.J. Deeming, G. Hogarth, M.-Y. Lee, M. Saha, S.P. Redmond,
H. Phetmung, A.G. Orpen, Inorg. Chim. Acta 309 (2000) 109.
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[10] G. Hogarth, N.J. Taylor, A.J. Carty, A. Meyer, J. Chem. Soc.,
Chem. Commun. (1988) 834.
3.11. Crystallographic data for cis-[Ru(CO)(PEt3)-
{S2P(OEt)2}2] (5)
[11] (a) R.D. Adams, J.E. Babin, M. Tasi, Inorg. Chem. 25 (1986) 4514;
(b) R.D. Adams, J.E. Babin, M. Tasi, Inorg. Chem. 26 (1987) 2807;
(c) R.D. Adams, J.E. Babin, J. Tanner, Organometallics 7 (1988)
2027.
Yellow block, dimensions 0.13 · 0.12 · 0.10 mm, mono-
˚
clinic, space group P21/c, a = 9.4611(8) A, b = 15.0380(12)
3
˚
˚
˚
A, c = 18.7286(15) A, b = 97.5590(10)ꢁ, V = 2641.5(4) A ,