Efficient transfer of dithiolene ligands from nickel to cyclopentadienyl ruthenium complexes

Article abstract of DOI:10.1016/j.jorganchem.2019.120888

The reaction of [CpRu(PPh₃)₂Cl] with [Ni(S₂C₂Ph₂)₂] in refluxing toluene produces the purple salt [CpRu(S₂C₂Ph₂)(PPh₃)][Cl], containing a rare ex

Full text of DOI:10.1016/j.jorganchem.2019.120888

Journal of Organometallic Chemistry 899 (2019) 120888
Contents lists available at ScienceDirect
Journal of Organometallic Chemistry
journal homepage: www.elsevier.com/locate/jorganchem
Efficient transfer of dithiolene ligands from nickel to cyclopentadienyl
ruthenium complexes
*
Harry Adams, Deena M. Alasali, Michael J. Morris , Sarah A. Morris, Craig C. Robertson,
Voirrey L. Robinson
Department of Chemistry, University of Sheffield, Sheffield, S3 7HF, UK
a r t i c l e i n f o
a b s t r a c t
Article history:
Received 4 July 2019
Received in revised form
The reaction of [CpRu(PPh ) Cl] with [Ni(S C Ph ) ] in refluxing toluene produces the purple salt
3
2
2
2
2 2
[
CpRu(S
Chemical or electrochemical reduction of [CpRu(S
formation of the corresponding neutral species [CpRu(S
CpRu(CO) Cl] with [Ni(S Ph ] under similar conditions was unsuccessful, but dithiolene transfer
could be induced at room temperature by the use of Me NO as a decarbonylating agent. In this case the
neutral paramagnetic complex [CpRu(S Ph )(CO)] was formed, together with a crystallographically
characterised dinuclear compound [Ru -S Ph )( -CO)(CO)Cp ]. The different outcomes of these re-
actions are related to the -donor and -acceptor properties of the ligands.
© 2019 Elsevier B.V. All rights reserved.
2
C
2
Ph
2
)(PPh
3
)][Cl], containing a rare example of a cationic dithiolene complex, in excellent yield.
Ph )- (PPh )][Cl] causes a colour change to blue and
Ph )(PPh )]. In contrast the reaction of
C
2 2
2
3
2
August 2019
C
2 2
2
3
Accepted 6 August 2019
Available online 6 August 2019
[
2
2
C
2
2 2
)
3
C
2 2
2
Keywords:
Nickel
Ruthenium
Dithiolene
Cyclopentadienyl
2
(
m
2
C
2
2
m
2
s
p
1
. Introduction
whereas in refluxing toluene the bis(dithiolene) complex
Ru(S Ph (PPh )] was formed instead [5]. By a combination of
crystallographic studies and C NMR spectroscopy, it was shown
that the dithiolene ligands in the latter were essentially bonded in
the monoanionic form, whereas in the former there was a greater
contribution of the dithioketone canonical form. More recently we
[
2
C
2
2
)
2
3
13
The chemistry of dithiolene complexes continues to attract in-
terest due to the redox-active nature of the ligand, which leads to
ambiguity in defining the oxidation state of the metal (non-inno-
cent behaviour) and access to multiple redox states [1]. Although
formally a dianionic ligand (1,2-enedithiolate, S
can also adopt monoanionic and neutral (dithioketone) canonical
forms (see Fig. 1).
We have recently been exploring the transfer of the dithiolene
ligand from one metal centre to another as a method to synthesize
new dithiolene complexes. In the case of transfer to molybdenum
carbonyl complexes, these reactions occurred under relatively
harsh thermal conditions (refluxing toluene) and resulted in the
displacement of all the carbonyls and their replacement by multiple
dithiolene ligands [2e4]. However we also wished to explore
dithiolene transfer reactions that might occur under milder con-
ditions, and perhaps lead to the incorporation of only one dithio-
lene ligand. For example, we showed that the reaction of the readily
2
e
2
C
2
R
2
), the ligand
showed that use of the decarbonylating agent Me
temperature was a viable alternative to a thermal reaction in the
synthesis of the iron dithiolene complexes [Fe -S Ph )(CO)
and [Fe(S Ph )(CO) (PPh )] [6].
3
NO at room
2
(m
2
C
2
2
6
]
2
C
2
2
2
3
As an extension of these studies we have now examined the
transfer of dithiolene ligands to the ruthenium cyclopentadienyl
complex [CpRu(PPh
3 2
) Cl] 1 and its dicarbonyl analogue [CpRu(-
CO) Cl] 2. These complexes are already known to display sub-
2
stantially different reactivities, with the presence of the donor
phosphines in 1 encouraging the formation of cationic species by
displacement of the chloride. However the only related reaction of
1 previously carried out appears to be that with the maleoni-
2
e
2e
2 2 2
triledithiolate dianion (S C (CN) , mnt ) to give the anionic
e
prepared nickel bis(dithiolene) complex [Ni(S
RuCl (PPh ] at room temperature resulted in the transfer of one
3 2
dithiolene ligand to ruthenium to give [RuCl (S )(PPh ) ]
2
C
2
Ph
2
)
2
]
with
species [CpRu(mnt) (PPh
2. Results and discussion
.1. Reactions of [CpRu(PPh
3 2
Treatment of [CpRu(PPh )
3
)] [7].
[
2
3 3
)
2
2
C
2
R
2
2
3
)
2
Cl] 1
Cl] with one equivalent of
*
Corresponding author.
E-mail address: M.Morris@sheffield.ac.uk (M.J. Morris).
https://doi.org/10.1016/j.jorganchem.2019.120888
022-328X/© 2019 Elsevier B.V. All rights reserved.
0

2
H. Adams et al. / Journal of Organometallic Chemistry 899 (2019) 120888
Fig. 1. Canonical forms of the dithiolene ligand.
[
Ni(S
2
C
2
Ph
2
)
2
] in refluxing toluene produced one major product,
[CpRu(S
2
C
2
Ph ) (PPh )][Cl] 3 (85% yield) which could only be eluted
2
3
from a chromatography column as a very highly coloured
purple band with a mixture of dichloromethane and methanol,
1
indicating its polar nature (Scheme 1). Its H NMR spectrum dis-
3
1
played phenyl and Cp protons in an integral ratio of 5:1, and its
P
13
NMR spectrum contained only a peak at 49.5 ppm. In the C NMR
spectrum the peak due to the dithiolene C]C carbon atoms was
observed at 199.0 ppm, indicating a considerable contribution of
the dithioketone canonical form; the corresponding peak in
Fig. 2. Molecular structure of the cation of complex 3 in the crystal. Selected bond
ꢂ
lengths (Å) and angles ( ): Ru(1)eP(1) 2.3337(8); Ru(1)eS(1) 2.2282(8); Ru(1)eS(2)
[
RuCl
2
(S
2
C
2
Ph
2
)(PPh
3
)
2
] occurred at 207.9 ppm. Hence although 3 is
2.2483(8); S(1)eC(1) 1.694(3); S(2)eC(2) 1.702(3); C(1)eC(2) 1.402(4); S(1)eRu(1)e
S(2) 84.55(3); S(1)eRu(1)eP(1) 94.78(3); S(2)eRu(1)eP(1) 91.29(3).
formally a complex of Ru(IV), it appears that a more accurate
description could be that it contains Ru(II). The UVevisible spec-
trum features a strong absorption at 533 nm, presumably of LMCT
character, with an extinction coefficient ε ¼ 1.5 ꢀ 10 M cm
and the solvent removed on the rotary evaporator, the resulting
spectra were sharp: Figs. S2eS4 (in the Supplementary Information)
were obtained in this way. Adding MeOH to this sample (or even
4
ꢁ1
ꢁ1
.
Diffusion of diethyl ether into a methanol solution of 3 gave
large blocks suitable for X-ray study. The molecule consists of
3
running the spectrum in CD OD) did not broaden the peaks. Variable
þ
[CpRu(S
2
C
2
Ph
2
)(PPh
3
)] cations and chloride anions. The structure
1
temperature studies of the recrystallised 3 showed that the H and
of the cationic ruthenium complex is shown in Fig. 2 with impor-
tant bond lengths and angles collected in the caption; the chloride
counter-ion and the two methanol molecules in the unit cell (the
OH groups of which are both hydrogen-bonded to the chloride)
have been omitted for clarity. The cation displays a three-legged
piano stool structure in which the two SeRueP angles are just
over 90 and the bite angle of the dithiolene slightly less than 90 .
The bond lengths within the dithiolene ligand are very similar to
those in [RuCl
13
C NMR spectra are broad at 223K, but sharper at 298K and 323K,
31
whereas the behaviour of the P NMR spectrum is the opposite, in
that at 223K it is sharp, but broadens with increasing temperature,
and at 323K is so broad as to be hardly discernible. One possible
explanation might be that the hydrogen-bonded structure is
retained to some extent in solution, leading to some degree of
restricted rotation of the Cp ligand and the phosphine phenyl
groups, but is not stable enough to assemble de novo in solution if
methanol is present; however this does not appear to explain the
ꢂ
ꢂ
2
(S
2
C
2
R
2
3
)(PPh )
2
], as are the RueS bond lengths. The
ꢂ
dithiolene ligand is almost planar, with a fold angle of 6.38 be-
tween the Ru(1)eS(1)eS(2) and S(1)eC(1)eC(2)eS(2) planes. It has
31
temperature dependence of the P NMR spectra, as one would
certainly expect such an interaction to break down at high
temperature.
been previously shown that in the 16-electron [(
Ru(S
whereas in their 18-electron Lewis base adducts [(
Ru(S )(L)] the dithiolene fold angle is larger [8,9].
We observed an interesting phenomenon in the NMR spectra of
recrystallised 3.2MeOH compared to those of unrecrystallised
samples. When the crystals of 3.2MeOH were dissolved directly in
h
-arene)
2
C
2
R
2
)] complexes the dithiolene is almost perfectly planar,
Initial difficulties in growing crystals of complex 3 led us to
h
-arene)
prepare the analogous species containing the
which was crystallised successfully from dichloromethane and
light petroleum as a CH Cl solvate. Its structure is shown in Fig. 3
5 4
h-C H Me ligand, 3′,
2 2 2
C R
2
2
with important bond lengths and angles collected in the caption.
All of the bond lengths and angles are very similar to those in 3, and
31
3
CDCl and used to record the P spectrum, the peak was very broad;
ꢂ
the dithiolene ligand displays an almost identical fold angle of 6.71
13
similarly a C NMR spectrum gave peaks for the Cp ligand and for
the phenyl carbons of the phosphine that were very broad or
completely absent, though the dithiolene peaks remained sharp. In
contrast, the spectra of unrecrystallised 3 were all sharp. Moreover
between the Ru(1)eS(1)eS(2) and S(1)eS(2)eC(6)eC(7) planes. No
anomalous NMR behaviour was observed for this complex.
Given their formally dianionic nature, and because synthetic
routes commonly lead to the incorporation of multiple dithiolene
ligands, the majority of dithiolene complexes are neutral or anionic.
Cationic examples are extremely rare, with the most important
2 2
when the crystals were first dissolved in CH Cl and light petroleum
1
þ
examples being the d [Cp
2
M(dithiolene)] (M ¼ Mo, W) cations
obtained by electrocrystallisation of the corresponding neutral
species [10e13].
The electrochemistry of complex 3 was studied in MeCN solu-
tion; the resulting cyclic voltammogram (Fig. 4) shows one
þ
reversible reduction at e 1.304 V (vs. Fc/Fc ) and a reversible
oxidation at e 0.505 V, with a further irreversible oxidation at
higher potential; the three smaller waves on the reverse scan do
not appear if the scan is truncated before this irreversible oxidation,
and so clearly represent the formation of secondary products.
Chemical reduction of 3 with sodium naphthalenide or lithium
phenylacetylide caused a clear colour change from purple to blue;
Scheme 1..

H. Adams et al. / Journal of Organometallic Chemistry 899 (2019) 120888
3
strategy for achieving substitution reactions of metal carbonyls
with, for example, phosphines, at room temperature in cases where
the corresponding thermal reaction may take many hours. Because
the reagent works by nucleophilic attack on the carbonyl ligand,
successful reactions are limited to cases where the amount of back-
bonding onto the CO ligand is relatively small, as indicated by the
rule of thumb that the IR stretching frequency of the CO ligand
ꢁ
1
should usually be above 2000 cm [14]. We therefore decided to
explore the use of Me NO to labilise the carbonyl ligands, which
seemed a distinct possibility given that the IR spectrum of [CpRu(-
3
ꢁ
1
CO)
2
Cl] shows
n
(CO) peaks at 2054 and 2008 cm in CH
2 2
Cl . Sur-
prisingly there is no record of Me
3
NO-induced substitution in this
compound: previous syntheses of phosphine-substituted de-
rivatives have used refluxing xylene or toluene [15,16]. Pleasingly a
test reaction showed that treatment of [CpRu(CO)
in MeCN solution, followed byaddition of PPh , produced a 91% yield
of [CpRu(CO)(PPh )Cl] within 1 h at room temperature.
In contrast to the thermal reaction, addition of Me NO to equi-
2
molar amounts of [CpRu(CO) Cl] and [Ni(S Ph ] in CH Cl /
2 3
Cl] with Me NO
3
3
3
2
2
C
2
2
)
2
2
MeCN solution [17] caused a rapid colour change to red-brown;
after 24 h the solution was dark purple. Column chromatography
allowed the isolation of two major products: purple
Fig. 3. Molecular structure of complex 3′ in the crystal. Selected bond lengths (Å) and
angles ( ): Ru(1)eP(1) 2.3434(13); Ru(1)eS(1) 2.2427(14); Ru(1)eS(2) 2.2269(13);
ꢂ
S(1)eC(7) 1.691(5); S(2)eC(6) 1.702(5); C(6)eC(7) 1.389(6); S(1)eRu(1)eS(2) 84.72(5);
S(1)eRu(1)eP(1) 92.26(5); S(2)eRu(1)eP(1) 92.93(5).
[CpRu(S
Cp ] 5 (Scheme 2).
Complex 4 proved to be unstable, turning brown both in solu-
2 2 2 2 2 2 2
C Ph )(CO)] 4 and apple-green [Ru (CO)(m-CO)(m-S C Ph )
2
tion and (more slowly) in the solid state, even under an inert at-
mosphere. It displayed a strong peak in its IR spectrum at
ꢁ
1
1
976 cm , indicating the retention of a carbonyl ligand, and a peak
at m/z 438 in its mass spectrum, with an additional peak at m/z 410
1
13
due to loss of the CO ligand. Its H and C NMR spectra were
however largely featureless. We therefore identified it as the
neutral paramagnetic species [CpRu(S C Ph )(CO)]. Although it is
2 2 2
purple, its position on the column strongly argues against its being
cationic like 3; one might also expect a higher v(CO) frequency if
that were the case. The formation of the neutral complex in this
case is presumably due to the lower oxidation state being stabilized
by the better
p-acceptor qualities of CO, whereas the better donor
PPh can stabilize the cationic species.
3
After several attempts, crystals of 4 were obtained by cooling an
ethyl acetate and light petroleum solution; although they proved to
be of poor quality, the resultant X-ray structure determination was
sufficient to confirm the formulation of the compound and the
absence of any counter-ion (see the Supplementary Information for
an ORTEP plot of the structure). The RueS bond lengths of 2.315(9)
and 2.277(11) Å are longer than in 3, though the overall geometry of
the molecule remains similar.
Fig. 4. Cyclic voltammogram of complex 3 in MeCN solution.
The dinuclear nature of complex 5 was indicated by its mass
spectrum and also by its IR spectrum, which displayed peaks due to
exposure of the reduced solution to air regenerated the purple
colour rapidly. When the reduction was conducted electrochemi-
cally in an OTTLE cell, the UVevisible spectrum peak of 3 at 533 nm
shifted to 605 nm. We therefore propose that the reduction product
is the neutral species [CpRu(S C Ph )(PPh )]; however attempts to
2 2 2 3
crystallise this compound were unsuccessful. Neither cationic 3 (or
ꢁ1
terminal and bridging carbonylsat 1959 and 1806 cm respectively.
1
13
In addition the H and C NMR spectra showed two inequivalent Cp
ligands as well as the incorporation of one dithiolene. The molecular
structure of complex 5 determined by X-ray diffraction is shown in
Fig. 5, with selected bond lengths and angles collected in the caption.
The two ruthenium atoms, each of which bears a Cp ligand, are
its reduced counterpart) reacted with CO (1 atm), and attempts to
8
displace the phosphine ligand with refluxing MeCN, S or dimethyl
acetylenedicarboxylate also resulted in no reaction.
2.2. Reactions of [CpRu(CO)
2
Cl] 2
No reaction occurred between [CpRu(CO)
2
2 2 2 2
Cl] and [Ni(S C Ph ) ]
in toluene solution at room temperature, and on heating to reflux,
extensive decomposition occurred and no identifiable compounds
could be isolated.
The use of trimethylamine-N-oxide, Me
3
NO, is a well established
Scheme 2..

4
H. Adams et al. / Journal of Organometallic Chemistry 899 (2019) 120888
argon using Schlenk techniques. Solvents for reactions were puri-
fied with a Grubbs-type purification system manufactured by
Innovative Technology, Newburyport, MA. Chromatographic sepa-
rations were carried out on Geduran 60 silica under a positive
pressure of nitrogen; columns were initially made up in light pe-
ꢂ
troleum (40e60 C fraction); polarity was increased by addition of
1
increasing proportions of dichloromethane. The H (400 MHz) and
13
C NMR (100 MHz) spectra were obtained in CDCl
Bruker Avance AV400 machine having an automated sample-
changer. Chemical shifts are given on the scale relative to SiMe
for H and C spectra. The C{ H} NMR spectra were routinely
recorded using an attached proton test technique (JMOD or DEPT
pulse sequence). Mass spectra were recorded on a VG AutoSpec
instrument operating in electron impact mode or a Waters LCT
instrument operating in electrospray mode. Solid state IR spectra
were recorded either as KBr disks or neat with a diamond ATR
3
solution on a
d
4
1
13
13
1
ꢁ
1
device over the range 4000-400 cm , and solution spectra in
CH Cl solution over the range 2200-1550 cm , on a PerkinElmer
ꢁ
1
2 2
Spectrum Two instrument. Elemental analyses were carried out by
the Microanalytical Service of the Department of Chemistry.
2 2 2 2 3 2
The complexes [Ni(S C Ph ) ] and [CpRu(PPh ) Cl] were pre-
pared by the literature methods [20,21].
2 2 2 3
4.2. Synthesis of [CpRu(S C Ph )(PPh )][Cl] 3
A solution of [CpRu(PPh
3 2
) Cl] (282.1 mg, 0.389 mmol) and
3
Fig. 5. Molecular structure of complex 5 in the crystal. Selected bond lengths (Å):
Ru(1)eRu(2) 2.7581(3); Ru(1)eS(1) 2.2969(5); Ru(2)eS(1) 2.3505(6); Ru(1)eS(2)
[Ni(S Ph ] (215.5 mg, 0.397 mmol) in toluene (150 cm ) was
2
C
2 2
)
2
heated to reflux for 4 h, turning from green to turquoise in the
process. The solvent was then removed in vacuo to give a purple
2.3621(6); Ru(1)eC(7) 1.993(2); Ru(2)eC(7) 2.103(2); C(13)eC(14) 1.353(3).
solid. The solid was redissolved in CH
5 g) which was then loaded onto a chromatography column made
up in light petroleum. Elution with light petroleum and CH Cl
4:1) produced a green band of residual nickel complex. Several
minor bands were removed by elution with CH Cl , followed by
CH Cl and acetone (19:1). Finally elution with CH Cl and meth-
anol (9:1 at first, then 4:1) produced a minor brown band followed
by a large purple band of 3 (233.3 mg, 85%). Diffusion of diethyl
ether into a concentrated methanol solution gave large purple
2 2
Cl and adsorbed onto silica
joined by a single bond, which is slightly asymmetrically bridged by
one CO ligand. In addition a terminal carbonyl ligand is bonded to
Ru(2). The dithiolene is bonded in the familiar ‘semi-bridging’ mode
in which S(1) bridges the two metals, albeit rather asymmetrically,
whereas S(2) is bonded only to Ru(1). Many previous examples of
this coordination mode have been reported, particularly in dimo-
lybdenum complexes [2,3], and it has also been observed in a dir-
uthenium complex [9]. The formation of 5 can be easily rationalised
by the reaction of 4 with an additional CpRu(CO) fragment.
(
2
2
(
2
2
2
2
2
2
shard-like crystals suitable for X-ray investigation.
The strategy of using complexes with labile ligands in dithiolene
transfer reactions is well established, for example Holm's improved
1
Data for 3: H NMR:
d 7.53-7.45 (m, 9 H, Ph), 7.37-7.22 (m, 12 H,
31
13
Ph), 6.90 (d, 4 H, Ph), 5.79 (s, 5 H, Cp). P NMR:
199.0 (CPh), 140.9 (Cipso of dithiolene), 133.3 (d, J ¼ 10 Hz, o- or m-
Ph of PPh ),130.0 (s,
),131.8 (s, p-Ph),130.3 (d, J ¼ 56 Hz, Cipso of PPh
p-Ph), 129.0 (d, J ¼ 11 Hz, o- or m-Ph of PPh ), 128.7, 128.2 (both s, o-
and m-Ph of dithiolene), 92.5 (s, Cp). UVevisible spectrum:
d 49.5. C NMR:
synthesis of [M(CO)
2
(dithiolene)
2
] (M ¼ Mo, W) using [M(CO)
3
(N-
NO as
d
CMe) ] instead of [M(CO)
3
6
] [18,19]. However the use of Me
3
3
3
an in situ labilizing agent in a reaction of this type does not appear
to have been previously explored [6].
3
l
max
4
ꢁ1
ꢁ1
þ
3
04 nm, 533 nm (ε ¼ 1.5 ꢀ 10 M cm ). Mass spectrum (ES ) m/z
þ
3
. Conclusions
671 (M ). Found: C, 60.63; H, 5.03; Cl, 4.74; S, 7.56. Calc. for
C
37
H
30RuS
An analogous reaction starting from [(
(680.5 mg, 0.920 mmol) and [Ni(S C Ph ) ] (511.5 mg, 0.943 mmol)
2
PCl$2MeOH: C, 60.82; H, 4.94; Cl, 4.61; S, 8.32%.
We have shown that transfer of one dithiolene ligand from nickel
h
-C H Me)Ru(PPh ) Cl]
5
4
3 2
to cyclopentadienyl ruthenium centres can be readily accomplished
if the appropriate conditions are chosen: in the case of the phos-
phine complex the reaction occurs in refluxing toluene to afford a
rare example of a cationic dithiolene complex, whereas for [CpRu(-
2
2
2 2
5 4 2 2 2 3
afforded [(h-C H Me)Ru(S C Ph )(PPh )][Cl] (3'; 608.6 mg, 92%) in
the same way. Diffusion of hexane into a dichloromethane solution
afforded very thin needle-like crystals that were suitable for X-ray
diffraction study. H NMR:
C H Me), 5.21 (s, br, 2 H, C H Me), 2.13 (s, 3 H, Me). P NMR:
5 4 5 4
d
1
CO)
2
Cl], milder reaction conditions involving the use of Me
3
NO as a
d
7.71-6.92 (m, 25 H, Ph), 5.61 (s, br, 2 H,
31
decarbonylating agent are required, leading to the formation of the
neutral dithiolene carbonyl complex. Although we were unable to
13
50.7. C NMR:
d 197.8 (CPh), 141.0 (Cipso of dithiolene), 133.5 (d,
coax any ligand substitution reactivity from [CpRu(S
2
C
2
Ph
2 3
)(PPh )]
J ¼ 10 Hz, o- or m-Ph of PPh ), 131.8 (s, p-Ph),131.1 (d, J ¼ 55 Hz, C
3
ipso
[
[
Cl], it is possible that the use of a more labile precursor such as
of PPh ), 130.2 (s, p-Ph), 129.2 (d, J ¼ 11 Hz, o- or m-Ph of PPh ),
3
3
þ
CpRu(NCMe)
3
] , might alleviate this problem in future.
129.0, 128.2 (both s, o- and m-Ph of dithiolene), 113.1 (CMe), 93.5
þ
(C
5
H
4
Me), 92.7 (C
5
H
4
Me), 15.5 (Me). Mass spectrum (ES ) m/z 685
þ
4
. Experimental section
(M ). HRMS: m/z 685.0727; calc. for C38
4.3. Synthesis of [CpRu(CO) (PPh )Cl] with Me
A solution of anhydrous Me NO (29.2 mg, 0.389 mmol) in
H32RuPS
2
: m/z 685.0721.
4.1. General information
3
3
NO
All reactions were performed under an inert atmosphere of
3

H. Adams et al. / Journal of Organometallic Chemistry 899 (2019) 120888
5
Table 1
Summary of crystallographic data for complexes 3.2MeOH and 3'.
3
.2MeOH
38ClO
3′
Empirical formula
Formula weight
T/K
C
39
H
2
PRuS
2
38 2
C H32ClPRuS
770.30
100
720.24
298.15
Crystal system
Space group
a/Å
monoclinic
P2 /c
13.319(2)
9.4362(17)
27.778(5)
90
95.738(10)
90
3473.6(10)
4
1.473
0.729
1584.0
0.6 ꢀ 0.5 ꢀ 0.32
2.948 to 55.454
20077
monoclinic
P2 /n
1
1
14.2764(10)
10.2659(8)
25.1262(17)
90
99.580(4)
90
3631.1(5)
4
1.317
b/Å
c/Å
ꢂ
ꢂ
a
/
b
/
ꢂ
g
/
3
V/Å
Z
ꢁ
3
Density (calcd)/Mgm
ꢁ
1
m
/mm
F(000)
Crystal size/mm3
range for data collection/
0.688
1472.0
0.21 ꢀ 0.1 ꢀ 0.03
ꢂ
2
q
4.294 to 50
Reflections collected
30693
Independent reflections
Data/restraints/parameters
Goodness-of-fit on F2
8076 [Rint ¼ 0.0411, Rsigma ¼ 0.0555]
6301 [Rint ¼ 0.0815, Rsigma ¼ 0.0696]
8076/0/419
1.081
6301/0/388
1.016
Final R1, wR2 [I > 2
all data)
Largest diff. peak and hole/e.Å
s
(I)]
R
R
1
1
¼ 0.0405, wR
2
2
¼ 0.0753
¼ 0.0822
R
R
1
1
¼ 0.0494, wR
2
2
¼ 0.1162
¼ 0.1328
(
¼ 0.0571, wR
¼ 0.0828, wR
ꢁ
3
0.56/e0.54
1.14/e0.47
3
acetonitrile (5 cm ) was added dropwise to a solution of [CpRu(-
4.5. X-ray crystallography
3
CO)
temperature. The solution was stirred for 1 h before the addition of
PPh (131 mg, 0.5 mmol). After stirring for a further 1 h, the solvent
was removed under vacuum and the solid recrystallised from
heptane to give yellow needles of [CpRu(CO)(PPh )Cl] (174 mg,
.354 mmol, 91%). The spectroscopic properties were identical to
those reported previously [22].
2
Cl] (100 mg, 0.389 mmol) in the same solvent (20 cm ) at room
Crystal data for the three structures are summarised in Tables 1
and 2. All diffraction data were collected on a Bruker X8 Apex II CCD
diffractometer at the temperatures shown (Mo-K radiation) from
crystals mounted in fomblin oil on a MiTiGen microloop and cooled
in a stream of cold N . Using OLEX2 [23] structures were solved
3
a
3
0
2
using the SHELXS [24] or SHELXT [25] programs using Intrinsic
Phasing and refined with the XL refinement package using Least
Squares minimisation [25]. Hydrogen atoms were constrained to
4
.4. Synthesis of [CpRu(CO)(S
2 2 2 2
C Ph )] and [Ru (CO)(m-CO)(m-
3
S
2
C
2
Ph )Cp
2
2
]
idealised geometries with C(aromatic)-H 0.95 Å and C(sp )-H
0.99 Å. All H displacement parameters were constrained to be
The complexes [CpRu(CO)
Ni(S Ph ] (642.4 mg, 1.18 mmol) were dissolved in a mixture of
acetonitrile (50 cm ) and dichloromethane (10 cm ). On addition of
anhydrous Me NO (115.2 mg, 1.54 mmol) the solution changed
2
Cl] (303.3 mg, 1.18 mmol) and
1.2 ꢀ Ueq. The structure of 3′ contained voids in which resided
[
2
C
2
2 2
)
3
3
Table 2
3
Summary of crystallographic data for complex 5.
colour from green to red-brown; after stirring for 24 h at r. t. the
solution was dark purple with some suspended solid. After addition
of silica (5 g) the solvent was removed in vacuo and the product
loaded onto a chromatography column.
5
Empirical formula
Formula weight
T/K
Crystal system
Space group
a/Å
26 20 2 2 2
C H O Ru S
630.68
150(2)
Monoclinic
P2 /n
12.3854(11)
10.3480(9)
19.1101(17)
90
108.6670(10)
90
2320.4(4)
4
1.805
1.503
Elution with CH
band of residual [Ni(S
the bright purple band of [CpRu(CO)(S
2
Cl
2
:light petroleum (1:9) produced a green
Ph ], which separated incompletely from
Ph )] which was eluted in
2
C
2
2 2
)
1
2
C
2
2
b/Å
the same solvent. The purple solid resulting from evaporation of
this band was redissolved in diethyl ether and filtered to remove
c/Å
ꢂ
ꢂ
ꢂ
g/
a
/
any remaining [Ni(S
2
C
2
Ph
2
)
2
]. The complex is air-sensitive both in
b/
solution and (more slowly) in the solid state. Yield 178.8 mg,
ꢁ
1
3
0
.41 mmol, 35%. IR (CH
Elution with a 1:4 mixture of the same solvents gave further
Ni(S Ph ] (total recovery 262.4 mg, 41%), followed by a diffuse
orange zone which contains several unidentified complexes as well
as [Ni(S Ph )] . Elution with CH Cl then produced a bright
apple-green band of [Ru -CO)( -S Ph )Cp ] (108.9 mg,
.17 mmol, 29%). IR (CH Cl ): 1978, 1798 cm . H NMR: 7.25-7.13
2
Cl
2
): 1976 cm
.
V/Å
Z
ꢁ
3
Density (calcd)/Mgm
[
2
C
2
2
)
2
ꢁ1
m/mm
F(000)
1248
Crystal size/mm3
0.43 ꢀ 0.43 ꢀ 0.39
2
C
2
2
6
2
2
ꢂ
2q range for data collection/
Reflections collected
Independent reflections
Data/restraints/parameters
Goodness-of-fit on F2
3.48 to 55.06
2
2
(CO)(
m
m
2
C
2
2
2
ꢁ
11
25950
0
(
2
d
5295 [R(int) ¼ 0.0292]
1
3
m, 5 H, Ph), 7.01 (s, 5 H, Ph), 5.30, 5.20 (both s, 5 H, Cp). C NMR:
5295/0/289
d
235.0 (
m
-CO), 198.8 (CO), 164.7 (CPh), 141.6, 141.3 (Cipso), 131.9
1.033
þ
(
CPh),129.1-125.8 (m, Ph), 87.4, 86.1 (Cp). MS: m/z 631 (M ). Found:
Final R1, wR2 [I > 2
all data)
Largest diff. peak and hole/e.Å
s
(I)]
R1 ¼ 0.0227, wR2 ¼ 0.0575
R1 ¼ 0.0269, wR2 ¼ 0.0594
0.529 and e 0.621
(
20 2 2 2
C, 49.24; H, 2.96; S, 10.08. Calc. for C26H O Ru S : C, 49.51; H, 3.20;
ꢁ3
S, 10.15%.

6
H. Adams et al. / Journal of Organometallic Chemistry 899 (2019) 120888
disordered dichloromethane molecules; a satisfactory disorder
model was not found and therefore the OLEX2 solvent mask [26]
was used to mask out the disordered density, which was consistent
[9] (a) M. Nomura, M. Fujii, K. Fukuda, T. Sugiyama, Y. Yokohama, M. Kajitani,
Reactivity and electrochemical behavior of ruthenium dithiolene complexes
with coordinatively unsaturated metal centers: cycloaddition and dimeriza-
tion reactions, J. Organomet. Chem. 690 (2005) 1627e1637;
with one molecule of CH
2
Cl
2
per complex molecule.
(b) M. Herberhold, H. Yan, W. Milius, The 16-electron dithiolene complexes
6
(
h
p-cymene)M[S
2
C
2
(B10
H
10)] (M¼Ru, Os) containing both
h
-(p-cymene) and
Crystallographic data for the structure determinations have
been deposited with the Cambridge Crystallographic Data Centre,
CCDC reference numbers 1938380 (3), 1938381 (3′) and 1938382
2
-(ortho-carborane-dithiolate): adduct formation with Lewis bases, and X-
ray crystal structures of (p-cymene)- Ru[S
cymene)- Ru[S (B10 10)]} -LL) (LL
Organomet. Chem. 598 (2000) 142e149.
2
C
Ph
2
(B10
H
10)](L) (L¼PPh
3
) and {(p-
), J.
C
2 2
H
2
(
m
¼
2
PCH
2
CH PPh and N H
2
2
2 4
(5). Copies of this information may be obtained free of charge from
[
[
[
[
[
[
10] M. Fourmigu eꢀ , B. Domercq, I.V. Jourdain, P. Molini eꢀ , F. Guyon, J. Amaudrut,
The Director, CCDC, 12 Union Road, Cambridge CB2 1EZ, UK or from
their website at www.ccdc.cam.ac.uk.
Interplay of structural flexibility and crystal packing in a series of para-
magnetic cyclopentadienyl/dithiolene Mo and W complexes: evidence for
molecular spin ladders, Chem. Eur J. 4 (1998) 1714e1723.
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Acknowledgements
adaptable molecular structure of Mo(V) and W(V) dithiolene complexes: from
three-dimensional antiferromagnet to spin ladder, Inorg. Chem. 40 (2001)
371e378.
We thank the University of Sheffield for support and Samantha
Peralta Arriaga for recording the UVevisible spectrum of complex
12] E.W. Reinheimer, I. Olejniczak, A. Lapinski, R. Swietlik, O. Jeannin,
M. Fourmigu eꢀ , Structural distortions upon oxidation in heteroleptic
3
. This research did not receive any specific grant from funding
[Cp W(dmit)] tungsten dithiolene complex: combined structural, spectro-
2
agencies in the public, commercial or not-for-profit sectors.
scopic, and magnetic studies, Inorg. Chem. 49 (2010) 9777e9787.
13] T. Bsaibess, M. Guerro, Y. Le Gal, D. Sarraf, N. Bellec, M. Fourmigu eꢀ , F. Barri eꢁ re,
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2
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