Functionalised dithiocarbamate complexes: Complexes based on indoline, indole and substituted piperazine backbones - X-ray crystal structure of [Ni(S2CNC3H6C6H4) 2]

Article abstract of DOI:10.1016/j.ica.2010.05.061

A range of new nickel, copper and zinc bis(dithiocarbamate) complexes has been prepared from secondary amines with functionalised backbones. These include complexes derived from iso-indoline, tetrahydro-isoindoline, 1,2,3,4-tetrahydroisoquinoline and a number of functionalised piperazines. The crystal structure of [Ni(S₂CNC₃H₆C ₆H₄)₂] derived from 1,2,3,4- tetrahydroisoquinoline is reported.

Full text of DOI:10.1016/j.ica.2010.05.061

Inorganica Chimica Acta 363 (2010) 3222–3228
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Inorganica Chimica Acta
journal homepage: www.elsevier.com/locate/ica
Functionalised dithiocarbamate complexes: Complexes based on indoline,
indole and substituted piperazine backbones – X-ray crystal structure
of [Ni(S2CNC3H6C6H4)2]
b
Charalampos Anastasiadis a, Graeme Hogarth a, , James D.E.T. Wilton-Ely
*
a Department of Chemistry, University College London, 20 Gordon Street, London WC1H OAJ, UK
b Department of Chemistry, Imperial College London, South Kensington Campus, London SW7 2AZ, UK
a r t i c l e i n f o
a b s t r a c t
Article history:
A range of new nickel, copper and zinc bis(dithiocarbamate) complexes has been prepared from second-
ary amines with functionalised backbones. These include complexes derived from iso-indoline, tetrahy-
dro-isoindoline, 1,2,3,4-tetrahydroisoquinoline and a number of functionalised piperazines. The crystal
structure of [Ni(S2CNC3H6C6H4)2] derived from 1,2,3,4-tetrahydroisoquinoline is reported.
Ó 2010 Elsevier B.V. All rights reserved.
Received 4 February 2010
Accepted 31 May 2010
Available online 4 June 2010
Keywords:
Dithiocarbamate
Piperazine
Pyridyl
Indole
Indoline
Nickel
1. Introduction
if it was possible to prepare such complexes easy and efficiently,
and then we hoped to investigate structural characteristics such
Dithiocarbamates are versatile ligands which have been shown
to bind to all the transition elements supporting a wide range of
oxidation states [1]. However, while dithiocarbamate complexes
have been known for over a century, with many thousands having
been prepared, the vast majority of these contain only simple alkyl
substituents such as methyl and ethyl. A developing interest in the
area of dithiocarbamate chemistry is the functionalization of the
backbone such that new applications and interactions can be
developed. This area is still in its early stages but already interest-
ing potential applications have been noted including the function-
alization of gold nanoparticles [2–7], the stepwise build-up of
multimetallic arrays [5–10], the synthesis of dithiocarbamate-con-
taining supramolecular systems which can be used for anion bind-
ing [11–17], the development of technetium radiopharmaceuticals
[18–22] and efficient chelators for the treatment of acute cadmium
intoxication [23–25].
as hydrogen-bonding, secondary amine coordination and
p p
ꢀ
stacking using X-ray crystallography. We herein report that while
such complexes are easy and efficiently prepared, the generation
of high quality single crystals required for X-ray crystallography
is much more of a challenge.
2. Results and discussion
Eight amines were utilised in this study (Chart 1). Tetrahydro-
iso-quinoline (A) and the substituted piperazines (E–G) were pur-
chased and used as supplied. Tetrahydro-isoindoline (B) [28] and
isoindoline (C) [29] were prepared from the respective phthali-
mides upon reduction with LiAlH4 and BH3ꢁthf respectively, while
iso-indole was also prepared from o-xylene dibromide via the sul-
phonamide [30] (Scheme 1). Better yields were obtained by this
latter route although the extra step makes it more time-consum-
ing. 1-p-Tolylpiperazine (D) [31] was easily prepared as an ammo-
nium salt upon heating bis(2-chloroethyl)amine [32] and p-
toluidene in diglyme for 24 h, and diamine (H) [33] was similarly
prepared from p-phenylenediamine (Scheme 2).
In this contribution we extend some of our recent work in the
area of functionalized dithiocarbamate complexes [26,27] and
report the synthesis of some simple homoleptic dithiocarbamate
complexes based on iso-indoline, iso-indole and functionalized
1-piperazine backbones. The aim of the work was initially to see
Dithiocarbamate salts of amines A–G were easily prepared upon
slow addition of carbon disulfide to a methanol solution of
equimolar amounts of KOH and the respective amine. No attempt
was made to isolate or characterise these salts. Rather, addition of
* Corresponding author.
E-mail address: g.hogarth@ucl.ac.uk (G. Hogarth).
0020-1693/$ - see front matter Ó 2010 Elsevier B.V. All rights reserved.
doi:10.1016/j.ica.2010.05.061

C. Anastasiadis et al. / Inorganica Chimica Acta 363 (2010) 3222–3228
3223
N
NH
NH
NH
N
N
D
N
NH
A
B
G
N
NH
N
E
HN
N
N
NH
H
NH
N
N
NH
C
F
Chart 1.
especially the case for complexes derived from isoindoline (3)
and 4-pyridylpiperazine (7). This can be an issue with dithiocarba-
mate salts derived from dimethylamine, but generally as the back-
bone are extended solubility increases markedly [1]. The poor
solubility of the majority of these complexes most likely relates
to the very intermolecular interactions we had hoped to probe. A
second issue was that many of the samples gave only very thin
plates upon recrystallisation and these proved to be unsuitable
for X-ray crystallography. We were able to obtain suitably sized
single crystals of 1a, the nickel complex derived from tetrahydro-
isoquinoline and the results of this study are summarised in Fig. 1.
The complex is similar to other structurally characterised nickel
bis(dithiocarbamate)complexes [1]. The metal atom lies on an
inversion centre and is bound by two dithiocarbamate ligands in
a square-planar array, the bite-angle of 79.02(5)° being typical.
Thirteen atoms lie approximately in a plane and then the molecule
folds about the C(2)–C(10) vector. The molecules pack in a herring-
bone-type manner (Fig. 2) and there are a series of short intermo-
O
LiAlH4
thf
NH
NH
O
48% yield
B
O
BH3.thf
NH
NH
78% yield
O
C
(i) HBr
(ii) propionic acid
93% yield
SO2
(iii) PhOH
p-TolSO2NH2
94% yield
Br
Br
N
lecular interactions. Most notable is the
p-stacking of the arene
0
components the distance between ring centroids0 being 3.659 ÅA
with the shortest carbon–carbon contact of 3.350 ÅA between C(4)
and C(6A). Other short intermolecular contacts include;0 S(1)–
Scheme 1. Synthesis of tetrahydro-iso-indoline and iso-indoline.
0
0
the metal(II) acetates (M = Ni, Cu, Zn) resulted in the clean forma-
tion of the bis(dithiocarbamate) complexes which were isolated by
filtration (Chart 2). Yields were typically between 50–90% and in
general isolation and purification were straightforward. All com-
plexes were characterised by IR spectroscopy and the majority
gave satisfactory elemental analyses. We had hoped to look
at the solid-state structures of many of these complexes in some
detail in order to probe packing and intermolecular interactions
but the recrystallisation of almost all proved problematic. For
many, solubility in common organic solvents was poor. This was
H(7A) 2.968 ÅA, C(7)–H(3A) 2.798 ÅA, C(1)–H(6A) 2.850 ÅA and
0
H(2B)–H(2B0) 2.388 ÅA. While a number of tetrahydro-isoquinoline
derived dithiocarbamate complexes have previously been reported
[34–37] this is the first to be crystallographically characterised.
The nickel and zinc complexes, when sufficiently soluble in
CDCl3 or other commonly available deuterated solvents, were
characterised by 1H NMR spectroscopy. The spectrum of 1a con-
firmed that the solid-state structure was maintained in solution.
Together with a multiplet in the aromatic region there were three
signals of equal intensity in the aliphatic region. A singlet at d 4.86
Cl
Δ
NH2
+
HN
N
NH
base
Cl
Cl
Cl
Δ
H2N
NH2
HN
2
+
HN
N
N
NH
base
Scheme 2. Synthesis of functionalised piperazines.

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S
S
S
N
N
N
M
N
S
S
S
S
S
N
N
N
M
N
N
1a-c
N
S
S
S
S
5a-c
M
N
S
S
N
N
N
N
M
N
N
2a-c
N
N
S
S
S
S
S
S
6a-c
M
N
N
S
S
S
S
3a-c
N
N
N
M
N
N
N
7a-c
S
S
S
S
N
N
M
N
a M = Ni
b M = Cu
c M = Zn
4a-c
Chart 2.
0
Fig. 1. Two views of the molecular structure of 1a with selected bond lengths (ÅA) and angles (°); Ni(1)–S(1) 2.208(1), Ni(1)–S(2) 2.198(1), C(1)–N(1) 1.315(4), S(1)–Ni(1)–S(2)
79.02(5), S(1)–C(1)–S(2) 109.5(2), S(1)–Ni(1)–S(2A) 100.98(5).
is assigned to the nitrogen-bound methylene unit, and triplets at d
3.96 and 2.95 (J 6.1 Hz) to the ethylene sub-unit; that shifted to
lower-field being nitrogen-bound. The nickel tetrahydro-isoindo-
line complex 2a was also readily characterised by 1H NMR spec-
troscopy, the vinylic protons appearing as a singlet at d 5.65
together with five equal intensity multiplets at d 3.63, 3.40, 2.43,
2.25 and 1.85; the two at lower-field being assigned to those on
carbons attached to nitrogen. The substituted piperazine com-
plexes all show equal intensity multiplets in the aliphatic region
associated with the methylene groups of the piperazine unit,

C. Anastasiadis et al. / Inorganica Chimica Acta 363 (2010) 3222–3228
3225
Fig. 2. Packing motiff for 1a showing
p-stacking between the arene rings.
PPh2
PPh2
S
Ru
S
PPh2
S
Ph2P
Ph2P
Ph2P
Ph2P
Ph2P
Ru
N
N
N
N
N
S
PPh2
N
10
8
9
2
PPh2
Ph2P
S
Ru
S
S
Ph2P
PPh2
PPh2
Ru
N
N
N
N
Ph2P
S
PPh2
Ph2P
11
Chart 3.
together with signals in the aromatic region. For example, 5a
shows multiplets at d 3.90 and 3.66 each integrating as eight
protons, together with four equal intensity multiplets (each
integrating to two protons) at d 8.19, 7.53, 6.70 and 6.66.
chose three of the monoamines to attach a cis-[Ru(dppm)2] moiety
in order to confirm that this simple strategy would be likely to
succeed.
Addition of a dichloromethane solution of cis-[RuCl2(dppm)2] to
methanol solutions of the dithiocarbamate salts of A, D and E, fol-
lowed by addition of a twofold excess of NaBF4, resulted in the
slow (ca. 20 min) deposition of cream precipitates which after
washing and drying were found to be the tetrafluoroborate salts
of 8–10 (Chart 3). These were readily characterised on the basis
of their 31P NMR spectra which in each case consisted of triplets
at ca. ꢀ4.7 and ꢀ18.2 ppm, being consistent with the formation
of the [cis-Ru(dppm)2(dtc)]+ cation [8,9]. The NMR spectra of 8
were more complicated than initially anticipated and showed tem-
perature dependence. At room temperature, the 31P NMR spectrum
consists of three sharp triplet resonances together with a poorly re-
solved multiplet at ꢀ5.03 ppm. Upon warming to 55 °C, the three
We have previously used piperazine bis(dithiocarbamate) to
link together metal centres in order to build-up multimetallic
arrays [5–10]. The addition of simple metal salts to piperazine
bis(dithiocarbamate), however, simply results in the rapid precip-
itation of solids that are presumably oligo- or polymeric. Their poor
solubility in any solvent makes them difficult to characterise. In
contrast, addition of two cis-[Ru(dppm)2] (dppm = bis(diphenyl-
phosphino)methane) moieties affords a soluble complex that we
have fully characterised in both solution and the solid-state [8].
We thus sought to extend this metal-linking strategy to bis(dithio-
carbamates) with longer organic backbones, which was the
rational behind the synthesis of diamine H. Firstly, however, we

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triplets remain unchanged but the multiplet broadens consider-
ably. The 1H NMR spectrum also shows temperature dependence,
most notably a triplet at d 3.86 (J 5.6 Hz) in the room temperature
spectrum is observed as a complex multiplet at 55 °C, while a
broad multiplet at d 4.94 resolves into two separate and better de-
fined multiplets at the higher temperature. We associate these
changes with restricted rotation about the nitrogen–carbon bond
of the dithiocarbamate and/or the flipping of the six-membered
NC5 ring. The latter would appear most likely as this would equil-
ibrate the methylene protons on each carbon atom in the ring
while having little effect on the phosphorus environments.
[I > 2r(I)]. At convergence, R1 = 0.0485, wR2 = 0.1236 [I > 2r(I)]
and R1 = 0.0614, wR2 = 0.1299 (all data), for 124 parameters.
4.3. Synthesis of amines
4.3.1. Tetrahydro-isoindoline (B)
A thf (40 ml) solution of 1,2,3,6-tertahydrophthalimide (3.93 g,
0.026 mmol) was added dropwise to a suspension of LiAlH4
(1.48 g, 0.039 mmol) in thf (15 ml) so as to maintain a gentle re-
flux. After addition the mixture was refluxed for a further 35 h.
After cooling to room temperature a mixture of thf (10 ml) and
water (3 ml) was added dropwise in order to destroy excess LiAlH4.
Addition of dietheyl ether (30 ml) resulted in formation of a precip-
itate. This was washed with water (3 ꢂ 15 ml) and then taken up in
diethyl ether (3 ꢂ 15 ml). After drying with MgSO4, removal of vol-
atiles afforded B as an orange oil (1.50 g, 48%). 1H NMR (CDCl3) d
5.63 (s, 2H), 2.98 (m, 2H), 2.14 (m, 4H), 1.86 (m, 2H).
In
a similar manner, we attempted the synthesis of the
bis(dithiocarbamate) salt of H and added two equivalents of cis-
[RuCl2(dppm)2] followed by a slight excess of NaBF4. This lead to
the slow deposition of a cream precipitates which was isolated in
the usual manner. The 31P NMR spectrum clearly showed the for-
mation of a new dithiocarbamate complex 11, and the 1H NMR
while being complex, was consistent with the proposed formula-
tion. Unfortunately we were unable to obtain an analytically pure
sample of this complex, possibly due to the inclusion of solvent.
4.3.2. Isoindoline (C)
A 1 M solution of BH3ꢁthf (100 ml) was added dropwise over ca.
30 min to
a thf (10 ml) suspension of phthalimide (5.50 g,
0.037 mmol). During the addition the solution became yellow–or-
ange. After addition the mixture was refluxed for 14 h. After cool-
ing to 0 °C, methanol (10 ml) was added dropwise and after stirring
for 20 min, 6 M HCl (10.5 ml) was slowly added. The resulting mix-
ture was refluxed for 1 h and then after cooling to 0 °C, 6 M NaOH
was slowly added until the pH was greater than 10. This solution
was then extracted with diethyl ether (3 ꢂ 20 ml) and dried with
MgSO4. Removal of volatiles afforded C as an orange oil (3.44 g,
78%). 1H NMR (CDCl3) d 7.22 (m 2H), 7.20 (m, 4H), 4.22 (s, 4H).
Alternatively; in a three-necked round-bottom flask equipped
with a reflux condensor to a vigorously stirred suspension of NaH
(60% dispersed in mineral oil, 2.34 g, 0.058 mmol) in dmf (60 ml)
was added dropwise a dmf (35 ml) solution of p-toluenesulfon-
amide (10.0 g, 0.058 mmol). After the addition the mixture was
stirred for a further 1 h and then heated at 65 °C for a further 1 h.
To this was then added a dmf (85 ml) solution of o-xylenedibro-
mide (6.17 g, 0.023 mmol) maintaining the temperature at 65 °C.
After 3 h the mixture was cooled to room temperature and iced
water was added. This was left overnight to give a light grey precip-
itate which was collected by filtration, washed with water and air
dried to afford para-tosylisoindoline (6.0 g, 94%). 1H NMR (CDCl3)
d 7.76 (d, J 8.3, 2H), 7.32 (d, J 8.3, 2H), 7.23 (m, 2H), 7.17 (m, 2H),
4.61 (s, 4H), 2.40 (s, 3H). In a three-necked round-bottom flask
equipped with a reflux condensor, p-tosyliso-indoline (1.20 g,
0.044 mmol), phenol (1.2 g), 48% HBr (9 ml) and propionic acid
(1.5 ml) were added sequentially. The mixture was refluxed for
2 h. After cooling to room temperature it was transferred to a sep-
arating funnel and washed with diethyl ether (2 ꢂ 50 ml). The
aqueous layer was then added dropwise to a NaOH solution
(7.50 g in 20 ml H2O) with vigorous stirring. The resulting solution
was extracted with diethyl ether (5 ꢂ 30 ml) and dried with MgSO4.
Removal of volatiles afforded C as a brown oil (0.48 g, 93%).
3. Conclusions
This work has shown that while bis(dithiocarbamate) com-
plexes with functionalised backbones are easily prepared their
crystallisation can be more problematic. We were able to grow sin-
gle crystals of 1a and here a
pꢀp interaction was found, together
with other short intermolecular interactions. It is likely that such
interactions are found in most if not all of the complexes of this
type but probing them in the absence of single crystals remains
challenging.
4. Experimental
4.1. General methods
Amine syntheses were carried out under a nitrogen atmosphere
using standard Schlenk-line techniques but all other reactions
were carried out in air using standard bench reagents. NMR spectra
were run on a Bruker AMX400 spectrometer and referenced inter-
nally to the residual solvent peak (1H) or externally to P(OMe)3
(
31P). Infrared spectra were run on a Nicolet 205 FT-IR spectrome-
ter as KBr discs. Elemental analyses were performed at UCL. Iso-
indoline (A) and N-substituted piperazines E–G were purchased
from Aldrich and used without further purification.
4.2. X-ray data collection and solution
Single crystals of 1a were mounted on glass fibres and all geo-
metric and intensity data were taken from these samples using a
Bruker SMART APEX CCD diffractometer using graphite-monochro-
mated Mo Ka radiation (k = 0.71073 Å) 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 cycles of least-squares
refinement and difference-Fourier synthesis. All non-hydrogen
atoms were refined anisotropically. Hydrogens were placed in
calculated positions (riding model). Structure solution used SHELXTL
PLUS V6.10 program package. Crystallographic data for 1a: green
4.3.3. 1-p-Tolylpiperazine (D)
In a three-necked round-bottom flask equipped with a reflux
condensor p-toluidine (3.50 g, 0.033 mmol) and bis(2-chloro-
ethyl)amine (5.89 g, 0.033 mmol) in diglyme (50 ml) were refluxed
for 16 h. This produced a very dark orange solid. After cooling,
methanol (ca. 100 ml) was added in order to dissolve all solids.
Addition of diethyl ether (ca. 200 ml) led to the precipitation of
1-p-tolylpiperazine (D) as its ammonium salt. This was filtered,
washed and dried to give the salt (5.96 g, 85%). A portion of this
(2.01 g) was dissolved in 1.5 M sodium carbonate. After stirring
for 1 h this was extracted with ethyl acetate (2 ꢂ 20 ml) and
removal of volatiles afforded D as an oily orange solid (0.95 g,
plate, dimensions 0.16 ꢂ 0.12 ꢂ 0.05 mm, triclinic, space group
ꢀ
P1,
a
= 7.019(4), b = 7.273(4), c = 10.462(6) Å, a = 78.675(9),
b = 107.425(2),
Dcalc = 1.579 g cmꢀ3
lected, 2209 unique [Rint = 0.0240] of which 1765 were observed
c
= 81.837(9)°, V = 499.7(5) Å3, Z = 1, F(000) 246,
= 1.397 mmꢀ1. 4045 reflections were col-
,
l

C. Anastasiadis et al. / Inorganica Chimica Acta 363 (2010) 3222–3228
3227
67%). 1H NMR (CDCl3) d 7.07 (d, J 7.7, 2H), 6.85 (d, J 7.7, 2H), 3.07
(m, 4H), 3.04 (m, 4H), 2.25 (s, 3H).
1b (0.80 g, 67%): IR (KBr) 1494 (C@N), 982 (C–S) cmꢀ1. Anal. Calc.
for Cu1S4N2C20H20: C, 49.58 (50.02); H, 5.22 (4.26); N, 5.67 (5.83).
2b (0.74 g, 63%): IR (KBr) 1499 (C@N), 982 (C–S) cmꢀ1. MS: m/z
460 (M+ 14%). Anal. Calc. for Cu1S4N2C18H24: C, 46.41 (46.98); H,
5.21 (5.26); N, 5.90 (6.09).
4.3.4. p-Phenylenebis(1-piperazine) (H)
In a three-necked round-bottom flask equipped with a reflux
condensor p-phenylenediamine (4.00 g, 0.036 mmol) and bis(2-
chloroethyl)amine (12.85 g, 0.072 mmol) in diglyme (100 ml) were
refluxed for 16 h. This produced a dark brown solid. After cooling,
methanol (ca. 200 ml) was added in order to dissolve all solids.
Addition of diethyl ether (ca. 200 ml) led to the precipitation p-
phenylenebis(1-piperazine) (H) as an ammonium salt. This was fil-
tered, washed and dried to give the salt (9.20 g, ca. 80%). A portion
of this (2.11 g) was dissolved in 2 M sodium hydroxide. After stir-
ring for 1 h this was extracted with ethyl acetate (2 ꢂ 30 ml) and
removal of volatiles afforded H as a dark oily solid (1.22 g, 75%).
1H NMR (CDCl3) d 6.89 (s, 4H), 3.63 (m, 8H), 3.56 (m, 4H). MS:
m/z 246 (M+ 12%).
3b (0.77 g, 75%): IR (KBr) 1484 (C@N), 987 (C–S) cmꢀ1. Anal. Calc.
for Cu1S4N2C18H16ꢁCHCl3: C, 40.68 (39.92); H, 3.04 (2.99); N, 4.96
(4.89).
4b (0.94 g, 70%): IR (KBr) 1508 (C@N), 1019 (C–S) cmꢀ1. Anal.
Calc. for Cu1S4N4C24H30ꢁCHCl3: C, 43.84 (43.79); H, 4.72 (4.56); N,
7.99 (8.17).
5b (0.82 g, 60%): IR (KBr) 1478 (C@N), 980 (C–S) cmꢀ1. Anal. Calc.
for Cu1S4N6C20H24ꢁCHCl3: C, 38.84 (38.24); H, 4.11 (3.79); N, 13.81
(12.71).
6b (0.85 g, 63%): IR (KBr) 1508 (C@N), 1016 (C–S) cmꢀ1. Anal.
Calc. for Cu1S4N8C18H22ꢁCHCl3: C, 34.31 (34.49); H, 3.66 (3.48); N,
16.41 (16.94).
7b (0.99 g, 73%): IR (KBr) 1512 (C@N), 1013 (C–S) cmꢀ1. Anal.
Calc. for Cu1S4N6C20H24ꢁCHCl3: C, 37.49 (38.23); H, 4.22 (3.79); N,
13.23 (12.75).
4.4. Synthesis of dithiocarbamate salts
1c (0.80 g, 65%): IR (KBr) 1495 (C@N), 980 (C–S) cmꢀ1 1H NMR
;
Amines (5.0 mmol) were added to MeOH (30 ml) and KOH
(0.28 g, 5.0 mmol) was added. This solution was left to stir for
5 min and CS2 (0.38 g, 5.0 mmol) was added dropwise and left to
stir for 1 h. This produced pale yellow solutions which were used
for all further experiments.
(CDCl3) d7.23–7.12 (m, 8H), 5.14 (s, 4H), 4.23 (t, J 6.0, 4H), 3.02 (t, J
6.0, 4H). Anal. Calc. for Zn1S4N2C20H20: C, 49.28 (49.83); H, 4.15
(4.18); N, 5.47 (5.81).
2c (0.72 g, 66%): IR (KBr) 1484 (C@N), 982 (C–S) cmꢀ1 1H NMR
;
(CDCl3) d 5.66 (s, 4H), 3.81 (m, 4H), 3.59 (m, 4H), 2.51 (m, 4H), 2.28
(m, 4H), 1.93 (m, 4H). Anal. Calc. for Zn1S4N2C18H24: C, 46.84
(46.79); H, 5.66 (5.24); N, 6.03 (6.06).
4.5. Synthesis of nickel, copper and zinc complexes
3c (0.90 g, 77%): IR (KBr) 1472 (C@N), 982 (C–S) cmꢀ1. Anal. Calc.
for Zn1S4N2C18H16: C, 46.80 (47.62); H, 3.69 (3.55); N, 5.63 (6.17).
4c (1.05 g, 75%): IR (KBr) 1515 (C@N), 1013 (C–S) cmꢀ1; 1H NMR
(CDCl3) d 7.09 (d, J 8.4, 4H), 6.83 (d, J 8.4, 4H), 4.24 (m, 8H), 3.25 (m,
8H), 2.28 (s, 6H). Anal. Calc. for Zn1S4N4C24H30: C, 51.93 (50.73); H,
5.54 (5.32); N, 9.63 (9.86).
Nickel acetate (0.62 g, 2.50 mmol) was added to the dithiocar-
bamate salts resulting in the immediate formation of a green pre-
cipitate. This was filtered and washed with water (3 ꢂ 15 ml),
methanol (2 ꢂ 15 ml) and diethyl ether (2 ꢂ 10 ml). The solid
was then air dried for 1 h and collected. Yields given below are
based on the amount of this crude product. Recrystallisation was
attempted for all complexes by the slow mixing of methanol into
5c (0.90 g, 65%): IR (KBr) 1474 (C@N), 980 (C–S) cmꢀ1 1H NMR
;
(CDCl3) d 8.20 (m, 2H), 7.50 (m, 2H), 6.70–6.63 (m, 4H), 4.24 (m,
8H), 3.70 (m, 8H). Anal. Calc. for Zn1S4N6C20H24ꢁCH2Cl2: C, 40.84
(40.23); H, 4.56 (4.18); N, 14.00 (13.50).
a
saturated dichloromethane solution. Similar reactions and
work-up were carried out using copper(II) acetate and zinc acetate.
1a (0.83 g, 70%): IR (KBr) 1523 (C@N), 982 (C–S) cmꢀ1 1H NMR
(CDCl3) d 7.23–7.13 (m, 8H), 4.86 (s, 4H), 3.96 (t, J 6.1, 4H), 2.95
(t,
6.1, 4H); MS: m/z 475 (M+ 12%). Anal. Calc. for
;
6c (0.96 g, 70%): IR (KBr) 1500 (C@N), 1014 (C–S) cmꢀ1; 1H NMR
(CDCl3) d 8.32 (d, J 7.4, 4H), 6.57 (t, J 7.4, 2H), 4.19 (t, J 5.4, 8H), 3.97
(t, J 5.4, 8H). Anal. Calc. for Zn1S4N8C18H22: C, 40.30 (39.74); H, 4.33
(4.08); N, 21.09 (20.60).
J
Ni1S4N2C20H20ꢁ0.5CH2Cl2: C, 48.21 (47.56); H, 4.04 (4.06); N, 5.34
(5.41).
7c (0.90 g, 67%): IR (KBr) 1525 (C@N), 1006 (C–S) cmꢀ1. Anal.
Calc. for Ni1S4N6C20H24ꢁCH2Cl2: C, 40.55 (40.23); H, 4.37 (4.18);
N, 13.22 (13.40).
2a (0.74 g, 65%): IR (KBr) 1512 (C@N), 982 (C–S) cmꢀ1 1H NMR
;
(CDCl3) d 5.65 (s, 4H), 3.63 (m, 4H), 3.40 (m, 4H), 2.43 (m, 4H), 2.25
(m, 4H), 1.85 (m, 4H); MS: m/z 455 (M+ 3%). Anal. Calc. for
Ni1S4N2C18H24ꢁ0.25CH2Cl2: C, 46.23 (46.01); H, 5.25 (5.15); N,
5.86 (5.88).
4.6. Synthesis of ruthenium complexes
3a (0.90 g, 77%): IR (KBr) 1505 (C@N), 985 (C–S) cmꢀ1. Anal. Calc.
for Ni1S4N2C18H16: C, 47.65 (48.33); H, 3.59 (3.61); N, 5.96 (6.26).
4a (0.88 g, 63%): IR (KBr) 1515 (C@N), 1019 (C–S) cmꢀ1; 1H NMR
(CDCl3) d 7.09 (d, J 8.2, 4H), 6.82 (d, J 8.2, 4H), 3.93 (m, 8H), 3.18 (m,
8H), 2.26 (s, 6H); MS: m/z 561 (M+ 92%). Anal. Calc. for
Ni1S4N4C24H30ꢁ0.5CH2Cl2: C, 49.59 (48.74); H, 5.38 (5.06); N, 9.08
(9.28).
A dichloromethane (10 ml) solution of cis-[RuCl2(dppm)2]
(0.136 g, 0.14 mmol) was added to a methanol solution of the
dithiocarbamate salt (0.14 mmol). This was stirred for 1 h resulting
in a slow formation of a cloudy cream solution. Solid NaBF4
(0.032 g, 0.30 mmol) was then added. The solution was filtered
and the filtrate collected. Removal of volatiles afforded a cream so-
lid which was washed consecutively with water (3 ꢂ 5 ml), meth-
anol (3 ꢂ 5 ml) and diethyl ether (3 ꢂ 5 ml). Air drying afforded the
product as a dry cream powder.
5a (0.82 g, 60%): IR (KBr) 1484 (C@N), 980 (C–S) cmꢀ1 1H NMR
;
(CDCl3) d 8.19 (m, 2H), 7.53 (m, 2H), 6.70 (m, 2H), 6.66 (m, 2H),
3.90 (m, 8H), 3.66 (m, 8H). Anal. Calc. for Ni1S4N6C20H24: C, 43.62
(44.88); H, 4.48 (4.49); N, 15.05 (15.71).
8 (0.13 g, 75%): IR (KBr) 1485 (C@N), 1000 (C–S) cmꢀ1 31P{1H}
;
NMR (CDCl3, 20 °C) ꢀ0.87 (t, J 35.2, 1P), ꢀ5.03 (m, 1P), ꢀ18.83 (t,
J 34.9, 1P), ꢀ27.14 (t, J 35.6, 1P); 31P{1H} NMR (CDCl3, 55 °C)
ꢀ0.85 (t, J 35.2, 1P), ꢀ5.24 (br, 1P), ꢀ18.71 (t, J 34.9, 1P), ꢀ6.41
(t, J 35.3, 1P); 1H NMR (CDCl3, 20 °C) d 8.21 (q, J 5.24, 4H, Ph),
7.94 (q, J 5.32, 4H, Ph), 7.67 (br, 4H, Ph), 7.46–6.95 (m, 28H, Ph),
6.79 (t, J 7.20, 2H, Ph), 6.57 (m, 4H, Ph), 4.94 (brm, 2H, PCH2P),
4.83 (d, J 16.7, 1H), 4.66 (brm, 2H, PCH2P), 4.50 (d, J 16.7, 1H),
3.82 (t, J 5.6), 2.86 (m, 1H), 2.77 (m, 1H); 1H NMR (CDCl3, 55 °C)
6a (0.75 g, 55%): IR (KBr) 1504 (C@N), 1014 (C–S) cmꢀ1; 1H NMR
(CDCl3) d 8.34 (d, J 7.5, 4H), 6.58 (t, J 7.5, 2H), 3.93 (m, 8H), 3.85 (m,
8H). Anal. Calc. for Ni1S4N8C18H22: C, 39.99 (40.23); H, 4.19 (4.13);
N, 20.72 (20.85).
7a (0.93 g, 70%): IR (KBr) 1508 (C@N), 1008 (C–S) cmꢀ1; MS: m/z
535 (M+ 26%). Anal. Calc. for Ni1S4N6C20H24ꢁCH2Cl2: C, 41.23
(40.66); H, 4.59 (4.22); N, 13.76 (13.55).

3228
C. Anastasiadis et al. / Inorganica Chimica Acta 363 (2010) 3222–3228
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d 8.23 (q, J 5.24, 4H, Ph), 7.96 (q, J 5.32, 4H, Ph), 7.71 (br, 4H, Ph),
7.46–6.95 (m, 28 H, Ph), 6.79 (t, J 7.20, 2H, Ph), 6.57 (br, 4H, Ph),
5.06 (m, 1H, PCH2P), 4.91 (m, 1H, PCH2P), 4.82 (d, J 16.7, 1H),
4.68 (brm, 2H, PCH2P), 4.50 (d, J 16.7, 1H), 3.82 (m, J 4.9), 2.88
(m, 1H), 2.80 (m, 1H). Anal. Calc. for Ru1P4S2N1C60H54B1F4: C,
61.16 (61.86); H, 4.60 (4.60); N, 1.05 (1.20).
9 (0.15 g, 70%): IR (KBr) 1480 (C@N), 978 (C–S) cmꢀ1 1H NMR
;
(CDCl3) d 8.22 (dd, J 4.9, 1.3, 1H), 7.65–6.52 (m, 43H), 4.96 (m,
2H), 4.64 (m, 4H), 3.82–3.64 (m, 4H), 3.52–3.40 (m, 4H); 31P{1H}
NMR (CDCl3) ꢀ4.91 (t, J 34.4, 2P), ꢀ18.3 (t, J 34.4, 2P); MS: m/z
1108 (M+ 5%). Anal. Calc. for Ru1P4S2N3C60H56B1F4: C, 60.16
(60.30); H, 4.72 (4.71); N, 3.27 (3.52).
10 (0.12 g, 68%): IR (KBr) 1514 (C@N), 1020 (C–S) cmꢀ1; 1H NMR
(CDCl3) d7.62–6.52 (m, 44H), 5.12 (m, 2H), 4.51 (m, 2H), 3.83–3.74
(m, 4H), 3.12–2.96 (m, 4H), 2.30 (s, 3H); 31P{1H} NMR (CDCl3)
ꢀ4.77 (t,
J
34.8), ꢀ18.03 (t,
J
34.8). Anal. Calc. for
Ru1P4S2N2C60H59B1F4: C, 62.80 (61.64); H, 5.28 (4.93); N, 2.01
(2.32).
11 (0.15 g, 63%): 1H NMR (CDCl3) d 7.73–6.39 (m, 84H), 4.97 (m,
4H), 4.55 (m, 4H), 3.82–3.64 (m, 8H), 3.06–2.82 (m, 8H); 31P{1H}
NMR (CDCl3) ꢀ4.7 (t, J 34.3), ꢀ17.9 (t, J 34.3).
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Appendix A. Supplementary material
Crystallographic data has been deposited with the Cambridge
Crystallographic Data Centre, CCDC No. 764857. Supplementary
data associated with this article can be found, in the online version,
at doi:10.1016/j.ica.2010.05.061.
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