Cationic palladium(II), platinum(II) and ruthenium(II) complexes containing a chelating difluoro-substituted thiourea ligand

Article abstract of DOI:10.1016/j.poly.2010.03.010

The fluorine substituted thiourea 2,6-F₂C₆H₃C(O)NHC(S)NEt₂ was prepared in good yield from the reaction of 2,6-F₂C₆H₃C(O)Cl with KSCN and Et₂NH in acetone. Using this compound several heteroleptic, monocationic Pd(II), Pt(II) and Ru(II) complexes of the type cis-[M{κ²S,O-2,6-F₂C₆H₃C(O)NC(S)NEt₂}(L)]PF₆ [M = Pt, Pd; L = (Ph₃P)₂, ^tBu₂bipy, 1,10-phen] as well as [Ru(η⁶-p-cym){κ²S,O-2,6-F₂C₆H₃C(O)NC(S)NEt₂}(PPh₃)]PF₆ were prepared in high yields. The compounds were characterised by spectroscopic methods and, in one case, by single crystal X-ray diffraction.

Full text of DOI:10.1016/j.poly.2010.03.010

Polyhedron 29 (2010) 1968–1972
Contents lists available at ScienceDirect
Polyhedron
journal homepage: www.elsevier.com/locate/poly
Cationic palladium(II), platinum(II) and ruthenium(II) complexes containing
a chelating difluoro-substituted thiourea ligand
Sabine Pisiewicz a, Jörg Rust b, Christian W. Lehmann b, Fabian Mohr a,
*
a Fachbereich C - Anorganische Chemie, Bergische Universität Wuppertal, 42119 Wuppertal, Germany
b X-ray Crystallography, Max Planck Institut für Kohlenforschung, 45470 Mülheim an der Ruhr, Germany
a r t i c l e i n f o
a b s t r a c t
Article history:
The fluorine substituted thiourea 2,6-F2C6H3C(O)NHC(S)NEt2 was prepared in good yield from the reac-
tion of 2,6-F2C6H3C(O)Cl with KSCN and Et2NH in acetone. Using this compound several heteroleptic,
Received 19 December 2009
Accepted 12 March 2010
Available online 18 March 2010
monocationic Pd(II), Pt(II) and Ru(II) complexes of the type cis-[M{j2S,O-2,6-F2C6H3C(O)NC(S)NEt2}(L)]
t
PF6 [M = Pt, Pd; L = (Ph3P)2, Bu2bipy, 1,10-phen] as well as [Ru(
g
6-p-cym){
j
2S,O-2,6-F2C6H3C(O)NC(S)-
NEt2}(PPh3)]PF6 were prepared in high yields. The compounds were characterised by spectroscopic meth-
ods and, in one case, by single crystal X-ray diffraction.
Keywords:
Thiourea
Chelating ligand
Palladium
Ó 2010 Elsevier Ltd. All rights reserved.
Platinum
Ruthenium
X-ray structure
1. Introduction
2. Results and discussion
N,N-Dialkyl-N-acylthiourea derivatives of the type Ar-
C(O)NHC(S)NR2 are an important class of versatile ligands which
have been used in coordination chemistry for many years. These
compounds are easily accessible from the reaction of an acid chlo-
ride with KSCN and subsequent reaction of the in situ formed
acylthioisocyanate with an amine. Upon deprotonation these com-
pounds can act as either monoanionic ligands via sulfur or as
monoanionic O–S chelate ligands towards a metal (Chart 1).
Coordination solely via sulfur is rare and so far only known for
some gold(I) compounds [1,2]. The chelating coordination mode,
especially the formation of bis(chelate) metal complexes of the type
The new thiourea 2,6-F2C6H3C(O)NHC(S)NEt2 was prepared in
95% yield as a pale yellow, crystalline solid from 2,6-F2C6H3C(O)Cl,
KSCN and Et2NH in acetone. The compound was characterised by
1H, 13C and 19F NMR spectroscopy, which unambiguously con-
firmed the structure as detailed in the Experimental section. At-
tempts to prepare the pentafluorophenyl derivative by an
analogous reaction from C6F5C(O)Cl gave only dark, oily materials
which could not be purified. The reaction of metal chloro com-
t
plexes of the type [MCl2(L)] [M = Pt, Pd; L = (Ph3P)2, Bu2bipy, or
1,10-phen] with 2,6-F2C6H3C(O)NHC(S)NEt2 in the presence of a
base gives good yields of the monocationic complexes cis-
cis-[M{
j
2S,O-ArC(O)NC(S)NR2}2] is however commonly encoun-
[M{j
2S,O-2,6-F2C6H3C(O)NC(S)NEt2}(L)]+ [M = Pt, Pd; L = (Ph3P)2,
tered and numerous examples of such compounds have been
reported. Interest in the chemistry of these metal complexes has
arisen from their varied applications including precious metal sepa-
ration and extraction [3,4], their use as single source precursors for
nano-materials [5] as well as their biological activity [6–11]. We
have been studying the synthesis, structures and applications of me-
tal complexes containing the NHC(E)R (E = S, Se) unit with gold
[12,13], palladium [14] and ruthenium [15]. In order to extend this
work, we report here some platinum, palladium and ruthenium
complexes containing a difluoro substituted monoanionic chelating
thiourea ligand.
tBu2bipy, 1,10-phen], which were isolated as their PF6 salts
(Scheme 1). Apart from the phenanthroline complex 5 which is
insoluble in common solvents except dmso, the salts 1–4 are solu-
ble in methylene chloride, acetone and acetonitrile but insoluble in
alcohols, ether and hexane.
Similarly, the reaction of [Ru(
lents of the thiourea in the presence of Ph3P, NH4PF6 and Et3N af-
fords the chiral, monocationic arene Ru(II) complex [Ru(
6-p-
cym){
2S,O-2,6-F2C6H3C(O)NC(S)NEt2}(PPh3)]PF6 in high yield
(Scheme 2).
g
6-p-cym)Cl2]2 with two equiva-
g
j
Complexes 1–6 were fully characterised by spectroscopic meth-
ods including NMR spectroscopy, high-resolution electrospray
mass spectrometry and, in the case of complex 3, by X-ray diffrac-
tion. The 31P{1H} NMR spectra of the palladium and platinum
* Corresponding author.
E-mail address: fmohr@uni-wuppertal.de (F. Mohr).
0277-5387/$ - see front matter Ó 2010 Elsevier Ltd. All rights reserved.
doi:10.1016/j.poly.2010.03.010

S. Pisiewicz et al. / Polyhedron 29 (2010) 1968–1972
1969
2
2
Chart 1.
complexes 1 and 2 show an AB system with P–P coupling of ca.
30 Hz, due to the chemical inequivalence of the two phosphorus
atoms imposed by the chelating thiourea ligands. In addition, the
31P{1H} NMR spectrum of complex 1 shows platinum satellites
with a coupling constant of greater than 3000 Hz, typical for cis
platinum phosphine complexes. Loss of symmetry upon coordina-
tion of the chelating thiourea is also evident from the doubling of
t
all signals of the Bu2bipy and 1,10-phen protons in the 1H NMR
spectra of complexes 3–5. The deprotonation of the thiourea ligand
is apparent from the disappearance of the NH signal in the 1H NMR
spectra of complexes 1–6. The chiral Ru complex 6 shows some
interesting features in its NMR spectra. Two distinct resonances
for the NCH2 groups are observed in the 1H NMR spectrum: one
quartet (2 protons) and two AB systems (1 proton each). The
metal-centred chirality is also apparent from the doubling of the
p-cymene ring resonances. For such a chiral system, two sets of
signals would also be expected in the 19F NMR spectrum of 6.
However, only one resonance is actually observed, probably due
to coincidental overlap of the 2 signals.
High-resolution electrospray mass spectra of complexes 1–6
show intense signals corresponding to the molecular ions of the
cations. In the case of the ruthenium complex 6, an additional peak
due to loss of one Ph3P can be observed. The measured isotope pat-
terns are in excellent agreement with those calculated for the pro-
Fig. 1. Molecular structure of complex 3. Ellipsoids show 50% probability. Hydrogen
atoms and the [PF6]ꢀ anion have been omitted for clarity. Selected bond distances
[Å]: Pt(1)–N(2) 2.0038(9), Pt(1)–N(3) 2.0295(9), Pt(1)–O(1) 1.9939(8), Pt(1)–S(1)
2.2543(3), C(1)–N(1) 1.3566(14), C(1)–S(1) 1.7306(11), C(2)–N(1) 1.3051(14), C(2)–
O(1) 1.2846(13). Selected bond angles [°]: O(1)–Pt(1)–N(2) 169.01(4), N(3)–Pt(1)–
S(1) 175.02(3), O(1)–Pt(1)–S(1) 94.76(3), N(2)–Pt(1)–S(1) 95.39(3), N(2)–Pt(1)–N(3)
80.31(4).
posed formulae. Overall, the spectral data is fully consistent with
the structures shown in Schemes 1 and 2. The proposed structure
was unambiguously confirmed by a single crystal X-ray diffraction
study of complex 3; the molecular structure of which is shown in
Fig. 1.
The cation consists of a square planar coordinated platinum
atom surrounded by the chelating tBu2bipy and the chelating
thiourea bound to the Pt via oxygen and sulfur atoms, forming
Scheme 1.
Scheme 2.

1970
S. Pisiewicz et al. / Polyhedron 29 (2010) 1968–1972
five- and six-membered metallacyclic rings, respectively. There are
no interactions between the cation and the PF6 anion in the solid
state. The Pt–O and Pt–S distances 1.9939(8) and 2.2543(3) Å lie
within two standard deviations of the average values retrieved
from the CSD [Cambridge Structural Database Ver. 5.30 Nov.
2008 + 4 updates] for N-acylthiourea ligands. There are 17 entries
for platinum complexes with at least one N,N-dialkyl-N0-acylthiou-
rea totalling 31 observations for distances and angles. These aver-
age values are: Pt–O 2.030(19) Å, Pt–S 2.26(2) Å, S–Pt–O 94.4(9)°,
C@S 1.732(13) Å, and C@O 1.269(10) Å. This elongation of the
C@O and C@S double bonds upon coordination to the metal atom
was observed previously by Koch [16].
(400 mL) and the solid that precipitated was isolated by filtration,
washed with H2O and dried in air. 5.8 g (95%) of a pale yellow solid
was obtained. 1H NMR (400 MHz, CDCl3, 25 °C): d = 8.82 (br. s, 1 H,
NH), 7.38 (m, 1 H, p-H), 6.92 (t, J = 8.1 Hz, 2 H, m-H), 3.58–4.01 (m,
4 H, NCH2), 1.29 (t, J = 7.1 Hz, 6 H, NCH2CH3). 13C NMR (100 MHz,
CDCl3, 25 °C): d = 177.73 (C@O), 161.17 (d, J = 6.4 Hz, CF), 158.64
(d, J = 6.4 Hz, CF), 157.78 (C@S), 132.57 (t, J = 9.6 Hz, p-C), 113.10
(t, J = 18.5 Hz, ipso-C), 111.96 (d, J = 25.7 Hz, m-C), 47.62 (NCH2),
12.94 (NCH2CH3), 11.19 (NCH2CH3). 19F NMR (376 MHz, CDCl3,
25 °C): d = ꢀ111.99 (t, J = 9.1 Hz). Anal. Calc. for C12H14F2N2OS
(272.31): C, 52.93; H, 5.18; N, 10.29. Found: C, 53.04; H, 5.19; N,
10.54%.
The Pt–N distances are 2.0038(9) and 2.0295(9) Å, the signifi-
cantly longer one being trans to the Pt–S bond. The CSD contains
126 entries of bipyridyl coordinated to platinum, excluding Pt clus-
ters. A total of 248 Pt-N distances averages 2.048(37) Å while the
145 N–Pt–N angles average 79.5(14)° encompassing within the
statistical error the present results. More important is a compari-
son between the Pt–N distances trans to Pt–O and Pt–S bonds. In
this case 146 trans N–Pt–O and 68 trans-N–Pt–S fragments were
found, applying restraints of tetra coordinated Pt, two bonds
formed by each S- and O-atom and three bonds formed by nitro-
gen. A trans conformation was assumed if the N–Pt–X angle was
between 170 and 180°. The resulting Pt–N distances of 1.98(3) Å
for O–Pt–N and 2.052(19) Å for S–Pt–N support the significant
trans-effect (the difference amounts to 0.0257(13) Å) observed in
the present complex, even though the two CSD values do not differ
significantly.
The difluoro-substituted aromatic ring is twisted by 55.55° rel-
ative to the plane defined by the six-membered Pt–S–C–N–C–O
ring. The root-mean-square-distance (RMSD) for the six-mem-
bered metallacycle from a least-squares plane is 0.09 Å.
In summary, we present here the preparation and full charac-
terisation of some Pt(II), Pd(II) and Ru(II) complexes containing a
fluoro-substituted chelating thiourea ligand. Further work to study
this class of compounds as well as their selenium counterparts is
ongoing in our laboratory.
3.3. Preparation of cationic cis-[M{
(L)]+ complexes
j
2S,O-2,6-F2C6H3C(O)NC(S)NEt2}
A mixture of the metal precursor (0.050 g), 2,6-F2C6H3C(O)NHC
(S)NEt2 (1 equiv) and NH4PF6 (slight excess) in MeCN (10 mL) and
excess base (Et3N or NaOAc) was heated to reflux until a clear solu-
tion had formed. The solution was concentrated in vacuum to a
volume of ca. 2 mL and H2O was added, resulting in precipitation
of the product. The solid was isolated by filtration, washed with
H2O, Et2O and was subsequently dried in vacuum.
3.4. cis-[Pt{j
2S,O-2,6-F2C6H3C(O)NC(S)NEt2}(PPh3)2]PF6 (1)
This was prepared as described above from cis-[PtCl2(PPh3)2]
(0.050 g, 0.063 mmol), 2,6-F2C6H3C(O)NHC(S)NEt2 (0.017 g, 0.063
mmol) and NH4PF6 (0.012 g, 0.074 mmol). 0.050 g (69%) of a yellow
solid was obtained. 1H NMR (400 MHz, CDCl3, 25 °C): d = 7.05–7.62
(m, 31 H, Ph3P, p-H Ar), 6.62 (t, J = 8.9 Hz, 2 H, m-H Ar), 3.64 (quart,
J = 6.8 Hz, 2 H, NCH2), 3.43 (quart, J = 6.8 Hz, 2 H, NCH2), 1.15 (t,
J = 6.8 Hz, 3 H, MeCH2N), 1.00 (t, J = 6.8 Hz, 3 H, MeCH2N). 31P{1H}
NMR (162 MHz, CDCl3, 25 °C): d = 22.15 (d, JP–P = 25 Hz, JP–Pt
3094 Hz), 10.27 (d, J = 27 Hz, JP–Pt = 3874 Hz), ꢀ143 (sept, JP–F
=
=
706 Hz). 19F NMR (376 MHz, CDCl3, 25 °C): d = ꢀ73.5 (d, J = 712
Hz, PF6), ꢀ112.9 (t, J = 6.6 Hz, ArF). HR-ES-MS: m/z (observed, cal-
culated) = 990.2183, 990.2187 [M]+.
3. Experimental
3.5. cis-[Pd{j
2S,O-2,6-F2C6H3C(O)NC(S)NEt2}(PPh3)2]PF6 (2)
3.1. General
This was prepared as described above from cis-[PdCl2(PPh3)2]
(0.050 g, 0.071 mmol), 2,6-F2C6H3C(O)NHC(S)NEt2 (0.019 g, 0.069
mmol) and NH4PF6 (0.014 g, 0.086 mmol). 0.061 g (81%) of a yellow
solid was obtained. 1H NMR (400 MHz, CDCl3, 25 °C): d = 7.12–7.59
(m, 31 H, Ph3P, p-H Ar), 6.63 (t, J = 8.3 Hz, 2 H, m-H Ar), 3.65 (quart,
J = 6.8 Hz, 2 H, NCH2), 3.45 (quart, J = 6.8 Hz, 2 H, NCH2), 1.14
(t, J = 6.8 Hz, 3 H, MeCH2N), 1.00 (t, J = 6.8 Hz, 3 H, MeCH2N).
31P{1H} NMR (162 MHz, CDCl3, 25 °C): d = 39.43 (d, JP–P = 29 Hz),
28.70 (d, J = 29 Hz), ꢀ143 (sept, JP–F = 712 Hz). 19F NMR (376
MHz, CDCl3, 25 °C): d = ꢀ74.3 (d, J = 712 Hz, PF6), ꢀ113.1 (t, J =
7.0 Hz, ArF). HR-ES-MS: m/z (observed, calculated) = 901.1596,
901.1774 [M]+.
1H, 13C, 19F and 31P{1H} NMR spectra were recorded on a
400 MHz Bruker ARX spectrometer. Chemical shifts are quoted rel-
ative to external SiMe4 (1H, 13C), Freon (19F) and 85% H3PO4 31P).
(
High-resolution electrospray mass spectra were measured on a
Bruker MicroTOF spectrometer in positive ion mode using acetoni-
trile solutions of the compounds. Elemental analyses were per-
formed by staff of the microanalytical laboratory of the
University of Wuppertal. Chemicals and solvents (HPLC grade)
were sourced commercially and used as received. The metal pre-
cursors cis-[MCl2(PPh3)2] (M = Pt, Pd) [17] and [Ru(g
6-p-cym)Cl2]2
[18] and were prepared by procedures as described in the
literature. The tBu2bipy and 1,10-phenanthroline metal complexes
cis-[MCl2(N-N)] (M = Pd, Pt) were prepared by reaction of the
appropriate nitrogen base with [PdCl2(PhCN)2] or K2[PtCl4],
respectively.
3.6. cis-[Pt{j
2S,O-2,3-F2C6H3C(O)NC(S)NEt2}(tBu2bipy)]PF6 (3)
This was prepared as above from cis-[PtCl2(tBu2bipy)] (0.052 g,
0.097 mmol), 2,6-F2C6H3C(O)NHC(S)NEt2 (0.032 g, 0.100 mmol)
and NH4PF6 (0.017 g, 0.104 mmol). 0.068 g (76%) of a yellow solid
was obtained. 1H NMR (400 MHz, dmso-d6, 25 °C): d = 8.75 (d,
J = 2.0 Hz, 1 H, H5-bipy), 8.69 (d, J = 2.0 Hz, 1 H, H5-bipy), 8.63 (d,
J = 6.1 Hz, 1 H, H3-bipy), 8.56 (d, J = 6.1 Hz, 1 H, H3-bipy), 8.01
(dd, J = 6.1/2.0 Hz, 1 H, H4-bipy), 7.81 (dd, J = 6.1/2.0 Hz, 1 H, H4-
bipy), 7.66 (m, 1 H, H4-arom), 7.26 (t, J = 8.6 Hz, 2 H, H3, H5-arom),
3.93 (quart, J = 7.1 Hz, 2 H, NCH2), 3.76 (quart, J = 7.1 Hz, 2 H,
3.2. 2,6-F2C6H3C(O)NHC(S)NEt2
To a solution of KSCN (2.43 g, 25 mmol) in acetone (20 mL) was
added 2,6-F2C6H3C(O)Cl (4.41 g, 25 mmol). The resulting suspen-
sion was heated to reflux for ca. 2 h. After this time, Et2NH
(2.6 mL, 25 mmol) was added and the mixture refluxed once again
for ca. 30 min. The yellow suspension was poured into water
t
t
NCH2), 1.44 (s, 9 H, Bu), 1.43 (s, 9 H, Bu), 1.40 (t, J = 7.1 Hz, 3 H,

S. Pisiewicz et al. / Polyhedron 29 (2010) 1968–1972
1971
MeCH2N), 1.18 (t, J = 7.1 Hz, 3 H, MeCH2N). 19F NMR (376 MHz,
Table 1
Crystallographic and refinement details of complex 3.
dmso-d6, 25 °C): d = ꢀ70.7 (d, J = 711 Hz, PF6), ꢀ112.9 (t,
J = 7.2 Hz, ArF). HR- ES-MS: m/z (observed, calculated) = 782.1749,
782.1748 [M]+. Crystals suitable for X-ray diffraction were grown
by slow diffusion of Et2O into a CH2Cl2 solution of the complex.
Formula
C30H37F8N4OPPtS
Colour
yellow
879.76
Formula weight (g molꢀ1
)
T (K)
100
k (Å)
Crystal system
Space group
0.71073
monoclinic
P21/n, (no. 14)
3.7. cis-[Pd{j
2S,O-2,3-F2C6H3C(O)NC(S)NEt2}(tBu2bipy)]PF6 (4)
This was prepared as above from cis-[PdCl2(tBu2bipy)] (0.050 g,
0.112 mmol), 2,6-F2C6H3C(O)NHC(S)NEt2 (0.031 g, 0.114 mmol)
and NH4PF6 (0.027 g, 0.166 mmol). 0.068 g (76%) of a yellow solid
was obtained. 1H NMR (400 MHz, acetone-d6, 25 °C): d = 8.75 (d,
J = 2.0 Hz, 1 H, H5-bipy), 8.74 (d, J = 2.0 Hz, 1 H, H5-bipy), 8.65 (d,
J = 6.1 Hz, 1 H, H3-bipy), 8.48 (d, J = 6.1 Hz, 1 H, H3-bipy), 7.98
(dd, J = 6.1/2.0 Hz, 1 H, H4-bipy), 7.90 (dd, J = 6.1/2.0 Hz, 1 H, H4-
bipy), 7.63 (m, 1 H, H4-arom), 7.18 (t, J = 8.6 Hz, 2 H, H3, H5-arom),
4.09 (quart, J = 7.1 Hz, 2 H, NCH2), 3.92 (quart, J = 7.1 Hz, 2 H,
NCH2), 1.48 (m, 21 H, tBu, MeCH2N), 1.27 (t, J = 7.1 Hz, 3 H,
MeCH2N). 19F NMR (376 MHz, acetone-d6, 25 °C): d = ꢀ73.1 (d,
J = 705 Hz, PF6), ꢀ113.8 (t, J = 9.2 Hz, ArF). HR-ES-MS: m/z (ob-
served, calculated) = 645.1689, 645.1691 [M]+.
Unit cell dimensions
a (Å)
b (Å)
c (Å)
b (°)
V (Å3)
Z
9.2032(8)
24.425(2)
15.0626(13)
104.051(2)
3284.5(5)
4
1.779
4.461
1736
0.02 ꢁ 0.02 ꢁ 0.02
1.62–36.81
ꢀ15 6 h 6 15, ꢀ41 6 k 6 40,
ꢀ25 6 l 6 25
191 684
Dcalc (Mg mꢀ3
)
Absorption coefficient (mmꢀ1
F(0 0 0)
)
Crystal size (mm)
h Range for data collection (°)
Index ranges
Reflections collected
Independent reflections (Rint
)
16 197 (0.0275)
15 112
98.1%
empirical
0.75 and 0.59
Reflections with I > 2 (I)
r
3.8. cis-[Pt{j
2S,O-2,3-F2C6H3C(O)NC(S)NEt2}(phen)]PF6 (5)
Completeness to h = 36.81°
Absorption correction
Maximum and minimum
transmission
This was prepared as above from cis-[PtCl2(1,10-phen)] (0.050 g,
0.112 mmol), 2,6-F2C6H3C(O)NHC(S)NEt2 (0.032 g, 0.117 mmol)and
NH4PF6 (0.027 g, 0.166 mmol). 0.042 g (47%) of a yellow solid was
obtained. 1H NMR (400 MHz, dmso-d6, 25 °C): d = 9.00 (m, 2 H, H2-
phen, 8.89 (m, 2H, H5-phen), 8.25 (m, 2H, H4-phen), 8.04 (t,
J = 5.4 Hz, 2H, H3-phen), 7.64 (t, J = 7.6 Hz, 2H, H3, H5-arom), 3.95
(quart, J = 6.8 Hz, 2 H, NCH2), 3.79 (quart, J = 6.8 Hz, 2 H, NCH2),
1.42 (t, J = 6.8 Hz, 3 H, MeCH2N), 1.23 (t, J = 6.8 Hz, 3 H, MeCH2N).
19F NMR (376 MHz, dmso-d6, 25 °C): d = ꢀ70.7 (d, J = 707.9 Hz,
PF6), ꢀ112.6 (t, J = 9.4 Hz, ArF). HR-ES-MS: m/z (observed, calcu-
lated) = 646.1112, 646.1052 [M]+.
Refinement method
Full-matrix least-squares on F2
16 197/0/423
Data/restraints/parameters
Goodness-of-fit (GOF) on F2
1.125
Final R indices [I > 2
r
(I)]
R1 = 0.0166, wR2 = 0.0367
R1 = 0.0196, wR2 = 0.0377
1.324 and ꢀ0.620
R indices (all data)
Largest difference in peak and hole
(e Åꢀ3
)
lowed by least-squares refinement (SHELXL-97) [21]. All non-hydro-
gen atoms were refined anisotropically, for hydrogen atoms a
riding model was employed. Table 1 contains further crystallo-
graphic details, atomic coordinates together with complete bond
distances and angles can be found in the CIF, which has been
deposited as CCDC 758884.
3.9. [Ru(
g
6-p-cym){
j
2S,O-2,6-F2C6H3C(O)NC(S)NEt2}(PPh3)]PF6 (6)
This was prepared as described above from [Ru(
g
6-p-cym)Cl2]2
(0.050 g, 0.082 mmol), 2,6-F2C6H3C(O)NHC(S)NEt2 (0.045 g, 0.165
mmol), Ph3P (0.043 g, 0.164 mmol) and NH4PF6 (0.029 g, 0.1789
mmol). 0.116 g (78%) of a yellow solid was obtained. 1H NMR
(400 MHz, CDCl3, 25 °C): d = 7.37–7.52 (m, 15 H, Ph3P), 7.31 (tt,
Crystallographic and refinement details are shown in Table 1.
4. Supplementary data
4
3JH–H = 8.3 Hz, JF–H = 6.4 Hz, 1 H, p-H), 6.87 (m, 2 H, m-H), 5.83
CCDC 758884 contains the supplementary crystallographic data
for complex 3. These data can be obtained free of charge via
www.ccdc.cam.ac.uk/conts/retrieving.html, or from the Cambridge
Crystallographic Data Centre, 12 Union Road, Cambridge CB2 1EZ,
UK; fax: (+44) 1223-336-033; or e-mail: deposit@ccdc.cam.ac.uk.
(d, J = 6.1 Hz, 1 H, p-cym), 5.38 (d, J = 6.1 Hz, 1 H, p-cym), 5.34 (d,
J = 6.1 Hz, 1 H, p-cym), 4.87 (d, J = 6.1 Hz, 1 H, p-cym), 3.72 (AB
quart, 1 H, NCH2), 3.57 (AB quart, 1 H, NCH2), 3.53 (q, J = 7.1 Hz,
2 H, NCH2), 2.77 (sept, J = 7.1 Hz, 1 H, HC p-cym), 1.84 (s, 3 H, Me
p-cym), 1.21 (d, J = 7.1 Hz, 6 H, Me2CH), 1.18 (t, J = 7.1 Hz, 3 H,
MeCH2N), 0.96 (t, J = 7.1 Hz,
3
H, MeCH2N). 31P{1H} NMR
Acknowledgements
(162 MHz, CDCl3, 25 °C): d = 35.62, ꢀ143.01 (sept, JP–F = 712.8 Hz,
PF6). 19F NMR (376 MHz, CDCl3, 25 °C): d = ꢀ73.9 (d, J = 712.5 Hz,
PF6), ꢀ112.6 (m, ArF). HR-ES-MS: m/z (observed, calcu-
lated) = 769.1768, 769.1767 [M]+, 507.0876, 507.0856 [M-PPh3]+.
F.M. gratefully acknowledges generous funding from the Fonds
der Chemischen Industrie as well as the University of Wuppertal
for this project.
3.10. X-ray crystallography
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