Anionic tungsten carbonyl complexes containing dithiocarboxylate, dithiocarbamate, and xanthate ligands

Article abstract of DOI:10.1515/znb-2006-0511

The reaction of Et₄N[W(CO)₅Cl] with sodium dithiobenzoate, ethylxanthate, or various dithiocarbamates gave the corresponding salts Et₄N[W(CO)₄(SSCX)] (X = Ph, NEt ₂, N(H)t-Bu, NPh₂, OEt) which contain the dithio ligand in a chelating bonding mode. Two of them (X = N(H)t-Bu, NPh₂) were characterized by X-ray crystallography. The tungsten atom resides in the center of a slightly distorted octahedron surrounded by a symmetrically bidentate planar dithio ligand and four CO groups. Reaction with PPh₃ or PMe₃ at elevated temperature gave the tricarbonyl complexes Et ₄N[W(CO)₃(PR₃)(SSCX)] and in one case a ring-opened addition product, Et₄N[W(CO)₄(PMe ₃)(SC(S)OEt)]. For two of them X-ray structure determinations were carried out. A comparison of the four structures shows that while the W-C bond length decreases progressively with increasing electron density at the tungsten atom, the W-S and W-P bond lengths remain essentially constant.

Full text of DOI:10.1515/znb-2006-0511

Anionic Tungsten Carbonyl Complexes Containing Dithiocarboxylate,
Dithiocarbamate, and Xanthate Ligands
Stefan Dilsky and Wolfdieter A. Schenk
Institut fu¨r Anorganische Chemie der Universita¨t Wu¨rzburg,
Am Hubland, D-97074 Wu¨rzburg, Germany
Reprint requests to Prof. Dr. W. A. Schenk. Fax: +49-(0)931/888-4605.
E-mail: wolfdieter.schenk@mail.uni-wuerzburg.de
Z. Naturforsch. 61b, 570 – 576 (2006); received February 22, 2006
The reaction of Et4N[W(CO)5Cl] with sodium dithiobenzoate, ethylxanthate, or various dithio-
carbamates gave the corresponding salts Et4N[W(CO)4(SSCX)] (X = Ph, NEt2, N(H)t-Bu, NPh2,
OEt) which contain the dithio ligand in a chelating bonding mode. Two of them (X = N(H)t-Bu,
NPh2) were characterized by X-ray crystallography. The tungsten atom resides in the center
of a slightly distorted octahedron surrounded by a symmetrically bidentate planar dithio lig-
and and four CO groups. Reaction with PPh3 or PMe3 at elevated temperature gave the tricar-
bonyl complexes Et4N[W(CO)3(PR3)(SSCX)] and in one case a ring-opened addition product,
Et4N[W(CO)4(PMe3)(SC(S)OEt)]. For two of them X-ray structure determinations were carried out.
A comparison of the four structures shows that while the W–C bond length decreases progressively
with increasing electron density at the tungsten atom, the W–S and W–P bond lengths remain essen-
tially constant.
Key words: Tungsten, Dithiocarboxylate Complexes, Dithiocarbamate Complexes,
Xanthate Complexes, Carbonyl Complexes
Introduction
vulcanization promotors, or analytical reagents [9].
Dithiocarbamate complexes of the group 6 metals fall
into roughly three categories: High oxidation state (d0,
d1, d2) complexes with additional π donor (mostly oxo
or sulfido) ligands [10 – 15], medium oxidation state
(d4) complexes with additional π acceptor (carbonyl,
alkyne) ligands [16 – 24], and anionic d6 carbonyl
complexes [25 – 31]. Similar compounds containing
xanthates [25, 27, 28, 32] or dithiocarboxylates [33 –
35] as ligands have also been reported in the literature.
In the d6 complexes the dithio anions may act as ei-
ther mono- or chelating bidentate ligands wheras the
chelating mode prevails for the electronic configura-
tions d0 – d4.
We have shown recently that certain tungsten car-
bonyl anions such as [W(CO)5(CN)]− or the thiolate
complexes [W(CO)5(SR)]− are sufficiently lipophilic
to be absorbed by the lipid bilayer membrane of liv-
ing cells [1 – 5]. This leads to a change in the dielec-
tric properties of the membrane which can be moni-
tored by a number of methods, most notably the “elec-
trorotation” experiment [6]. Some of the tungsten car-
bonyl anions exhibit stronger effects and a markedly
lower cytotoxicity compared to more conventional an-
ions such as dipicrylamide or tetraphenylborate, which
can be very important when in comes to practical
applications [7]. In order to gain some insight into
the relationship between structure and activity we de-
cided to include tungsten tetracarbonyl complexes of
dithiocarboxylates, dithiocarbamates, and xanthates in
our studies. The bidentate coordination of these an-
ions was expected to confer improved stability to these
systems.
Results and Discussion
Synthesis
Tetraethylammonium-chloropentacarbonyltung-
state [36] reacts readily with the sodium salts of
the various dithioanions to give the tetracarbonyl-
tungstates 1 – 3 (eq (1)).
Dithiocarbamates and xanthates have been used ex-
tensively as ligands [8]. Their metal complexes are
Monitoring the progress of the reaction by in-
found in applications as diverse as agrochemicals, frared spectroscopy showed that the corresponding
c
0932–0776 / 06 / 0500–0570 $ 06.00 ꢀ 2006 Verlag der Zeitschrift fu¨r Naturforschung, Tu¨bingen · http://znaturforsch.com
Unauthenticated
Download Date | 7/12/17 4:06 PM

St. Dilsky – W. A. Schenk · Anionic Tungsten Carbonyl Complexes
571
Table 2. Characteristic 13C NMR resonances of the tetracar-
bonyltungstates 1 – 3, recorded from [D6]-acetone solutions.
CO (cis) 1J(W-C) (Hz) CO (trans) 1J(W-C) (Hz) CX
1
203.1
128
128
128
127
128
213.5
214.0
214.1a
213.7
212.7
168
172
248.1
214.5
217.8
219.3
229.9
2a 204.6
2b 204.8
2c 204.3
3
a
173
175
203.3
Broad.
Table 3. Characteristic 13C and 31P NMR resonances of the
tricarbonyltungstates 4a, 4b, 5, recorded from [D6]-acetone
solutions.
Table 1. Characteristic infrared absorptions (cm−1) of the
tetracarbonyltungstates 1 – 3, recorded from acetonitrile so-
lutions.
13C NMR
31P NMR
PR3 1J(W-P)
(Hz)
A1
A1
B1
B2
CO 2J(P-C) CO
2J(P-C) CX
1
1994
1995
1995
1996
2002
1877
1865
1866
1868
1874
1859
1843
1842
1845
1854
1822
1801
1801
1804
1812
(cis) (Hz)
4a 217.3 48
4b 218.4 49
(trans) (Hz)
2a
2b
2c
3
219.8
221.2
218.6
6
6
6
213.4
24.8 190
215.1a −27.9 193
5
214.7 43
227.3b
29.0 205
a 3J(P-C) 4 Hz; b 3J(P-C) 6 Hz.
pentacarbonyl anions were involved as intermedi-
ates, but no particular effort was made to isolate
them. The products were obtained as microcrys-
talline, air-stable compounds. The dithiobenzoate com-
plex 1 has a deep purple color while the dithio-
carbamate and xanthate derivatives are bright yel-
low. 2a had previously been synthesized in 55%
yield directly from [W(CO)6], Et4NCl and sodium-
diethyldithiocarbamate [30]. Due to their ionic struc-
ture, 1 – 3 are soluble only in polar organic solvents
such as THF, acetone, dichloromethane or acetoni-
trile. Their infrared spectra in the CO stretching region
(Table 1) display the expected four bands which are
shifted to low wavenumbers as a result of the negative
charge. The 13C NMR signals of the carbonyl groups
(Table 2) are shifted to low field and exhibit the ex-
pected couplings with 183W [34].
CO/PR3 exchange
The reactions of 2a and 3 with triphenylphos-
The phosphine derivatives are again yellow, air-
phine and trimethylphosphine were checked in or- stable compounds which are, like their precursor com-
der to test the lability of the ligands at tungsten and plexes, also soluble in polar solvents. That 6 is a
to increase the lipophilicity of the anion. In contrast tetracarbonyl complex is immediately obvious from
to an earlier notion [37] we found that 2a and 3 its infrared spectrum which exhibits bands at 1998,
do react with triphenylphosphine to give the tricar- 1882, 1866 and 1824 cm−1, very similar to the spectra
bonyl complexes 4a and 5 (eq. (2)). 4a had previously of 1 – 3 or the complexes Et4N[W(CO)4(PR3)Cl] [38]
been obtained from [W(CO)3(py)3], PPh3 and sodium- to which it might be reasonably compared. The tricar-
ethylxanthate in unspecified yield [37]. With the bet- bonyl complexes 4a, 4b, and 5 have still lower CO fre-
ter donor trimethylphosphine, the dithiocarbamate 2a quencies. The 13C resonances of the CO ligands are
gave the analogous substitution product 4b; the xan- shifted even further downfield and exhibit the requisite
thate 3, however, yielded the ring opened complex 6 31P–13C couplings (Table 3). Interestingly, and perhaps
(eq. (3)).
disappointingly, the chemical shift of the dithiocar-
Unauthenticated
Download Date | 7/12/17 4:06 PM

572
St. Dilsky – W. A. Schenk · Anionic Tungsten Carbonyl Complexes
Fig 1. Structure of the anion of Et4N[W(CO)4
(SSCN(H)tBu)] (2b), hydrogen atoms [except for H(1)]
omitted for clarity. Space group P21/n. Selected bond
lengths [pm], angles [◦], and torsion angles [◦] (estimated
standard deviations in parentheses): W(1)–S(1) 257.68(8),
W(1)–S(2) 258.90(8), S(1)–C(5) 170.8(3), S(2)–C(5)
172.3(3), N(1)–C(5) 132.8(4), W(1)–C(1) 195.3(3),
W(1)–C(2) 194.0(3), W(1)–C(3) 202.6(4), W(1)–C(4)
202.6(3); S(1)–W(1)–S(2) 68.06(2), S(1)–C(5)–S(2)
114.77(17), S(1)–W(1)–C(2) 167.86(9), S(2)–W(1)–C(1)
167.88(10), C(1)–W(1)–C(2) 91.45(13), C(3)–W(1)–C(4)
176.94(13); S(1)–C(5)–N(1)–C(6) −4.5(5).
Fig 2. Structure of the anion of Et4N[W(CO)4(SSCNPh2)]
(2c), hydrogen atoms omitted for clarity. Space group
◦
¯
P1. Selected bond lengths [pm], angles [ ], and torsion
angles [◦] (estimated standard deviations in parentheses):
W(1)–S(1) 257.59(7), W(1)–S(2) 259.59(7), S(1)–C(5)
170.3(3), S(2)–C(5) 170.7(3), N(1)–C(5) 134.7(3),
W(1)–C(1) 200.6(3), W(1)–C(2) 194.5(3), W(1)–C(3)
195.6(3), W(1)–C(4) 202.4(3); S(1)–W(1)–S(2) 67.78(2),
S(1)–C(5)–S(2) 115.49(15), S(1)–W(1)–C(3) 168.04(9),
S(2)–W(1)–C(2) 167.72(9), C(1)–W(1)–C(4) 171.11(11),
C(2)–W(1)–C(3) 90.45(12); S(1)–C(5)–N(1)–C(30) 11.3(4),
S(2)–C(5)–N(1)–C(20) 15.6(4). The second independent
anion in the cell has nearly identical geometric data.
bamate and xanthate carbon changes very little upon
CO/PR3 exchange and, at least when compounds 5
and 6 are compared, does not allow any distinction be-
tween mono- and bidentate coordination.
Structures
The structures of the anions of 2b (Fig. 1),
2c (Fig. 2), 4a (Fig. 3), and 5 (Fig. 4) exhibit a fairly
regular octahedral coordination of the tungsten atom.
Deviations arise from the small bite angle of the
bidentate sulfur ligand which restricts the S–W–S an-
gle to 68◦. The trans pair of ligands is slightly bent
away from the coordinated dithio ligand such that the
C–W–C (trans) angles in 2b and 2c, and the P–W–C
(trans) angles in 4a and 5, are reduced to values be-
tween 171 and 177◦. The W–S bond lengths are close
to those in 2a [30], and the W–P bond lengths in 4a group P1. Selected bond lengths [pm], angles [ ], and torsion
and 5 are almost identical to those in the neutral com-
plex [W(CO)5(PPh3)] [39]. The dithio ligands are co-
ordinated symmetrically, i. e. the two W–S and C–S
Fig 3. Structure of the anion of Et4N[W(CO)3(PPh3)
(SSCNEt2)] (4a), hydrogen atoms omitted for◦clarity. Space
¯
angles [◦] (estimated standard deviations in parentheses):
W(1)–S(1) 258.95(11), W(1)–S(2) 258.17(10), W(1)–P(1)
254.12(10), S(1)–C(4) 171.6(4), S(2)–C(4) 171.5(4),
N(1)–C(4) 133.4(5), W(1)–C(1) 196.5(5), W(1)–C(2)
bond lengths in each complex are almost identical.
The four-membered rings are nearly planar, the largest
deviation occurs in 2b where the planes defined by
S(1)–W(1)–S(2) and S(1)–C(5)–S(2) span an angle
of 12.3(2)◦. Inspection of the unit cell reveals that in
this case the distortion is caused by close packing of
192.9(5), W(1)–C(3) 194.1(5); S(1)–W(1)–S(2) 67.87(3),
S(1)–W(1)–P(1) 98.88(4), S(2)–W(1)–P(1) 90.11(3),
S(1)–C(4)–S(2) 114.6(2), S(1)–W(1)–C(3) 168.68(16),
S(2)–W(1)–C(2) 167.33(18), P(1)–W(1)–C(1) 173.33(16),
C(2)–W(1)–C(3) 90.5(2); S(1)–C(4)–N(1)–C(5) 2.9(6),
S(2)–C(4)–N(1)–C(7) 4.8(6).
the N(H)t-Bu group against the Et4N+ cation. The tively]. In these cases the dithio ligands are bent away
phosphine substitution products 4a and 5 have even from the PPh3 ligand indicating that the distortion is
smaller interplanar angles [9.0(3)◦ and 4.0(2)◦, respec- caused by steric repulsion. In 2b, 4a and 5 the dithio
Unauthenticated
Download Date | 7/12/17 4:06 PM

St. Dilsky – W. A. Schenk · Anionic Tungsten Carbonyl Complexes
573
CO groups by the better donors PPh3 or dithiocarba-
mate, the W–C bonds become shorter due to the in-
creased back donation into the π ∗ levels of the remain-
ing CO ligands. This contraction is roughly three times
as big for the W–C bonds trans to the new ligand than
those cis (e. g. −4.2 vs. −1.5 pm for the pair [W(CO)6]
and [W(CO)5(PPh3)], and −9.8 vs. −3.3 pm for the
pair [W(CO)6] and 2c). This rule of thumb even holds
for the pair 2c / 4a, where the W–C bond trans to P
(and cis to S) contracts by −5.0 pm while the other two
shrink only by −1.5 pm. The interrelation of M–C and
M–P bond lengths and electron density has been noted
quite some time ago and is usually discussed within
a σ / π bonding model [41, 42]. The similarity of the
W–P bond lengths of [W(CO)5(PPh3)], 4a, and 5 then
indicates that σ bonding effects, which should give
rise to a lengthening of the W–P bond upon replacing
two CO ligands by a dithiocarbamate or xanthate, and
π bonding effects, which should lead to a contraction,
almost cancel. This is perfectly in line with the notion
that PR3 ligands are to some degree capable of under-
going π interactions with low-valent transition metal
complexes [43].
Fig 4. Structure of the anion of Et4N[W(CO)3(PPh3)
(SSCOEt)] (5), hydrogen atoms omitted for clarity. Space
group P21/n. Selected bond lengths [pm], angles [◦], and
torsion angles [◦] (estimated standard deviations in parenthe-
ses): W(1)–S(1) 261.10(7), W(1)–S(2) 259.72(7), W(1)–P(1)
256.26(7), S(1)–C(4) 168.7(3), S(2)–C(4) 168.6(3),
O(4)–C(4) 133.6(3), W(1)–C(1) 192.8(3), W(1)–C(2)
193.1(3), W(1)–C(3) 195.6(3); S(1)–W(1)–S(2) 67.60(2),
S(1)–W(1)–P(1) 87.94(2), S(2)–W(1)–P(1) 96.01(2),
S(1)–C(4)–S(2) 118.39(17), S(1)–W(1)–C(2) 168.16(9),
S(2)–W(1)–C(1) 171.90(9), P(1)–W(1)–C(3) 171.30(9),
C(1)–W(1)–C(2) 86.53(12); S(2)–C(4)–O(4)–C(5) −1.2(4).
ligands are almost perfectly planar. In 2c the dihedral
angles around the C(5)–N(1) bond deviate significantly
from the expected 0 or 180◦, certainly as a result of the
bulkiness of the two phenyl groups.
Conclusions
The synthesis of anionic tungsten carbonyl com-
plexes designed for their possible application as
reagents to modify the dielectric properties of lipid
membranes was the principal goal of this work. In
our hands, the reaction of Et4N[W(CO)5Cl] with salts
of the anionic ligands gave cleaner products than any
other method [25 – 35, 37]. The characterization of
these compounds by IR and 13C NMR spectroscopy
(Tables 1, 2) gave the expected results. The data listed
in Table 1 show that the dithiocarbamate ligands are
even better electron donors than dithiobenzoate or
ethylxanthate. This points to a contribution of a res-
onance structure with a C=N double bond (eq. (4))
which is in line with the observed NMR resonance of
this C atom at higher field (Table 2) and also with the
planar geometry around the N atom.
Experimental Section
All experiments were carried out in Schlenk tubes under
an atmosphere of nitrogen using suitably purified solvents.
– IR: Bruker IFS 25. – 1H NMR: Bruker AMX 400, Jeol
JNM-LA 300, δ values relative to TMS. The signals of the
Et4N+ cation [δ = 1.35 (tt, J = 7.3 Hz, Jꢀ = 1.8 Hz, 12 H,
NCH2CH3), 3.40 (q, J = 7.3 Hz, 8 H, NCH2CH3)] are sim-
ilar for all compounds and have therefore been omitted from
the lists of spectral data. – 13C NMR: Bruker AMX 400, Jeol
JNM-LA 300, δ values relative to TMS, assignments rou-
tinely checked by DEPT spectra. In some cases the signals of
quarternary carbon atoms were too weak to be detected. The
signals of the Et4N+ cation [δ = 7.6 (s, NCH2CH3), 53.0
(t, J = 3 Hz, NCH2CH3)] are similar for all compounds and
have therefore been omitted from the lists of spectral data.
Some regular geometric trends emerge when the
structures of 2c and 4a are compared with those
of their parent compounds [W(CO)6] [40] and
[W(CO)5(PPh3)] [39]. With successive replacement of
–
31P NMR: Bruker AMX 400, Jeol JNM-LA 300, δ val-
Unauthenticated
Download Date | 7/12/17 4:06 PM

574
St. Dilsky – W. A. Schenk · Anionic Tungsten Carbonyl Complexes
Table 4. Details of the
structure determinations
of compounds 2b, 2c, 4a,
and 5.
2b
2c
4a
5
Empirical formula
Formula mass
C17H30N2O4S2W C25H30N2O4S2W C34H45N2O3PS2W C32H40NO4PS2W
574.42
670.51
808.70
781.63
Crystal colour/habit
Crystal system
Space group
yellow plate
monoclinic
P21/n
11.0161(11)
11.9892(12)
17.6605(17)
90
orange block
triclinic
¯
P1
yellow prism
triclinic
¯
P1
yellow plate
monoclinic
P21/n
9.0861(6)
16.8115(11)
21.2534(14)
90
˚
a [A]
10.8057(7)
15.1922(10)
16.7423(11)
88.127(1)
84.885(1)
80.161(1)
2696.8(3)
1.81 – 28.28
−14 to 14
−20 to 19
−22 to 21
4
9.5615(8)
10.3885(8)
17.6669(14)
100.503(1)
94.924(1)
90.823(1)
1718.3(2)
1.99 – 28.29
−12 to 12
−13 to 13
−23 to 23
2
˚
b [A]
˚
c [A]
α [◦]
β [◦]
γ [◦]
106.399(2)
90
93.123(1)
90
3
˚
V [A ]
2237.6(4)
1.96 – 28.26
−14 to 14
−15 to 15
−23 to 23
4
3241.7(4)
2.39 – 28.29
−12 to 12
−22 to 22
−27 to 28
4
θ [◦]
h
k
l
Z
µ(Mo-Kα ) [mm−1
Crystal size [mm]
]
5.371
4.470
3.565
3.778
0.15×0.15×0.05 0.20×0.20×0.15 0.20×0.15×0.15 0.20×0.20×0.10
Dcalcd. [gcm−3
T [K]
]
1.705
173(2)
43621
5316
246
1.651
173(2)
61863
12521
621
1.563
173(2)
39365
7992
364
1.601
173(2)
54554
7600
375
Reflections coll.
Indep. reflections
Parameter
R1(I > 2σ(I))
R1 (all data)
wR2(I > 2σ(I))
wR2 (all data)
Diff. peak/hole [eA
CCDC
0.0272
0.0327
0.0578
0.0595
1.161/−0.627
298204
0.0248
0.0275
0.0536
0.0547
1.038/−0.426
298202
0.0364
0.0383
0.0925
0.0936
2.258/−2.317
298203
0.0267
0.0280
0.0576
0.0583
1.037/−0.354
298201
−3
˚
]
ues relative to 85% H3PO4. – Elemental analyses: Analyt- Et4N[W(CO)4(SSCX)] (2a – c, 3)
ical Laboratory of the Institut fu¨r Anorganische Chemie. –
A solution of Et4N[W(CO)5Cl] (980 mg, 2.00 mmol) and
sodium dithiocarbamate or xanthate (2.05 mmol) in acetoni-
trile (20 ml) was heated under reflux for 2 h. Gas evolution
was observed, and the yellow solution turned dark brown.
The solvent was removed under vacuum, and the residue dis-
solved in THF/acetone 10 : 1 and filtered over a layer of silica
gel (1 cm) and celite (5 cm). The yellow-brown filtrate was
evaporated to dryness and the residue washed with diethyl
ether.
The following starting materials were obtained as described
in the literature: Et4N[W(CO)5Cl] [36], Et4N[SSCPh] [44],
xanthates and dithiocarbamates [45]. All other reagents were
used as purchased.
Et4N[W(CO)4(SSCPh)] (1)
A solution of Et4N[W(CO)5Cl] (490 mg, 1.00 mmol) and
Et4N[SSCPh] (290 mg, 1.02 mmol) in THF (15 ml) was
heated under reflux for 30 min. More THF (20 ml) was
◦
2a: Yield 0.89 g (78%), yellow powder. – M. p. 68 C
1
◦
added, and the mixture filtered over silica/celite. The fil- (dec). – H NMR (400 MHz, acetone-d6, 20 C): δ = 1.19
trate was evaporated to dryness and the residue washed with (t, J = 7.0 Hz, 6 H, NCH2CH3), 3.67 (q, J = 7.0 Hz,
diethyl ether. Yield 270 mg (47%), dark purple microcrys- 4 H, NCH2CH3). – 13C{ H} NMR (100 MHz, acetone-d6,
1
talline powder.
20 ◦C): δ = 12.6 (s, NCH2CH3), 44.2 (s, NCH2CH3), 204.6
(s, J(W,C) = 128 Hz, cis-CO), 214.0 (s, J(W,C) = 172 Hz,
trans-CO), 214.5 (s, SSCN). – C17H30N2O4S2W (574.42):
calcd. C 35.55, H 5.26, N 4.88, S 11.16; found C 35.35,
H 5.29, N 4.95, S 11.05.
◦
M. p. 52 C (dec). – 1H NMR (400 MHz, acetone-d6,
20 ◦C): δ = 7.31 – 7.38 (m, 2 H, C6H5), 7.47 – 7.52 (m,
1
1 H, C6H5), 8.02 – 8.09 (m, 2 H, C6H5). – 13C{ H} NMR
(100 MHz, acetone-d6, 20 ◦C): δ = 123.1 (s, C6H5), 128.3 (s,
C6H5), 132.0 (s, C6H5), 147.7 (s, C6H5), 203.1 (s, J(W,C) =
◦
2b: Yield 0.77 g (67%), brown powder. – M. p. 55 C
128 Hz, cis-CO), 213.5 (s, J(W,C) = 168 Hz, trans-CO), (dec). – 1H NMR (400 MHz, acetone-d6, 20 ◦C): δ = 1.50 (s,
248.1 (s, SSC). – C19H25NO4S2W (579.39): calcd. C 39.39, 9 H, NC(CH3)3), NH signal not detected. – 13C{ H} NMR
1
H 4.35, N 2.42, S 11.07; found C 38.89, H 4.38, N 2.32, (100 MHz, acetone-d6, 20 ◦C): δ = 28.8 (s, NC(CH3)3),
S 11.50.
55.3 (s, NC(CH3)3), 204.8 (s, J(W,C) = 128 Hz, cis-CO),
Unauthenticated
Download Date | 7/12/17 4:06 PM

St. Dilsky – W. A. Schenk · Anionic Tungsten Carbonyl Complexes
575
214.2 (s, trans-CO), 217.8 (s, SSCN). – C17H30N2O4S2W 215.1 (d, J = 4 Hz, SSCN), 218.4 (d, J(W,C) = 165 Hz,
(574.42): calcd. C 35.55, H 5.26, N 4.88, S 11.16; found J(P,C) = 49 Hz,CO), 221.2 (d, J(W,C) = 179 Hz, J(P,C) =
1
C 35.24, H 4.86, N 4.31, S 11.52.
6 Hz, CO). – 31P{ H} NMR (162 MHz, acetone-d6, 20 ◦C):
δ = −27.9 (s, J(W,P) = 193 Hz). – C19H39N2O3PS2W
(622.49): calcd. C 36.66, H 6.32, N 4.50, S 10.30; found
C 36.41, H 5.91, N 4.22, S 10.05.
2c: Yield 0.66 g (49%), yellow-brown powder. – M. p.
52 ◦C (dec). – 1H NMR (400 MHz, acetone-d6, 20 ◦C): δ =
7.23 – 7.44 (m, 10 H, C6H5). – 13C{ H} NMR (100 MHz,
1
5: Yield 0.19 g (97%), orange-yellow solid. M. p. 66−◦1C
◦
acetone-d6, 20 C): δ = 127.8 (s, C6H5), 129.1 (s, C6H5),
˜
(dec). – IR (CH3CN): ν = 1898, 1784, 1767 (CO) cm
.
129.8 (s, C6H5), 144.9 (s, C6H5), 204.3 (s, J(W,C) =
127 Hz, cis-CO), 213.7 (s, J(W,C) = 173 Hz, trans-CO),
219.3 (s, SSCN). – C25H30N2O4S2W (670.51): calcd.
C 44.78, H 4.51, N 4.18, S 9.56; found C 43.95, H 4.78,
N 3.98, S 9.52.
–
1H NMR (400 MHz, acetone-d6, 20 ◦C): δ = 1.11 (t,
J = 7.0 Hz, 3 H, OCH2CH3), 3.96 (q, J = 7.0 Hz, 2 H,
OCH2CH3), 7.26 – 7.31 (m, 8 H, PC6H5), 7.36 – 7.40 (m,
2 H, PC6H5), 7.62 – 7.68 (m, 5 H; PC6H5). – 13C{ H} NMR
1
◦
◦
(100 MHz, acetone-d6, 20 C): δ = 14.0 (s, OCH2CH3),
3: Yield 1.01 g (93%), yellow powder. – M. p. 74 C
1
◦
65.5 (s, OCH2CH3), 128.0 – 135.2 (m, PC6H5), 137.7 (d,
J = 30 Hz, i-PC6H5), 214.7 (d, J = 43 Hz, CO), 218.6 (d,
J = 182 Hz, J = 6 Hz, CO), 227.3 (d, J = 6 Hz, SSCO).
(dec). – H NMR (400 MHz, acetone-d6, 20 C): δ = 1.34
(t, J = 7.0 Hz, 3 H, OCH2CH3), 4.43 (q, J = 7.0 Hz,
1
2 H, OCH2CH3). – 13C{ H} NMR (100 MHz, acetone-d6,
1
◦
20 ◦C): δ = 14.0 (s, OCH2CH3), 66.7 (s, OCH2CH3), 203.3
(s, J(W,C) = 128 Hz, cis-CO), 212.7 (s, J(W,C) = 175 Hz,
trans-CO), 229.9 (s, SSCO). – C15H25NO5S2W (547.35):
calcd. C 32.92, H 4.60, N 2.56, S 11.72; found C 32.64,
H 4.47, N 2.44, S 11.72.
–
31P{ H} NMR (162 MHz, acetone-d6, 20 C): δ = 29.0
(s, J(W,P) = 205 Hz). – C32H40NO4PS2W (781.63): calcd.
C 49.17, H 5.16, N 1.79, S 8.21; found C 48.96, H 5.13,
N 1.63, S 7.79.
6: Yield 0.15 g (96%), yellow microcrystalline powder.
◦
˜
M. p. 62 C. – IR (THF): ν = 1998, 1882, 1866, 1824
(CO) cm−1. – 1H NMR (400 MHz, acetone-d6, 20 ◦C):
δ = 1.34 (t, J = 7.0 Hz, 3 H, OCH2CH3), 1.48 (d, J =
Et4N[W(CO)3(PR3)(SSCX)] (4a, 4b, 5) and
Et4N[W(CO)4(PMe3)(SC(S)OEt)] (6)
7.4 Hz, 9 H, PCH3), 4.46 (q, J = 7.0 Hz, 2 H, OCH2CH3).
1
–
13C{ H} NMR (100 MHz, acetone-d6, 20 ◦C): δ =
A solution of 2a or 3 (0.25 mmol) and PPh3 (0.10 g,
0.38 mmol) or PMe3 (80 µl, 0.77 mmol) in acetonitrile
(10 ml) was heated under reflux until the starting material
was completely consumed (IR). The mixture was evaporated
to dryness and the excess phosphine removed by extraction
with diethyl ether and hexane.
14.4 (s, OCH2CH3), 19.3 (d, J = 25 Hz, PCH3), 68.6 (s,
OCH2CH3), 206.3 d, J(W,C) = 127 Hz, J(P,C) = 9 Hz
CO), 212.3 (d, J(W,C) = 153 Hz, J(P,C) = 31 Hz, CO),
212.3 (d, J(W,C) = 160 Hz, J(P,C) = 5 Hz, CO), 227.2
(d, J(P,C) = 4 ◦Hz, SSCO). – 31P{ H} NMR (162 MHz,
1
4a: Yield 0.18 g (90%), yellow solid. – M. p. 34 −◦1C
acetone-d6, 20 C): δ = −32.8 (s, J(W,P) = 220 Hz). –
C18H34NO5PS2W (623.43): calcd. C 34.68, H 5.50, N 2.25,
S 10.29; found C 34.08, H 5.31, N 2.01, S 10.16.
˜
(dec). – IR (CH3CN): ν = 1889, 1772, 1757 (CO) cm
.
– 1H NMR (400 MHz, acetone-d6, 20 ◦C): δ = 0.94 (t, J =
3
7.0 Hz, 6 H, NCH2CH3), 3.34 (q, J(H,H) = 7.0 Hz, 4 H,
X-ray structure determinations
NCH2CH3), 7.22 – 7.30 (m, 8 H, PC6H5), 7.35 – 7.40 (m,
2 H, PC6H5), 7.61 – 7.68 (m, 5 H; PC6H5). – 13C{ H} NMR
1
Single crystals of 2b, 2c, 4a, or 5 were sealed to a
glass fiber with frozen hydrocarbon oil. A Bruker Smart
Apex CCD instrument with D8 goniometer was used for
data collection (graphite monochromator, Mo-Kα radiation,
(100 MHz, acetone-d6, 20 ◦C): δ = 12.6 (s, NCH2CH3),
44.0 (s, NCH2CH3), 127.8 (d, J = 8 Hz, m-PC6H5), 128.8
(d, J = 1 Hz, p-PC6H5), 135.4 (d, J = 11 Hz, o-PC6H5),
137.9 (d, J = 28 Hz, i-PC6H5), 213.4 – 213.5 (br, SSCN),
217.3 (d, J = 48 Hz, CO), 219.8 (d, J = 6 Hz, CO). –
˚
λ = 0.71073 A). The structures were solved using Patterson
methods and refined with full-matrix least squares against F2
(SHELXS-97) [46]. Hydrogen atoms were included in their
calculated positions and refined in a riding model. The details
of the measurements are summarized in Table 4. Further data
may be obtained from the Cambridge Crystallographic Data
Centre. 2b: CCDC 298204, 2c: CCDC 298202, 4a: CCDC
298203, 5: CCDC 298201. These data can be obtained free
of charge at www.ccdc.cam.ac.uk/conts/retrieving.html.
1
31P{ H} NMR (162 MHz, acetone-d6, 20 ◦C): δ = 24.8 (s,
J(W,P) = 190 Hz). – C34H45N2O3PS2W (808.70) – calcd.
C 50.50, H 5.61, N 3.46, S 7.93; found C 50.31, H 5.52,
N 3.22, S 8.13.
4b: Yield 0.12 g (76%), yellow microcrystalline pow-
◦
˜
der. M. p. 24 C (dec). – IR (THF): ν = 1883, 1766, 1746
(CO) cm−1. – 1H NMR (400 MHz, acetone-d6, 20 ◦C):
δ = 1.17 (t, J = 7.0 Hz, 6 H, NCH2CH3), 1.36 (d, J =
6.2 Hz, 9 H, PCH3), 3.55 – 3.73 (m, 4 H, NCH2CH3). –
Acknowledgment
1
13C{ H} NMR (100 MHz, acetone-d6, 20 ◦C): δ = 12.8 (s,
We are indebted to the Deutsche Forschungsgemeinschaft
NCH2CH3), 16.6 (d, J = 19 Hz, PCH3), 44.2 (s, NCH2CH3), for the generous support of this work.
Unauthenticated
Download Date | 7/12/17 4:06 PM

576
St. Dilsky – W. A. Schenk · Anionic Tungsten Carbonyl Complexes
[1] K. Nielsen, W. A. Schenk, M. Kriegmeier, V. L. Sukho-
rukov, U. Zimmermann, Inorg. Chem. 35, 5762 (1996)
[23] J. R. Morrow, T. L. Tonker, J. L. Templeton, J. Am.
Chem. Soc. 107, 6956 (1985).
[2] M. Ku¨rschner, K. Nielsen, C. Andersen, V. L. Sukho-
rukov, W. A. Schenk, R. Benz, U. Zimmermann, Bio-
phys. J. 74, 3031 (1998).
[3] M. Ku¨rschner, K. Nielsen, J. von Langen, W. A.
Schenk, U. Zimmermann, V. L. Sukhorukov, Biophys.
J. 79, 1490 (2000).
[24] R. S. Herrick, J. L. Templeton, Inorg. Chem. 25, 1270
(1986).
[25] M. R. Houchin, K. Mitsios, Inorg. Chim. Acta 64, L147
(1982).
[26] E. C. Alyea, A. Somogyvari, Inorg. Chim. Acta 83, L49
(1984).
[4] V. L. Sukhorukov, M. Ku¨rschner, S. Dilsky, T. Lisec,
B. Wagner, W. A. Schenk, R. Benz, U. Zimmermann,
Biophys. J. 81, 1006 (2001).
[5] O. R. Reuss, M. Ku¨rschner, S. Dilsky, M. Horbaschek,
W. A. Schenk, U. Zimmermann, V. L. Sukhorukov,
J. Electrostatics 56, 419 (2002).
[6] G. Fuhr, U. Zimmermann, S. G. Shirley, in U. Zimmer-
mann, G. A. Neil (eds): Electromanipulation of Cells,
p. 259. CRC Press, Boca Raton (1996).
[27] A. E. Sa´nchez-Pela´ez, M. F. Perpin˜a´n, A. Santos,
J. Organomet. Chem. 296, 367 (1985).
[28] A. E. Sa´nchez-Pela´ez, M. F. Perpin˜a´n, E. Gutierrez-
Puebla, A. Monge, C. Ruiz-Valero, J. Organomet.
Chem. 384, 79 (1990).
[29] B. Zhuang, L. Hang, L. He, Y. Yang, J. Lu, Inorg.
Chim. Acta 145, 225 (1988).
[30] B. Zhuang, P. Yu, L. Hang, L. He, J. Lu, Inorg. Chim.
Acta 177, 239 (1990).
[7] V. L. Sukhorukov, R. Reuss, D. Zimmermann, C. Held,
K. J. Mu¨ller, M. Kiesel, P. Geßner, A. Steinbach, W. A.
Schenk, E. Bamberg, U. Zimmermann, J. Membrane
Biology 206, 187 (2005).
[8] J. A. Cras, J. Willemse, in G. Wilkinson, R. D. Gillard,
J. A. McCleverty (eds): Comprehensive Coordination
Chemistry Vol. 2, p. 579. Pergamon, Oxford (1987).
[9] F. A. Cotton, G. Wilkinson, Advanced Inorganic
Chemistry, 5th ed., p. 536. Wiley, New York (1988).
[10] E. C. Alyea, G. Ferguson, M. Parvez, A. Somogyvari,
Polyhedron 4, 783 (1985).
[31] K.-H. Yih, S.-C. Chen, Y.-C. Lin, G.-H. Lee, Y. Wang,
J. Organomet. Chem. 494, 149 (1995).
[32] D. J. Darensbourg, K. M. Sanchez, J. H. Reibenspies,
A. L. Rheingold, J. Am. Chem. Soc. 111, 7094 (1989).
[33] D. J. Darensbourg, A. Rokicki, M. Y. Darensbourg,
J. Am. Chem. Soc. 103, 3223 (1981).
[34] W. Buchner, W. A. Schenk, Inorg. Chem. 23, 132
(1984).
[35] M. Nakamoto, K. Tanaka, T. Tanaka, Inorg. Chim. Acta
132, 193 (1987).
[36] E. W. Abel, I. S. Butler, J. G. Reid, J. Chem. Soc. 2068
(1963).
[37] A. E. Sa´nchez-Pela´ez, M. F. Perpin˜a´n, J. Organomet.
Chem. 405, 101 (1991).
[38] W. A. Schenk, J. Organomet. Chem. 179, 253 (1979).
[39] M. J. Aroney, I. E. Buys, M. S. Davies, T. W. Hambley,
J. Chem. Soc., Dalton Trans. 2827 (1994).
[40] V. Jonas, W. Thiel, Organometallics 17, 353 (1998),
and references cited therein.
[11] M. S. Reynolds, J. M. Berg, R. H. Holm, Inorg. Chem.
23, 3157 (1984).
[12] S. Yu, R. H. Holm, Inorg. Chem. 28, 4385 (1989).
[13] C. G. Young, S. A. Roberts, R. B. Ortega, J. H. Ene-
mark, J. Am. Chem. Soc. 109, 2938 (1987).
[14] D. C. Brower, T. L. Tonker, J. R. Morrow, D. S. Rivers,
J. L. Templeton, Organometallics 5, 1093 (1986).
[15] M. A. Ansari, J. Chandasekaran, S. Sarkar, Inorg.
Chem. 27, 763 (1988).
[16] R. Colton, G. G. Rose, Aust. J. Chem. 23, 1111 (1970).
[17] E. Carmona, K. Doppert, J. M. Marin, M. L. Poveda,
L. Sa´nchez, R. Sa´nchez-Delgado, Inorg. Chem. 23, 530
(1984).
[18] M. A. Bennett, I. W. Boyd, J. Organomet. Chem. 290,
165 (1985).
[19] P. K. Baker, S. G. Fraser, Trans. Met. Chem. 11, 273
(1986).
[20] B. C. Ward, J. L. Templeton, J. Am. Chem. Soc. 102,
1532 (1980).
[21] J. L. Templeton, B. C. Ward, J. Am. Chem. Soc. 102,
6568 (1980).
[41] F. A. Cotton, D. J. Darensbourg, W. H. Ilsley, Inorg.
Chem. 20, 578 (1981).
[42] M. J. Wovkulich, J. L. Atwood, L. Canada, J. D. At-
wood, Organometallics 4, 867 (1985).
[43] a) A. G. Orpen, N. G. Connelly, Organometallics
9, 1206 (1990); b) G. Frenking, K. Wichmann,
N. Fro¨hlich, J. Grobe, W. Golla, D. Le Van, B. Krebs,
M. La¨ge, Organometallics 21, 2921 (2002).
[44] G. Drosten, P. Mischke, J. Voß, Chem. Ber. 120, 1757
(1987).
[45] A. Scho¨berl, A. Wagner, in Houben-Weyl, Methoden
der organischen Chemie, 4. Aufl., Vol. 9, p. 945 (1955).
[46] G. M. Sheldrick, SHELX-97, Programs for Crystal
Structure Analysis, University of Go¨ttingen, Go¨ttin-
gen, Germany (1997).
[22] S. J. N. Burgmayer, J. L. Templeton, Inorg. Chem. 24,
2224 (1985).
Unauthenticated
Download Date | 7/12/17 4:06 PM