Syntheses of trifluoromethanethiolato platinum(II) complexes - Crystal structures of cis-Pt(SCF3)2(PPh3)2 and trans-Pt(SCF3)Cl(PPh3)2

Article abstract of DOI:10.1002/zaac.200500349

Ligand exchange reactions of cis-PtCl₂(PPh₃) ₂ and [NMe₄]SCF₃ in different ratios were studied. Depending on the stoichiometry reactions proceeded with formation of products expected for the chosen ratio, i. e. cis-Pt(SCF₃)Cl(PPh ₃)₂, cis-Pt(SCF₃)₂(PPh ₃)₂, and [NMe₄][Pt(SCF₃) ₃(PPh₃)]. Starting from cis-PtCl₂(MeCN) ₂ and [NMe₄]SCF₃ and adding PPh₃ after substitution, product mixtures were dominated by the corresponding trans-isomers. Results of the single crystal structure analyses of cis-Pt(SCF₃)₂(PPh₃)₂ and trans-Pt(SCF₃)Cl(PPh₃)₂ are discussed.

Full text of DOI:10.1002/zaac.200500349

DOI: 10.1002/zaac.200500349
Syntheses of Trifluoromethanethiolato Platinum(II) Complexes ؊ Crystal
Structures of cis-Pt(SCF3)2(PPh3)2 and trans-Pt(SCF3)Cl(PPh3)2
Natalya V. Kirija, Wieland Tyrrab*, Dieter Naumannb*, Ingo Pantenburgb, and Yurii L. Yagupolskiia
a Kiev / Ukraine, Institute of Organic Chemistry of the National Academy of Sciences of Ukraine,
b Köln / Germany, Institut für Anorganische Chemie der Universität
Received August 26th, 2005.
Dedicated to Professor Bernhard Lippert on the Occasion of his 60th Birthday
Abstract. Ligand exchange reactions of cis-PtCl2(PPh3)2 and
[NMe4]SCF3 in different ratios were studied. Depending on the
stoichiometry reactions proceeded with formation of products
expected for the chosen ratio, i. e. cis-Pt(SCF3)Cl(PPh3)2,
cis-Pt(SCF3)2(PPh3)2, and [NMe4][Pt(SCF3)3(PPh3)]. Starting from
cis-PtCl2(MeCN)2 and [NMe4]SCF3 and adding PPh3 after substi-
tution, product mixtures were dominated by the corresponding
trans-isomers. Results of the single crystal structure analyses of
cis-Pt(SCF3)2(PPh3)2 and trans-Pt(SCF3)Cl(PPh3)2 are discussed.
Keywords: Platinum; Trifluoromethanethiolate; Crystal structure
Introduction
Platinum(II) trifluoromethanethiolato derivatives are estab-
lished since middle of the 1970s [1Ϫ3]. Composition and
behaviour in solution was studied in detail. The compounds
were prepared either by oxidative addition of CF3SSCF3 to
Pt0(PPh3)4 or by halide substitutions using AgSCF3. The
easy accessibility of [NMe4]SCF3 [4] together with the low
solubility of tetramethylammonium halides, [NMe4]X (X ϭ
Cl, Br, I), in common organic solvents opens a new syn-
thetic approach for halide substitutions [4, 5]. Herein, we
report on the syntheses of trifluoromethanethiolato plati-
num derivatives.
Both known compounds were isolated as raw materials
and identified in comparison with literature data [1, 3]. In
addition to the known 19F NMR data [1, 3], the missing
data (Table 1) were determined from 1D-31P NMR,
2D-195Pt HMBC and 2D-13C HMQC spectra. The cis/trans
isomerization process is slow for both derivatives unless
triphenylphosphane is added.
In dichloromethane solution, replacement of the PPh3
ligands by SCF3 groups is not observed. The exchange is
finished on the stage of cis-Pt(SCF3)2(PPh3)2; excess of
[NMe4]SCF3 can be recovered unchanged from the solu-
tions.
Results and Discussion
Ligand exchange reactions between cis-PtCl2(PPh3)2
and [NMe4]SCF3
Replacement of one PPh3 group by a SCF3 group is
achieved using MeCN as a solvent. In this case, a salt with
the [Pt(SCF3)3(PPh3)]Ϫ anion is formed (Eq. (3)). However,
the compound [NMe4][Pt(SCF3)3(PPh3)] could not be iso-
lated in pure state but the anion was identified unambigu-
ously by 19F NMR spectroscopy. No evidence for the re-
placement of the second PPh3 ligand as observed in nucleo-
philic trifluoromethylations with the reagent combination
Me3SiCF3 / FϪ / glyme to give [Pt(CF3)4]2Ϫ [6] was found.
Reactions of cis-PtCl2(PPh3)2 and [NMe4]SCF3 at ambient
temperature in CH2Cl2 solutions allow more or less selec-
tive the syntheses of cis-Pt(SCF3)Cl(PPh3)2 and cis-
Pt(SCF3)2(PPh3)2 depending on the stoichiometry (Eq. (1)
and (2)).
* Dr. W. Tyrra, Prof. Dr. D. Naumann
Institut für Anorganische Chemie, Universität zu Köln
Greinstr. 6
D-50939 Köln
Fax: 0221-4705196
E-mail: tyrra@uni-koeln.de, d.naumann@uni-koeln.de
284
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Syntheses of Trifluoromethanethiolato Platinum(II) Complexes
Table 1 Compilation of NMR Chemical Shifts and Couplings of PtSCF3 Compounds (21 °C, CD2Cl2)
cis-Pt(SCF3)Cl(PPh3)2
trans-Pt(SCF3)Cl(PPh3)2
cis-Pt(SCF3)2(PPh3)2
trans-Pt(SCF3)2(PPh3)2
δ(19F)a)
Ϫ22.5
63
17.6 / 14.8
3033 / 3725
11 / ഠ 0.8
17
Ϫ4511
132.5
303
Ϫ26.5
118
20.2
2625
ഠ 1.5
Ϫ23.3
70
17.8
3147
Ϫ25.3
83
22.6
2634
ഠ 1.5
3JPt, F / Hz
δ(31P)
b)
1JPt, P / Hz
4JP, F / Hz
2JP, P / Hz
δ(195Pt)
b)
b)
b)
ഠ 7 / ഠ 2
Ϫ4480
129.3
303
Ϫ4621
132.7
303
Ϫ4673
129.9
303
δ(13C)
1JF, C / Hz
a) 19F NMR chemical shifts are in excellent agreement with literature data [1, 3]. b) First value: PPh3 standing trans to SCF3; second value: PPh3 standing cis
to SCF3.
The fact that in all spectra signals of cis-Pt(SCF3)2-
(PPh3)2 and SCF3Ϫ were observed together with the charac-
teristic signal groups of the anion suggests an equilibrium
between those species (Eq. (4)).
[11]. A view onto available structural data reveals that sul-
phur ligands carrying electron withdrawing groups cause an
elongation of the PtϪS bonds [12, 13] and a weak shorten-
ing of the PtϪP bonds. Significantly shorter PtϪS bonds
are found in derivatives, trans-Pt(SCϵC-t-Bu)2(PPh3)2 [14]
and trans-Pt(SC6F5)2(SEt2)2 [15]. A comparison of the mo-
lecular structures of cis- [16] and trans-PtCl2(PPh3)2 [17] to-
gether with the data given in [14] shows that PtϪP bond
lengths in trans-complexes are elongated by approximately
4 pm compared with the cis-derivatives.
Not even spectroscopic evidence was found for the
formation of [Pt(SCF3)4]2Ϫ if
a manifold excess of
[NMe4]SCF3 was used indicating that phosphorous donors
are better accepted by platinum(II) atoms than sulphur do-
nors although the sulphur ligands are negatively charged.
Molecular structure of cis-Pt(SCF3)2(PPh3)2
Cis-Pt(SCF3)2(PPh3)2 crystallizes in the monoclinic non
centrosymmetric space group P21 (No. 4) in the shape of
yellow blocks. A view on the molecule is depicted in Fig-
ure 1
Ligand exchange reactions between
cis-PtCl2(MeCN)2 and [NMe4]SCF3
In a similar manner as described above reactions of cis-
PtCl2(MeCN)2 and [NMe4]SCF3 in acetonitrile proceed
nearly exclusively with formation of the trans isomers after
addition of PPh3 to the reaction mixtures (Eq. (5, 6)).
Again, cis/trans isomerization proceeds very slowly.
Results of 1D-31P-NMR, 2D-195Pt-HMBC and 2D-13C-
HMQC are added to the record (Table 1), while 19F-NMR
values matched with those known from the literature [1Ϫ3].
Results of Crystal Structure Analyses
General remarks
The number of structurally analyzed compounds with the
kernel cis-Pt(SR)2(PRЈ3)2 is comparably large with respect
to the corresponding trans-isomers. This must be attributed
to the fact that merely bi-dentate ligands Ϫ either SϪS li-
gands [7, 8], PϪP ligands [9] or both types [7, 10] Ϫ were
used allowing exclusively cis-arrangement. Examples of mo-
tifs with exclusively mono-dentate S- and P-ligands are rare
Fig. 1 Molecular structure of cis-Pt(SCF3)2(PPh3)2 (1) (50 % pro-
bability ellipsoids; H-atoms have been omitted). Interatomic di-
stances in pm and angles in degrees (with estimated standard devia-
tions in parantheses):
Pt1ϪP1 228.5(2), Pt1ϪP2 228.0(2), Pt1ϪS1 238.1(2), Pt1ϪS2 237.7(2),
S1ϪC1 175.9(9), S2ϪC2 178.5(10), P1ϪPt1ϪP2 100.0(1), P2ϪPt1ϪS2
167.8(1), P1ϪPt1ϪS2 84.1(1), P2ϪPt1ϪS1 85.6(1), P1ϪPt1ϪS1 168.7(1),
S2ϪPt1ϪS1 92.4(1).
Z. Anorg. Allg. Chem. 2006, 284Ϫ288
© 2006 WILEY-VCH Verlag GmbH & Co. KGaA, Weinheim
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285

N. V. Kirij, W. Tyrra, D. Naumann, I. Pantenburg, Y. L. Yagupolskii
It forms square planar moieties with the bulky phos-
phane ligands in a cis orientation. The SCF3 substituents
exhibit anti conformation (Figure 1). The PtϪS bond
lengths of 237.7(2) and 238.1(2) pm are found to be at the
upper end of the normal range for bonds of this type
[7Ϫ13], while the PtϪP bond lengths of 228.0(2) and
228.5(2) pm are within the normal range [11Ϫ13]. Due to
the bulky triphenylphosphane group the PϪPtϪP angle of
100.0(1)° is more obtuse than the ideal right angle, while
the angles SϪPtϪP (84.1(1) and 85.6(1)°) become more
acute. The SϪPtϪS angle of 92.4(1)° only slightly deviates
from the ideal. The SϪC bonds of 175.9(9) and
178.5(10) pm are longer than in (Cp2MoH2)2AgSCF3
(173.4(5) pm [18]), another example of a derivative with a
terminal SCF3 moiety, while angles PtϪSϪC of 102.5(1)
and 102.8(1)° only slightly deviate from the AgϪSϪC angle
101.7(2)° found in (Cp2MoH2)2AgSCF3.
In the molecule the PPh3 groups are in a trans orien-
tation. As a consequence distortion around the platinum
centre is lower than in cis derivatives. The PϪPtϪP angle of
170.0(1)° deviates by 10° from linearity, while the SϪPtϪCl
angle of 175.6(1)° is even closer to 180°. Consequently,
SϪPtϪP (92.7(1) and 91.3(1)°) as well as ClϪPtϪP (88.5(1)
and 88.2(1)°) differ less from the right angle than compar-
able angles in the cis derivative, cis-Pt(SCF3)2(PPh3)2. The
PtϪP bond lengths of 232.0(1) and 232.7(1) pm are in abso-
lute agreement with data collected for related trans com-
pounds [14, 17], while the PtϪS bond length of 229.9(1) pm
is somewhat shorter than in other trans thiolato complexes
[14, 15]. On the other hand, the PtϪCl bond of 234.2(1) pm
is elongated by 3.4 pm compared with the parent molecule
trans-PtCl2(PPh3)2 [17]. These deviations might be attri-
buted to the more electron withdrawing effects of the chloro
ligand in comparison with the SCF3 group.
Experimental Part
Molecular structure of trans-Pt(SCF3)Cl(PPh3)2
Schlenk techniques were used throughout all manipulations. cis-
PtCl2(PPh3)2 (ABCR) and cis-PtCl2(MeCN)2 (Aldrich) were used
as received. [NMe4]SCF3 was prepared according to [4]. All sol-
vents were dried by routine methods prior to use. NMR spectra
were recorded on Bruker spectrometers AC200 and AVANCE 400
(1H, 19F, 13C, 31P, 195Pt). External standards were used in all cases
(1H, 13C: Me4Si; 19F: CCl3F; 31P: H3PO4 (85 %); 195Pt: Na2PtCl6).
Acetone-d6 was used as an external lock (5 mm tube) in reaction
control measurements while an original sample of the reaction mix-
ture was measured in a 4 mm insert. HMQC and HMBC tech-
niques were employed to determine the 195Pt chemical shifts and
to locate the SCF3 groups. Complicated coupling patterns were cal-
culated using the program gNMR [19]
Trans-Pt(SCF3)Cl(PPh3)2 crystallizes in the monoclinic
centrosymmetric space group P21/c (No. 14) in the shape of
yellow polyhedrons. A view on the molecule is depicted in
Figure 2.
Single crystals were grown from saturated dichloromethane solu-
tions of the crude materials at Ϫ21 °C. Both compounds cis-
Pt(SCF3)2(PPh3)2 (1) and trans-Pt(SCF3)Cl(PPh3)2 (2) form yellow
single crystals which were sealed in glass capillaries and the suit-
ability was checked with the help of an IP-diffractometer (STOE
IPDS II) [20, 21]. The same device was used to collect the reflection
data of the respective best specimen. Structure solution and refine-
ment were carried out using the programs SIR-92 [22]
and SHELXL-97 [23]. Details of crystal data and structure refine-
ment parameters for cis-Pt(SCF3)2(PPh3)2 (1) and trans-
Pt(SCF3)Cl(PPh3)2 (2) are summarised in Table 2.
Synthesis of cis-Pt(SCF3)Cl(PPh3)2
Fig. 2 Molecular structure of trans-Pt(SCF3)Cl(PPh3)2 ·2CH2Cl2
(2) (50 % probability ellipsoids; H-atoms and CH2Cl2 molecules
have been omitted). Interatomic distances in pm and angles in de-
grees (with estimated standard deviations in parantheses):
To a solution of 0.79 g (1.0 mmol) cis-PtCl2(PPh3)2 in 10 mL
CH2Cl2 0.19 g (1.1 mmol) [NMe4]SCF3 were added at room
temperature. The mixture was stirred for 30 minutes. [NMe4]Cl
which has precipitated was filtered off and the crude material
dried. Analysis by 19F and 31P NMR spectroscopic methods re-
Pt1ϪS1 229.9(1), Pt1ϪP1 232.0(1), Pt1ϪP2 232.7(1), Pt1ϪCl1 234.2(1),
S1ϪC1 176.2(5), S1ϪPt1ϪP1 92.7(1), S1ϪPt1ϪP2 91.3(1), P1ϪPt1ϪP2
170.0(1), S1ϪPt1ϪCl1 175.6(1), P1ϪPt1ϪCl1 88.5(1), P2ϪPt1ϪCl1 88.2(1).
vealed
a composition of 70 % cis-Pt(SCF3)Cl(PPh3)2, 12 %
cis-Pt(SCF3)2(PPh3)2 and 18 % of the starting material,
cis-PtCl2(PPh3)2.
Each molecule has a square planar arrangement of the
ligands around the platinum centre. No contacts are found
between adjacent molecules. Two dichloromethane mol-
ecules co-crystallize. While one has a fixed position, the
other is disordered.
Synthesis of cis-Pt(SCF3)2(PPh3)2
In
a similar manner as described above, 0.38 g (2.2 mmol)
[NMe4]SCF3 were added to a solution of 0.79 g (1.0 mmol)
286
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Syntheses of Trifluoromethanethiolato Platinum(II) Complexes
crude material dried. The composition of the crude material was
determined to consist of 4 % cis-Pt(SCF3)Cl(PPh3)2, 92 %
cis-Pt(SCF3)2(PPh3)2 and 4 % of the starting material,
cis-PtCl2(PPh3)2.
Table 2 Crystal Data and Structure Refinement Parameters for
cis-Pt(SCF3)2(PPh3)2 (1) and trans-Pt(SCF3)Cl(PPh3)2 ·2CH2Cl2 (2)
1
2
empirical formula
C38H30F6P2S2Pt
C39H34F3P2SCl5Pt
1026.00
formula mass / g molϪ1 921.77
Attempted synthesis of [NMe4][Pt(SCF3)3(PPh3)]
data collection
diffractometer
radiation
temperature / K
index range
STOE IPDS II
Mo-Kα (graphite monochromator, λ ϭ 71.073 pm)
150(2)
Ϫ11 Յ h Յ 12
Ϫ25 Յ k Յ 25
Ϫ12 Յ l Յ 12
STOE IPDS II
To a solution of 0.79 g (1.0 mmol) cis-PtCl2(PPh3)2 in 10 mL
MeCN, 0.57 g (3.3 mmol) [NMe4]SCF3 were added. Stirring was
continued for 24 hours. After this period, two multiplets in the
150(2)
Ϫ20 Յ h Յ 20
Ϫ18 Յ k Յ 18
Ϫ22 Յ l Յ 22
integrative ratio 1:2 were detected for the anion beside the low-
Ϫ
intensity resonances of cis-Pt(SCF3)2(PPh3)2 and SCF3
.
rotation angle range
0° Յ ω Յ 180°; γ ϭ 0° 0° Յ ω Յ 180°; γ ϭ 0°
3
4
19F NMR (MeCN): δ ϭ Ϫ20.2 (m, 3F, JPt, F ϭ 77 Hz; JP, F
ϭ
0° Յ ω Յ 180°; γ ϭ 90° 0° Յ ω Յ 29°; γ ϭ 90°
3
4
increment
no. of images
Δω ϭ 1°
360
Δω ϭ 1°
209
14 Hz), Ϫ23.0 (m, 6F, JPt, F ϭ 88 Hz; JP, F ഠ 1 Hz).
exposure time / min
detector distance / mm
2θ range / deg
total data collected
unique data
observed data
Rmerg
4
120
1.9 Ϫ 54.8
24365
7654
7345
0.0735
4
120
1.9 Ϫ 54.8
33936
8286
7071
0.0346
Syntheses of trans-Pt(SCF3)Cl(PPh3)2 and trans-
Pt(SCF3)2(PPh3)2
0.35 g (1.0 mmol) cis-PtCl2(MeCN)2 were dissolved in 10 mL
MeCN. 0.19 g (1.1 mmol) respective 0.38 g (2.2 mmol)
[NMe4]SCF3 were added. 0.52 g (2.0 mmol) PPh3 were added to
both reaction mixtures. After one hour stirring was terminated, all
insoluble material was filtered off and all volatile materials were
removed in vacuo giving raw materials of the composition
92 % trans-Pt(SCF3)Cl(PPh3)2 and 8 % trans-Pt(SCF3)2(PPh3)2,
respectively 8 % trans-Pt(SCF3)Cl(PPh3)2 and 92 % trans-
Pt(SCF3)2(PPh3)2.
absorption correction
transmission min / max 0.2244 / 0.5848
numerical, after crystal shape optimization [20, 21]
0.3673 / 0.6493
crystallographic data
crystal size / mm
colour, habit
crystal system
space group
a / pm
b / pm
c / pm
0.3·0.3·0.2
yellow, block
monoclinic
P21 (no. 4)
954.4(1)
1992.1(1)
1011.6(1)
111.07(1)
1794.7(2)
2
0.2·0.2·0.1
yellow, polyhedron
monoclinic
P21/c (no. 14)
1567.9(1)
1481.5(1)
1787.3(1)
114.61(1)
3774.2(3)
4
β / deg
NMR data of all compounds are summarized in Table 1.
volume / 106 pm3
Z
ρcalc / g cmϪ3
μ / mmϪ1
F(000)
1.706
4.173
904
1.806
4.257
2016
Acknowledgement. This work was generously supported by the
Deutsche Forschungsgemeinschaft (436 UKR 113).
structure analysis and
refinement*
structure determination
no. of variables
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Pt(SCF3)2(PPh3)2)
and
CCDC
275937
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from the Cambridge Crystallographic Data Centre via
www.ccdc.cam.ac.uk/datarequest/cif.
288
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© 2006 WILEY-VCH Verlag GmbH & Co. KGaA, Weinheim
Z. Anorg. Allg. Chem. 2006, 284Ϫ288