Bis(trifluoromethylselenato(0))metallates(I) of silver and gold, [M(SeCF3)2]- (M = Ag, Au)

Article abstract of DOI:10.1002/zaac.200500115

Ligand exchange reactions of [NMe₄]SeCF₃ or [Cs(15-Crown-5)₂]SeCF₃ with Ag[BF₄] and AuCl gave the corresponding bis(trifluoromethylselenato(0))metallates [Ag(SeCF ₃)₂]^- and [Au(SeCF₃) ₂]^- in good yields. All compounds were characterized by NMR spectroscopic means and ESI mass spectrometry. Cation exchange with [PNP]Cl ([PNP] = bis(triphenylphosphoranylidene)-ammonium) yielded the corresponding [PNP] salts. The single crystal structure of [PNP][Au(SeCF₃) ₂] was elucidated by XRD measurements (P2₁/a; a = 1712.0(1), b = 1142.5(1), c = 2013.6(1) pm; β = 112.10(1)°; Z = 4).

Full text of DOI:10.1002/zaac.200500115

Bis(trifluoromethylselenato(0))metallates(I) of Silver and Gold, [M(SeCF3)2]؊
(M ؍ Ag, Au)
Dieter Naumanna,*, Wieland Tyrraa,*, Silke Quadta, Sigrid Busleia, Ingo Pantenburga, and Mathias Schäferb
Köln, a Institut für Anorganische Chemie und b Institut für Organische Chemie der Universität
Received March 14th, 2005.
Dedicated to Professor Herbert W. Roesky on the Occasion of his 70th Birthday
Abstract. Ligand exchange reactions of [NMe4]SeCF3 or [Cs(15-
stal structure of [PNP][Au(SeCF3)2] was elucidated by XRD me-
asurements (P21/a; a ϭ 1712.0(1), b ϭ 1142.5(1), c ϭ 2013.6(1) pm;
β ϭ 112.10(1)°; Z ϭ 4).
Crown-5)2]SeCF3 with Ag[BF4] and AuCl gave the corresponding
bis(trifluoromethylselenato(0))metallates
[Ag(SeCF3)2]Ϫ
and
[Au(SeCF3)2]Ϫ in good yields. All compounds were characterized
by NMR spectroscopic means and ESI mass spectrometry. Cation
exchange with [PNP]Cl ([PNP] ϭ bis(triphenylphosphoranylidene)-
ammonium) yielded the corresponding [PNP] salts. The single cry-
Keywords: Silver; Gold; Trifluoromethylselenates(0); Synthesis;
Structure
F2CϭSe ϩ AgF Ǟ AgSeCF3
(3)
Introduction
In previous papers we have presented a more or less general
approach for the syntheses of trifluoromethylchalcogen-
ates(0), [ECF3]Ϫ (E ϭ S [1], Se [2], Te [3]) (Eq. (1)) starting
from tetramethylammonium fluoride, [NMe4]F, trimethyl(-
trifluoromethyl)silane, Me3SiCF3, and the corresponding
chalcogen.
AgSeCF3 has alternatively been prepared from the reac-
tions of B(SeCF3)3 and AgF [7] (Eq. (4)) or AgCF3 and
elemental selenium [8] (Eq. (5)).
150 °C
B(SeCF3)3 ϩ 3 AgF ——Ǟ 3 AgSeCF3 ϩ BF3
(4)
(5)
Me3SiCF3 ϩ E ϩ [NMe4]F Ǟ [NMe4]ECF3 ϩ Me3SiF
(1)
r.t.
AgCF3 ϩ Se ——Ǟ AgSeCF3 ϩ ...
EtCN
These convenient syntheses open new possibilities to in-
vestigate ligand exchange reactions of these derivatives with
inorganic [4] and organic [5] substrates. The good access to
the corresponding tellurates [4] encouraged us to investigate
bis(trifluoromethylselenato(0))metallates of group 11 ele-
ments.
CuSeCF3 [6] or AgSeCF3 [7] have been used for the direct
introduction of a SeCF3 group into organic, inorganic and
metal-organic compounds under different conditions but
characterization is solely based on 19F NMR spectroscopic
data. CuSeCF3 was prepared via the reaction of (CF3Se)2
and elemental copper [6] according to Eq. (2).
In this paper, we report about syntheses and characteriz-
ation of salts with the anions [M(SeCF3)2]Ϫ (M ϭ Ag, Au).
Results and Discussion
The number of selenato complexes of group 11 elements is
still limited to few structurally characterized examples
[9Ϫ11]. Among them mainly polymeric compounds of gen-
eral formula [AgSeR]n (n ϭ 4, 6, 8, ϱ; R ϭ organic group)
are mentioned. By contrast, gold(I) chemistry with these
class of ligands is dominated by mononuclear [9] and di-
nuclear [10] complexes incorporating organophosphorus li-
gands. To our knowledge, the carborane-selenato aurate(I),
[Au(SeC2B10H11)2]Ϫ, displays the only (so far not structur-
ally characterized) example of a gold species with the gold
atom exclusively co-ordinated by two selenium atoms [11].
In a similar manner as described for the corresponding
trifluoromethyl tellurato derivatives [4], the tetramethylam-
monium derivatives [NMe4][Ag(SeCF3)2] and [NMe4][Au(-
SeCF3)2] are obtained from the reactions of [NMe4]SeCF3
with Ag[BF4] and AuCl, respectively, in 2 : 1 molar ratios.
Reactions with [Cs(15-crown-5)2]SeCF3 proceed in a similar
manner but do not allow the isolation of pure compounds
(Eq. (6)).
CF3SeSeCF3 ϩ 2 Cu Ǟ 2 CuSeCF3
(2)
Although reactions of C(Se)F2 with AgF are mentioned
in the literature [7] (Eq (3)), few details are reported about
stability and reactivity of the resulting compound, Ag-
SeCF3.
* Prof. Dr. Dieter Naumann; Dr. Wieland Tyrra
Institut für Anorganische Chemie
Universität zu Köln
Greinstr. 6
D-50939 Köln
E-mail addresses: d.naumann@uni-koeln.de; tyrra@uni-koeln.de
Z. Anorg. Allg. Chem. 2005, 631, 2733Ϫ2737
DOI: 10.1002/zaac.200500115
 2005 WILEY-VCH Verlag GmbH & Co. KGaA, 69451 Weinheim
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r.t.
MX ϩ 2[CAT]SeCF3 ——Ǟ [CAT][M(SeCF3)2] ϩ [CAT]X
(6)
EtCN
MX ϭ Ag[BF4], AuCl; [CAT] ϭ [NMe4], [Cs(15-Crown-5)2]
The low solubility of [NMe4][BF4] and [NMe4]Cl, respec-
tively, in EtCN opens a direct access to the corresponding
selenato metallates after distilling off all volatile compo-
nents under reduced pressure. Unfortunately, the cesium
salts [Cs(15-crown-5)2][Ag(SeCF3)2] and [Cs(15-crown-
5)2][BF4] respectively [Cs(15-crown-5)2][Au(SeCF3)2] and
[Cs(15-crown-5)2]Cl could not be separated from each other
so far neither by extraction nor by fractionated crystalliza-
tion.
Ligand exchange of [NMe4] into [PNP] proceeds nearly
quantitatively again making use of the low solubility of
[NMe4]Cl in MeCN (Eq. (7)).
r.t.
[NMe4][M(SeCF3)2] ϩ [PNP]Cl —Ǟ [PNP][M(SeCF3)2] ϩ [NMe4]Cl
MeCN
(7)
Fig. 1 View of [PNP][Au(SeCF3)2] showing the labeling scheme of
the anion and the displacement ellipsoids at the 50 % probability
level; interatomic distances/pm and angles/deg (with estimated
standard deviations in parentheses):
M ϭ Ag, Au; PNP ϭ Ph3PϭNϭPPh3
While the [NMe4] and [PNP] derivatives are isolated as
colourless to ochre solids decomposing above 100 °C,
[Cs(15-Crown-5)2][M(SeCF3)2] (M ϭ Ag, Au) form waxy
materials melting not significantly above room temperature
(Ag) or even below (Au) due to significant impurities of
[Cs(15-crown-5)2][BF4] and [Cs(15-crown-5)2]Cl, respec-
tively.
Se1-Au1 238.8(1), Se2-Au1 239.3(1), Se1-C1 190.9(7), Se2-C2 191.8(6), C1-
F11 133.3(7), C1-F12 133.7(8), C1-F13 135.6(7), C2-F23 133.3(7), C2-F22
134.3(7), C2-F21 135.0(6), N1-P1 158.4(4), N1-P2 158.7(4), Se1-Au1-Se2
172.7(1), Au1-Se1-C1 102.7(2), Au1-Se2-C2 101.3(2), P1-N1-P2 138.0(3). H-
atoms are omitted for clarity.
Room temperature 19F, 77Se and 13C NMR spectra of
[CAT][M(SeCF3)2] (CAT ϭ NMe4, PNP, Cs(15-crown-5)2)
in CD3CN at room temperature do not deviate from each
other indicating complete dissociation. Sharp signals are
detected for the argentate at δ(19F) ϭ Ϫ15.8 (s, 2J(77Se,F)ϭ
54 Hz, W1/2 ഠ 8 Hz), δ(77Se) ϭ 128 (q, 2J(77Se,F) ϭ 54 Hz)
and δ(13C) ϭ 125.9 (q, 1J(F,C) ϭ 329 Hz) and the aurate at
δ(19F) ϭ Ϫ17.0 (s, 2J(77Se,F)ϭ 44 Hz, W1/2 ഠ 5 Hz),
2
δ(77Se) ϭ 237 (q, J(77Se,F) ϭ 44 Hz) and δ(13C) ϭ 126.8
1
(q, J(F,C) ϭ 330 Hz)
The negative ESI mass spectrum of the argentate
[Ag(SeCF3)2]Ϫ shows the anion peak (MϪ ϭ 405 m/z) with
100 % intensity and the peak of [Ag2(SeCF3)3]Ϫ with 76 %
intensity. No evidence is found for higher aggregates as ob-
served in mass spectra of the corresponding tellurium de-
rivative [4]. Signals of low intensity with masses of 530 and
275 m/z indicate the formation of the ions [Ag2(SeCF3)2F]Ϫ
and [Ag(SeCF3)F]Ϫ, respectively, which are formed by loss
of SeCF2.
Fig. 2 The packing diagram for [PNP][Au(SeCF3)2] viewed along
b-axis.
that [Au(SeCF3)2]Ϫ is monomeric in solution and does not
tend to build higher aggregates as the argentate does.
Among the selenato gold compounds analyzed by XRD
measurements [10, 11], [PNP][Au(SeCF3)2] (Figures 1 and
2, Table 1) represents the first example of a gold-selenato
The mass spectrum of the aurate, [Au(SeCF3)2]Ϫ, is
dominated by the anion peak (100 %) and a peak of 34 %
intensity for [Au(SeCF3)F]Ϫ. This fragmentation is similar
to that of the corresponding tellurato aurate [4] exhibiting
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Z. Anorg. Allg. Chem. 2005, 631, 2733Ϫ2737

Table 1 Crystal Data and Structure Refinement Parameters for
[PNP][Au(SeCF3)2]
Au-Se bond lengths of 238.8 pm and 239.3 pm are
shorter than those in the derivative [Au(SeC2B10H11)PPh3]
(241.7 pm) [11] and further compounds mentioned [10].
This shortening might be attributed to the strong electron
withdrawing nature of the trifluoromethyl group bond to
selenium compared with less electron withdrawing groups
in the other structures.
[PNP][Au(SeCF3)2]
empirical formula
formula mass /g molϪ1
data collection
diffractometer
radiation
temperature /K
index range
C38H30NF6P2AuSe2
1031.46
STOE IPDS II
Mo-Kα, λ ϭ 71.073 pm
150(2)
Ϫ21 Յ h Յ 19
Ϫ14 Յ k Յ 14
Ϫ25 Յ l Յ 25
0° Յ ω Յ 180°; γ ϭ 0°
0° Յ ω Յ 94°; γ ϭ 90°
∆ω ϭ 1°
Experimental Part
Schlenk techniques were used throughout all manipulations. NMR
spectra were recorded on Bruker AC 200 (1H, 19F, 13C) and AV-
ANCE 400 (77Se) spectrometers. External standards were used in
all cases (1H, 13C: Me4Si; 19F: CCl3F; 77Se: Me2Se). Acetone-d6
was used as an external lock (5 mm tube) in reaction control meas-
urements while an original sample of the reaction mixture was
measured in a 4 mm insert. Negative ESI mass spectra in MeCN
solutions were run on a Finnigan MAT 900 apparatus with a flow
rate of 2 µl/min. Intensities are referenced to the most intense peak
of a group. Isotope patterns for comparison were calculated with
the program Isopro [12]. Visible decomposition points were deter-
mined using the Stuart melting point apparatus SMP10. C, H and
N analyses were carried out with a HEKAtech Euro EA 3000 ap-
paratus. Details of crystal data and structure refinement param-
eters for [PNP][Au(SeCF3)2] are summarised in Table 1.
rotation angle range
increment
no. of images
274
exposure time /min
detector distance /mm
2·θ range /deg
total data collected
unique data
observed data
Rmerg
4
120
1.9 Ϫ 54.8
42807
7994
6811
0.0817
absorption correction
numerical, after crystal shape
optimization [16, 17]
0.0941 / 0.3815
transmission min / max
crystallographic data [18]
crystal size /mm
colour, habit
crystal system
space group
a /pm
b /pm
c /pm
0.2 · 0.2 · 0.2
colourless, block
monoclinic
P21/a (no. 14)
1711.98(6)
1142.54(4)
2013.64(9)
112.097(3)
3.6494(2)
4
The following derivatives were prepared according to literature pro-
cedure: [NMe4]SeCF3 [2], [PNP]Cl [13], AuCl [14]. Ag[BF4]
(Apollo) was used as received.
β /deg
volume /nm3
Z
ρcalc /Mg mϪ3
µ /mmϪ1
1.877
6.174
Synthesis of bis(15-crown-5)cesium
trifluoromethylselenate(0), [Cs(15-Crown-5)2]SeCF3
F(000)
1984
structure analysis and refinement*
structure determination
no. of variables
R indexes [I>2σI]
wR2 ϭ 0.1108
R indexes (all data)
R1 ϭ 0.0517
3.80 g (25 mmol) well-dried and finely powdered CsF are dissolved
in a solution of 9.74 ml (50 mmol) 15-crown-5 in 200 ml dimethox-
yethane at ambient temperature. After cooling to Ϫ30 °C, 1.97 g
(25 mmol) red selenium are added in one portion. Finally 3.75 ml
(28 mmol) Me3SiCF3 are poured into the well-stirred suspension.
Stirring is maintained for 30 minutes at Ϫ30 °C and afterwards the
reaction mixture is allowed to warm to room temperature over-
night. After a total reaction time of approximately 16 hours the
colour of the mixture has changed into orange and some grey-
ochre solid has precipitated. The composition is controlled by 19F
NMR spectroscopy. Volatile products (Me3SiF, excess Me3SiCF3,
traces of CF3H and Se(CF3)2) and the solvent are removed under
reduced pressure giving a grey residue. [Cs(15-crown-5)2]SeCF3 is
separated from the residue by repeated extraction with MeCN (3-
4 times). The selenate crystallizes upon removal of MeCN under
reduced pressure at ambient temperature. The pale ochre product
is vacuum dried and obtained in a yield of 30 % (5.40 g).
SIR-92 [19] and SHELX-97 [20]
453
R1 ϭ 0.0443
wR2 ϭ 0.1145
goodness of fit (Sobs
goodness of fit (Sall
)
)
1.029
1.029
Ϫ1.794 / 5.410
largest difference map
hole / peak /e 10Ϫ6pmϪ3
R1 ϭ Σ ʈFoΗ - ΗFcʈ / Σ ΗFoΗ, wR2 ϭ [ Σ w ( ΗFoΗ2 - ΗFcΗ2 )2 / Σ w ( ΗFoΗ2
)2 ]1/2, S2 ϭ [ Σ w ( ΗFoΗ2 - ΗFcΗ2 )2 / (n-p) ]1/2, with w ϭ 1 / [σ2 (Fo)2
ϩ (0.0428·P)2 ϩ 18.5046·P], were P ϭ (Fo2 ϩ 2Fc ) / 3. Fc* ϭ k Fc
2
[1ϩ0,001 · ΗFcΗ2 λ3 / sin(2θ)]Ϫ1/4
.
* All H atoms were placed in idealized positions and constrained
to ride on their parent atom.
compound with a discrete quasi-linear Se-Au-Se unit
(172.7°) where neither gold atoms nor selenium atoms are
co-ordinated by more than two ligands. It crystallizes isos-
tructurally with the corresponding tellurato aurate in the
monoclinic space group P21/a (a ϭ 1712.0(1), b ϭ
1142.5(1), c ϭ 2013.6(1) pm; β ϭ 112.10(1)°; Z ϭ 4) with
well separated cations and anions. In the crystal packing,
the anions are layered in channels formed by the space-
demanding [PNP]ϩ ions.
Bis(15-crown-5)cesium trifluoromethylselenate(0),
[Cs(15-Crown-5)2]SeCF3
Pale ochre crystals, visible m.p. 102-104 °C (molten glas-capillary),
160-165 °C (onset of dec.).
NMR data (CD3CN) and MS spectra (neg. ESI) of the anion are
in absolute agreement with those published in a previous paper [2].
1
NMR data for [Cs(15-crown-5)2]ϩ: H NMR (CD3CN): δ ϭ 3.56
1
(s). 13C NMR (CD3CN): δ ϭ 69.5 (t, J(C,H) ϭ 141 Hz).
Z. Anorg. Allg. Chem. 2005, 631, 2733Ϫ2737
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Analytical data C21H40F3O10CsSe (721.40): C 35.69 (calc. 34.96);
H 5.86 (5.59) %.
109Ag-NMR spectra or 109Ag, 19F HMBC spectra failed through
rapid ligand exchange of the SeCF3-groups.
Elemental analysis for C38H30F6NAgP2Se2 (942.39) at ambient
temperature was not sufficient due to rapid decomposition of the
compound on exposure to ambient atmosphere.
Reactions of [NMe4]SeCF3 and Ag[BF4]
In a typical procedure, 0.57 g (2.57 mmol) [NMe4]SeCF3 were dis-
solved in 10 ml EtCN at ambient temperature. Directly after ad-
dition of 0.25 g (1.28 mmol) Ag[BF4] to the primarily rose-coloured
solution, a colourless solid began to precipitate, while the colour
of the reaction mixture changed into pale yellow. The reaction mix-
ture was stirred for one hour and ongoing of the reaction was
monitored by 19F NMR spectroscopy. Stirring was terminated after
approximately two hours and [NMe4][BF4] was filtered off. Evapor-
ation of MeCN in vacuo afforded [NMe4][Ag(SeCF3)2] in 91 %
yield (0.56 g) as an ochre solid.
Reactions of [Cs(15-crown-5)2]SeCF3 and Ag[BF4]
To a well stirred solution of pale brown solution of 0.69 g
(0.96 mmol) [Cs(15-Crown-5)2]SeCF3 in 10 ml EtCN 0.10 g
(0.51 mmol) Ag[BF4] was added in one portion at room tempera-
ture. The colour of the mixture changed into dark brown directly
after addition of the silver salt. Stirring was maintained for one
hour; during this period the reaction mixture became turbid. The
solution was decanted from a minor amount of solid and evapo-
rated to dryness. Repeated washing of the residue with diethylether
followed by evaporation gave a waxy material which contained ca.
55 % [Cs(15-Crown-5)2][Ag(SeCF3)2] and ca. 45 % [Cs(15-Crown-
5)2][BF4] (19F NMR; elemental analysis).
Tetramethylammonium[bis(trifluoromethylselenato(0))
argentate(I)], [NMe4][Ag(SeCF3)2]
NMR data (CD3CN) of the product mixture were in absolute
agreement with those given above.
Colourless crystals, visible m.p. 170 °C (onset of decomposition
(darkening); complete decomposition with gas evolution at 195 Ϫ
200 °C).
Analytical data C6H12AgF6NSe2 (477.95): C 15.71 (calc. 15.08); H
2.67 (2.53); N 2.97 (2.93) %.
Reactions of [NMe4]SeCF3 and AuCl
In a similar manner as described for the argentate, [NMe4][Au(-
SeCF3)2] was prepared from 0.21 g (0.90 mmol) AuCl and 0.40 g
(1.80 mmol) [NMe4]SeCF3 in 78 % yield (0.40 g) after re-crystalli-
zation from cold MeCN as a colourless solid.
2
1
19F NMR (CD3CN): δ ϭ Ϫ15.9 (s, J(77Se,F) ϭ 54 Hz; J(F,C) ϭ
322.9 Hz). 1H NMR (CD3CN): δ ϭ 3.16 (s). 77Se NMR (CD3CN):
δ ϭ 128 (q, 2J(Se,F) ϭ 54 Hz). 13C NMR (CD3CN): δ ϭ 125.9
1
1
(q, J(F,C) ϭ 329 Hz, CF3), 55.6 (q of decets, J(C,H) ϭ 144 Hz,
3J(C,H) ϭ 3.5 Hz, NMe4).
Tetramethylammonium[bis(trifluoromethylselenato(0))
aurate(I)], [NMe4][Au(SeCF3)2]
MS (neg. ESI in MeCN): m/z ϭ 659.9 ([Ag2(SeCF3)3]Ϫ, 76 %),
530.1 ([Ag2(SeCF3)2F]Ϫ, 4 %); 404.5 ([Ag(SeCF3)2]Ϫ, 100 %), 274.7
([Ag(SeCF3)F]Ϫ, 9 %).
Colourless crystals, visible m.p. 120 °C (onset of decomposition
(darkening)).
All attempts to grow single crystals suitable for XRD measure-
ments failed.
Analytical data C6H12AuF6NSe2 (567.04) C 13.41 (calc. 12.71); H,
2.60 (2.13); N 2.87 (2.47) %.
2
1
19F NMR (CD3CN): δ ϭ Ϫ17.0 (s, J(77Se,F) ϭ 44 Hz; J(F,C) ϭ
Synthesis of [PNP][Ag(SeCF3)2]
329 Hz). H NMR (CD3CN): δ ϭ 3.16 (s). 77Se NMR (CD3CN):
1
δ ϭ 237 (q, 2J(Se,F) ϭ 44 Hz). 13C NMR (CD3CN): δ ϭ 126.8
To a solution of 0.13 g (0.27 mmol) [NMe4][Ag(SeCF3)2] in 5 ml
MeCN a solution of 0.16 g (0.28 mmol) [PNP]Cl in 5 ml MeCN
was added in one portion. Directly after mixing both solutions, the
reaction mixture became turbid and stirring was maintained for 30
minutes until the signal of [NMe4]ϩ could no more be detected in
the 1H-NMR spectrum. After inert filtration from [NMe4]Cl, all
volatile components were distilled off in vacuo giving [PNP][Ag(-
SeCF3)2] as a pale-brown crystalline solid in 90 % yield (0.23 g).
1
1
(q, J(F,C) ϭ 330 Hz, CF3), 55.6 (q of decets, J(C,H) ϭ 144 Hz,
3J(C,H) ϭ 3.5 Hz, NMe4).
MS (neg. ESI in MeCN): m/z ϭ 494.4 ([Au(SeCF3)2]Ϫ, 100 %),
364.6 ([Au(SeCF3)F]Ϫ, 34 %).
Synthesis of [PNP][Au(SeCF3)2]
In the same manner as described for the argentate, the tetrameth-
ylammonium derivative was converted into the [PNP]-salt starting
from 0.31 g (0.55 mmol) [NMe4][Au(SeCF3)2] and 0.31 g
(0.55 mmol) [PNP]Cl. 0.48 g (85 % yield) of [PNP][Au(SeCF3)2]
were collected of sufficient purity. Re-crystallisation from MeCN
(Ϫ21 °C) gave single crystals suitable for XRD measurements.
Bis(triphenylphosphoranyliden)ammonium
bis(trifluoromethyselenato(0))argentate(I),
[PNP][Ag(SeCF3)2]
Pale brown crystals, visible m.p. 135 °C (onset of decomposition,
> 170 °C complete decomposition with gas evolution).
NMR data collected at room temperature in CD3CN for the cation
[PNP]ϩ (1H, 13C, 31P) are in absolute agreement with literature data
[15], those of the anion [Ag(SeCF3)2]Ϫ (13C, 19F, 77Se) in absolute
agreement with those of the tetramethylammonium salt. Also val-
ues in negative ESI mass spectra do not deviate from those ob-
tained for the tetramethylammonium salt. Attempts to measure 1D-
Bis(triphenylphosphoranyliden)ammonium
bis(trifluoromethylselenato(0))aurate(I),
[PNP][Au(SeCF3)2]
Pale orange-brown crystals, visible m.p. 115 °C (onset of decompo-
sition(darkening)).
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NMR data collected at room temperature in CD3CN for the cation
[PNP]ϩ (1H, 13C, 31P) are in absolute agreement with literature data
[15], those of the anion [Au(SeCF3)2]Ϫ (13C, 19F, 77Se) as well as
values in the negative ESI mass spectra are in absolute agreement
with those obtained for the tetramethylammonium salt.
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Bonasia, G. P. Mitchell, F. J. Hollander, J. Arnold, Inorg.
Chem. 1994, 33, 1797Ϫ1802.
[10] a) S. Canales, O. Crespo, M. C. Gimeno, P. G. Jones, A. La-
guna, Inorg. Chem. 2004, 43, 7234Ϫ7238; b) W. Eikens, C. Ki-
enitz, P. G. Jones, C. Thöne, J. Chem. Soc., Dalton Trans. 1994,
83Ϫ90; c) P. G. Jones, J. Lautner, C. Thöne, Z. Kristallogr.
1993, 208, 354Ϫ357; d) P. G. Jones, C. Thöne, Z. Naturforsch.
1992, 47b, 600Ϫ602; e) P. G. Jones, C. Thöne, Chem. Ber. 1990,
123, 1975Ϫ1978.
Analytical data C38H30F6NAuP2Se2 (1031.49): C 46.75 (calc.
47.92); H 3.57 (3.17); N 2.16 (1.47) %.
Reactions of [Cs(15-crown-5)2]SeCF3 and AuCl
To a well stirred solution of pale brown solution of 0.62 g
(0.86 mmol) [Cs(15-Crown-5)2]SeCF3 in 10 ml EtCN 0.10 g
(0.43 mmol) AuCl was added in one portion at room temperature.
Directly after addition of AuCl, small quantities of a colourless
solid were formed. Stirring of the reaction mixture was terminated
as soon as all AuCl had been visibly dissolved. The mixture was
decanted and all volatile components were removed in vacuo. The
oily residue was washed twice with n-pentane and afterwards dis-
solved in diethylether. Storage of the ethereal solution overnight at
Ϫ21 °C led to the precipitation of some colourless crystalline mate-
rial which readily dissolved upon warming to ambient temperature.
Evaporation of diethylether gave an orange-brown waxy material
consisting of ca. 40 % [Cs(15-Crown-5)2][Au(SeCF3)2] and ca. 60 %
[Cs(15-Crown-5)2]Cl (elemental analysis).
[11] S. Canales, O. Crespo, M. C. Gimeno, P. G. Jones, A. Laguna,
P. Rom e ro, Dalton Trans. 2003, 4525Ϫ4528.
[12] M. Senko, Isopro 3.0, Shareware, Sunnyvale, CA.
[13] J.K. Ruff, W.J. Schlientz, Inorg. Synth. 1974, 15, 84Ϫ96.
[14] G. Brauer, Handbuch der Präparativen Anorganischen Chemie,
2nd ed., Vol. II, F. Enke, Stuttgart 1962, p. 927.
NMR data (CD3CN) of the product mixture were in absolute
agreement with those given above.
Acknowledgements. Financial support by the Fonds der Chem-
[15] Z.-H. Choi, W. Tyrra, A. Adam, Z. Anorg. Allg. Chem. 1999,
625, 1287Ϫ1292.
ischen Industrie is gratefully acknowledged.
[16] X-RED 1.22, Stoe Data Reduction Program (C) 2001 Stoe &
Cie GmbH Darmstadt.
References
[17] X-Shape 1.06, Crystal Optimisation for Numerical Absorption
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[18] Crystallographic data for the structure have been deposited
with the Cambridge Crystallographic Data Centre as sup-
plementary publication no. CCDC 264586. Copies of the data
can be optained, free of charge, on application to CHGC, 12
Union Road, Cambridge CB2 1EZ, UK (fax: ϩ44 1223
336033 or e-mail: deposit@ccdc.cam.ac.uk).
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