Journal of Inorganic and General Chemistry
ARTICLE
Zeitschrift für anorganische und allgemeine Chemie
(
215 mL). IIIa (2.01 g, 6.92 mmol, 2.30 equiv.) was added in portions m/z = 1912 (100%) [Ag
6
(C21
H
23 10 2 6 3 6 42 46 20 4
H N ) (PF ) C H N P F24: C
]+. Ag
2.70 (calcd. 2.25%); N 12.83 (calcd.
to the solution. The solution was heated to reflux for 4 d at 90 °C.
Afterwards, the solvent was removed in vacuo. The red-brownish solid
was dried at a high vacuum line overnight. The dried solid was sus-
pended in ethanol (16 mL) and a mixture of HCl/EtOH (6 m) was
24.27 (calcd. 24.51%);
13.61%).
Synthesis of [Ag
6
(L2)
2
](PF
6
)
4
: [H
5
L ](PF
2
6
)
4
(350 mg, 340 μmol,
added. The suspension was stirred for 30 min and Et
until a precipitation appeared. The brownish solid was filtered off,
washed with Et O and was dried at the high vacuum line for several
2
O was added 1.00 equiv.) was dissolved in MeCN (100 mL) and silver(I) oxide
(237 mg, 1.02 mmol, 3.00 equiv.) was added. The resulting suspension
was heated at 55 °C for 25 h. The solid material was removed by fil-
2
®
hours. An off-white solid was obtained in 54% yield (1.56 g, tration through Celite , after the suspension was cooled down to room
1
1
.62 mmol). [H
dissolved in demineralized water (250 mL). Excess of NH
added in portions to the solution and stored at –30 °C overnight. The white solid was obtained in 60% yield (214 mg, 101 μmol) by
6
L ]X
5
(X = Cl, I) (1.54 g, 1.60 mmol, 1.00 equiv.) was
temperature. The solvent of the brown solution was removed under
was reduced pressure and acetone (50 mL) was added to the brown oil. A
4
PF
6
+
2
off-white precipitate was filtered off, washed several times with water fractionated precipitation of the compound with Et O. MS (ESI ,
+
and was dried at the high vacuum line. An off-white solid was obtained MeCN): m/z = 1969 (5%) [Ag
6
(C23
H
N
27
N
10
)
F
2
(PF
6
)
3
] , 912 (63%)
in 52% yield (0.829 g, 0.829 mmol). 1H NMR (500 MHz, 298 K, [Ag
(C23
H
27
N
10
)
2
(PF
6
)
2
] . Ag
+
C
H
54
P
:
C 26.04 (calcd.
5
6
46
20
4
24
[
D
3
]MeCN): δ = 11.45 (br. s, 1 H, NH), 8.80 (br. s, 2 H, ImH), 8.70
26.13%); H 2.91 (calcd. 2.58%); N 13.10 (calcd. 13.25%).
3
(
s, 2 H, ImH), 7.59 (br. s, 2 H, ImH), 7.57 (dd, JHH = 1.99 Hz, 2 H,
ImH), 7.48 (br. s, 2 H, ImH), 7.45 (dd, 3JHH = 1.80 Hz, 2 H, ImH), 6.59
Supporting Information (see footnote on the first page of this article):
NMR spectra, ESI mass spectra and additional characterization data;
]MeCN): δ crystallographic details.
pz
(s, 1 H, H ), 6.36 (s, 4 H, CH
2
), 5.45 (s, 2 H, CH
). C{ H} NMR (126 MHz, 298 K, [D
146.4 (Cquart.), 138.4, 137.9, 126.0, 124.8, 124.6, 123.6, 123.3, 123.0,
2
), 5.38 (s, 2 H, CH
2
),
13
1
3
=
1
(
[
.88 (s, 6 H, CH
3
3
+
08.0, 59.8, 48.0, 44.8, 37.5 ppm. MS (ESI , MeCN): m/z = 855
+
+
Acknowledgements
18.8%) [C21
10(PF
28 6 3 21
H N10(PF ) ] , 401 (36.5%) [C20H N10] 355 (100%)
2+
+
C
21
H
28
N
6
)
2
] , 163 (91.3%) [C
8
H
11
N
4
] . C21
H
28
N
10
P
4
F24: C
This work was performed in the framework of the international PhD
program Catalysis for Sustainable Synthesis (CaSuS). S.G.R. thanks
R. Schöne for technical support with NMR measurements and
T. Grothe for his synthetic contributions to this work.
2
1
5.35 (calcd. 25.21%);
4.00%).
H
2.71 (calcd. 2.82%);
N
14.02 (calcd.
2
Synthesis of [H
5
L ](PF
6
)
4
: 3,5-Bis(iodomethyl)-1-tetrahydropyran-2-
yl pyrazole (621 mg, 1.43 mmol, 1.00 equiv.) was dissolved in MeCN
150 mL). IIIb (1.06 g, 3.48 mmol, 2.42 equiv.) was added in portions
(
Keywords: Pyrazole ligands; N-heterocyclic carbenes;
Silver; Oligonuclear complexes; Prototropy
to the solution. The solution was heated to reflux for 6 d at 90 °C.
Afterwards, the solvent of the separated solution was removed in
vacuo. The red-brownish solid was dried at a high vacuum line over-
night. The dried solid was dissolved in EtOH (30 mL) and a mixture
of HCl/EtOH (6 m, 15 mL) was added. The solution was stirred for
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3
0 min and Et
The yellow solid was filtered off, washed with Et
the high vacuum line for several hours. An off-white solid was dis-
solved in demineralized water (150 mL). Excess of NH PF was added
2
O (60 mL) was added until a precipitation appeared.
O and was dried at
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[D
6
]DMSO): δ = 13.22 (br. s, 1 H, NH), 9.07 (d, JHH = 10.5 Hz, 2 H,
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HH
J =
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2
.70 Hz, 2 H, ImH), 6.43 (s, 1 H, H ), 5.48 (s, 2 H, CH ), 5.39 (s, 2
13
1
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75 MHz, 298 K, [D ]DMSO): δ = 145.8 (Cquart.), 137.1, 136.8, 124.0,
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23.1, 122.3, 105.2, 48.6, 48.3, 46.2, 43.2, 36.0 ppm. MS (ESI ,
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MeCN): m/z 10(PF
[
=
883 (100%) [C23
H
32
N
6 3
) ] , 369 (65)
2+
C
23
H
32
N
10(PF ) ] . C23H N P F24: C 27.34 (calcd. 26.86%); H
6 2 32 10 4
3.28 (calcd. 3.14%); N 13.82 (calcd. 13.62%).
[
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(
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(L1)
2
](PF
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4
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5
L ](PF
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243 mg, 1.05 mmol, 3.00 equiv.) was added. The resulting suspension
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tration through Celite , after the suspension was cooled down to room
temperature. The solvent of the brown solution was removed under
reduced pressure and MeCN (50 mL) was added to the black residue.
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+
tionated precipitation of the compound with Et
2
O. MS (ESI , MeCN):
Z. Anorg. Allg. Chem. 0000, 0–0
www.zaac.wiley-vch.de
7
© 0000 WILEY-VCH Verlag GmbH & Co. KGaA, Weinheim