F. Hung-Low, A. Renz, K. K. Klausmeyer
FULL PAPER
resulting in a yellow oil. The yield of crude product was 81%. Puri-
fication of the product was carried out by several extractions with
hexane which resulted in a white solid in 70% yield based on 2-
0.396 mmol) in CH3CN (5 mL). Solvent was removed in vacuo to
obtain an off-white powder. This was then re-dissolved in a small
amount of CH2Cl2 and precipitated with hexane, repeating until
compound 4 was obtained as a white powder upon drying in 51%
(0.180 g, 0.202 mmol) yield. 1H NMR (CDCl3, 298 K): δ = 4.35
(m, 8 H, CH2), 7.58 (m, 14 H, aromatic), 7.98 (m, 8 H, aromatic),
8.60 (d, 4 H, aromatic) ppm. 31P NMR [(CD3)2CO, 298 K]: δ = 9.9,
s; [(CD3)2CO, 231 K]: δ = 11.2 (d) ppm. C37H36Ag2B2Cl2F8N4P2
(1058.91): calcd. C 41.97, H 3.43, N 5.29; found C 42.21, H 3.48,
N 5.47.
1
picoline. H NMR (CD3Cl, 298 K): δ = 3.41 (q, 4 H, CH2), 7.02
(m, 4 H, aromatic), 7.33 (m, 3 H, aromatic), 7.49 (m, 4 H, aro-
matic), 8.52 (m, 2 H, aromatic) ppm. 31P NMR (CDCl3, 298 K): δ
= –13.7 (s) ppm.
Bis(pyrid-2-ylmethyl) Phenylphosphonite (2): In a nitrogen-purged
addition funnel, 1.39 mL of degassed triethylamine (10 mmol) was
added via syringe to a stirred solution of pyridine-2-methanol
(1.09 g, 10 mmol) in toluene (20 mL) at room temperature. The
solution was cooled to 0 °C and shielded from light with aluminum
foil. A solution of dichlorophenylphosphane (0.896 g, 5 mmol) in
toluene (20 mL) was then added dropwise over 10 min. The solu-
tion was stirred for 1 h, and warmed to room temperature, followed
by stirring for an additional 30 min. The resultant mixture was fil-
tered through Celite. The triethylammonium chloride salt was
washed with an additional 5 mL of cold toluene, and the solvent
was removed from the yellow liquid at reduced pressure to leave a
yellow oil. The oil was then extracted with 100 mL of hexane to
leave 2 as a pale yellow oil in 84% yield (1.36 g, 4.36 mmol). 1H
NMR (CH3CN, 298 K): δ = 5.01 (m, 4 H, CH2), 7.09 (t, 3 H,
aromatic), 7.66 (m, 7 H, aromatic), 8.43 (d, 3 H, aromatic) ppm.
31P NMR (CD3CN, 298 K): δ = 160.1 (s) ppm.
Synthesis of [AgOTf(1)]2 (5): To a stirred solution of AgOTf
(0.109 g, 0.399 mmol) in CH3CN (5 mL) was added 1 (0.116 g,
0.399 mmol) in CH3CN (5 mL). The compound was re-crystallized
upon drying in 49% (0.210 g, 0.194 mmol) yield. 1H NMR (CDCl3,
298 K): δ = 4.31 (m, 8 H, CH2), 7.32 (m, 6 H, aromatic), 7.49 (m,
8 H, aromatic), 7.85 (t, 4 H, aromatic), 7.96 (m, 4 H, aromatic),
8.45 (d, 4 H, aromatic) ppm. 31P NMR [(CD3)2CO, 298 K]: δ =
11.8, s; [(CD3)2CO, 298 K]: δ = 12.1, t ppm. C39H36Ag2Cl2F6-
N4O6P2S2 (1169.39): calcd. C 39.58, H 3.07, N 5.23; found C 40.13,
H 3.16, N 4.91.
Synthesis of [CuPF6(1)]2 (6): A solution of 1 (0.116 g, 0.399 mmol)
in CH3CN (5 mL) was added to [Cu(CH3CN)4][PF6] (0.149 g,
0.399 mmol) dissolved in CH3CN (5 mL). Compound 6 was ob-
tained as
a white powder upon drying in 85% (0.170 g,
Synthesis of [Agtfa(1)]2 (3): This reaction used
1
(0.116 g,
0.170 mmol) yield. 1H NMR (CDCl3, 298 K): δ = 3.83 (m, 4 H,
CH2), 7.47 (m, 11 H, aromatic), 8.21 (m, 2 H, aromatic) ppm. 31P
NMR [(CD3)2CO, 298 K]: δ = –15.5, s; [(CD3)2CO, 228 K]: δ =
–31.2 (s, br), –2.2 (s) ppm. C36H34Cu2F12N4P4 (1001.65): calcd. C
43.17, H 3.42, N 5.59; found C 43.12, H 3.31, N 5.62.
0.398 mmol) in CH3CN (5 mL) added to a stirred solution of Agtfa
(0.880 g, 0.398 mmol) in CH3CN (5 mL) to leave a fluffy off-white
solid. The compound was re-crystallized upon drying in 48%
(0.190 g, 0.185 mmol) yield. 1H NMR (CDCl3, 298 K): δ = 4.05
(m, 8 H, CH2), 7.31 (m, 14 H, aromatic), 7.68 (m, 4 H, aromatic),
7.85 (m, 4 H, aromatic), 8.47 (d, 4 H, aromatic) ppm. 31P NMR
[(CD3)2CO, 298 K]: δ = 8.7, s; [(CD3)2CO, 238 K]: δ = 11.2, t ppm.
C41H36Ag2Cl2F6N4O4P2 (1111.54): calcd. C 44.31, H 3.26, N 5.04;
found C 43.82, H 3.33, N 4.84.
Synthesis of [CuPF6(2)]2 (7): To a stirred solution of [Cu(CH3CN)4]-
[PF6] (0.111 g, 0.297 mmol) in CH2Cl2 (5 mL), was added to 2
(0.097 g, 0.299 mmol) in CH2Cl2 (5 mL). This solution was stirred
for 5 min, and then 45 mL of ether were added. Upon stirring for
10 min a white precipitate formed. The colorless solvent was re-
moved via cannula, and the residual solvent was removed in vacuo
to leave a white solid, 7, in 81% (0.278 g, 0.358 mmol) yield. 1H
Synthesis of [AgBF4(1)]2 (4): The reaction was done in a 1:1 ratio
of 1 (0.117 g, 0.396 mmol) in CH3CN (5 mL) to AgBF4 (0.077 g,
Table 4. Crystallographic data for compounds 3–5.
3
4
5
Empirical formula
Formula mass
C42H38Ag2Cl4F4N4O4P2
1196.24
C36H34Ag2B2F8N4P2
973.97
C39H36Ag2Cl2F6N4O6P2S2
1183.42
a /Å
b /Å
c /Å
α /°
9.9151(8)
10.5773(9)
11.8770(10)
81.442(4)
79.351(4)
75.428(4)
1177.90(17)
1
10.4667(8)
13.3392(8)
14.1342(11)
102.466(2)
104.341(2)
93.595(2)
1852.7(2)
2
9.7199(7)
13.9612(10)
16.5420(11)
79.481(3)
80.510(3)
82.583(3)
2165.5(3)
2
β /°
γ /°
V /Å3
Z
Crystal system
Space group
T /K
triclinic
P1
110(2)
1.686
1.195
triclinic
P1
110(2)
1.746
1.218
triclinic
P1
110(2)
1.815
1.276
¯
¯
¯
Dcalcd. /gcm–3
µ /mm–1
2θmax. /°
Reflections measured
Reflections used (Rint
Restraints/parameters
R1 [IϾ2σ(I)]
wR2 [IϾ2σ(I)]
R(Fo2) (all data)
Rw(Fo2) (all data)
GOF on F2
26.37
23421
25.00
17285
25.00
37239
)
4759 (0.0290)
0/289
0.0307
0.0800
0.0331
0.0816
1.036
7388 (0.0350)
0/487
0.0353
0.0742
0.0506
0.0824
1.017
7565 (0.0423)
0/568
0.0525
0.1517
0.0592
0.1593
1.010
3000
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Eur. J. Inorg. Chem. 2009, 2994–3002