9440 Inorganic Chemistry, Vol. 49, No. 20, 2010
Ferrer et al.
and two-dimensional (2D) 1H NMR (δ(TMS) = 0.0 ppm) spectra
were obtained on a spectrometers at 25 °C unless otherwise stated.
A ledbpgs2s (2D sequence with bipolar gradients for diffusion using
stimulated echo and LED) was used for the diffusion experiment.53
Electrospray mass spectra were recorded on a LC/MSD-TOF
(Agilent Technologies) spectrometer at the Universitat de
Barcelona and on a LTQ-FT Ultra (Thermo Scientific) at the
Biomedical Research Institute (PCB-Universitat de Barcelona).
Elemental analyses of C, H, N, and S were carried out at the Serveis
suspension of 4,40-bis(4-pyridyl)octafluorobiphenyl (9 mg,
0.02 mmol) in CH3NO2 (2 mL). The resulting mixture was warmed
to 60 °C and stirred for 5 h, and then, 3 mL of diethylether were
added to precipitate 24 mg of 2a/2b as an orange solid (90% yield).
2a: 1H NMR (400.1 MHz, acetone-d6, 298 K), δ(ppm): 9.33
(d, J(H-H) = 5.6 Hz, 16 H, HR-pyr), 7.89-7.45 (m, 80 H, Ph),
7.55 (d, J(H-H) = 5.6 Hz, 16 H, Hβ-pyr), 3.54 (brs, 16 H,
-P-CH2-CH2-), 2.41 (brs, 8 H, -P-CH2-CH2). 31P NMR (101.3
MHz, acetone-d6, 298 K), δ(ppm): -14.8 (s, J(P-Pt) = 3035
Hz). 19F NMR (376.5 MHz, acetone-d6, 298 K), δ(ppm): -139.7
(m, 16 F, FA), -143.1 (m, 16 F, FB).
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Cientıfico-Tecnics in Barcelona.
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Molecular Modeling and Semiempirical Calculations. Geom-
etry optimization of the molecules was calculated with PM3
semiempirical methods included in the software package
Spartan’04 V1.0.0.
2b: 1H NMR (400.1 MHz, acetone-d6, 298 K), δ(ppm): 9.22
(d, J(H-H) = 5.6 Hz, 12 H, HR-pyr), 7.89-7.45 (m, 96 H, Ph þ
Hβ-pyr), 3.54 (brs, 12 H, -P-CH2-CH2), 2.41 (brs, 6 H, -P-CH2-
CH2). 31P NMR (101.3 MHz, acetone-d6, 298 K), δ(ppm):
-14.3 (s, J(P-Pt) = 3035 Hz). 19F NMR (376.5 MHz, acet-
one-d6,298K),δ(ppm):-139.9(m,12F,FA),-143.4 (m, 12 F, FB).
2a/2b: ES-MS(þ) m/z = 1887.7 ([2b - 2OTf]2þ, calcd:
1887.7), 1661.5 ([2a - 3OTf]3þ, calcd: 1661.2), 1208.1 ([2a -
4OTf]4þ, [2b - 3OTf]3þ, ([Pt(dppp)(L1)(OTf)]þ, calcd: 1208.1).
Synthesis and Characterization. Synthesis of 4,40-Bis(4-pyridyl)-
octafluorobiphenyl (L1). n-BuLi (10.1 mL, 16.2 mmol) was added
dropwise to a precooled (-78 °C) diethylether solution (20 mL) of
4-bromopyridine (15.0 mmol) prepared from 3 g (15.0 mmol) of
4-bromopyridine hydrochloride.54 After 30 min of stirring the
solution was allowed to warm to -40 °C, and the initial beige
solution turned pale pink after 2 h. A solution of decafluorobiphenyl
(1.71 g, 5.10 mmol) in diethylether (30 mL) was then added, and a
Bourdeaux color was immediately acquired. The resulting mixture
wasallowedtowarmtoroomtemperature. After24hofstirring, the
solution was treated with an aqueous solution of NH4Cl and
extracted with CH2Cl2 until the aqueous phase became colorless.
The organic phase was concentrated to dryness, washed with
diethylether and cold dichloromethane, and 1.0 g of a pale beige
solid was obtained (43% yield).
Anal. Calcd for (C51H34F14N2O6P2PtS2)n (1357.09 n): C, 45.10;
3
H, 2.51; N, 2.06; S, 4.72. Found: C, 45.15; H, 2.49; N, 2.08; S, 4.74.
Synthesis of Square [Pd(dppf)(L1)]4(OTf)8 /Triangle [Pd(dppf)-
(L1)]3(OTf)6 (3a/3b). A solution of [Pd(H2O)2(dppf)](OTf)2
(20 mg, 0.02 mmol) in dichloromethane (4 mL) was added
dropwise to a suspension of 4,40-bis(4-pyridyl)octafluorobiphenyl
(9 mg, 0.02 mmol) in dichloromethane (2 mL). After 2 h of stirring
at room temperature, the solution was concentrated to about 3 mL
and diethylether (4 mL) was added to precipitate 25 mg of 3a/3b as
a violet solid (90% yield).
1H NMR (400.1 MHz, CDCl3, 298 K), δ(ppm): 8.83 (d,
J(H-H) = 6.0 Hz, 4H, HR-pyr), 7.48 (d, J(H-H) = 6.0 Hz,
4H, Hβ-pyr). 19F-RMN (376.5 MHz, CDCl3, 298 K), δ(ppm):
-137.6 (m, 4F, FA), -142.3 (m, 4F, FB). ES-MS(þ): m/z =
453.1 ([MþH]þ, calcd: 453.1). IR (KBr, cm-1): 1585 (CdN),
1456 (CdC), 971 (C-F). Anal. Found.: C, 58.45; H, 1.80; N;
6.23. Calcd: C, 58.41; H, 1.77; N, 6.19.
3a: 1H NMR (250.1 MHz, CDCl3, 298 K), δ(ppm): 9.12
(brs, 16 H, HR-pyr), 7.94-7.59 (m, 80 H, Ph), 7.16 (brs, 16 H,
Hβ-pyr), 4.91 (brs, 16 H, HR-Cp), 4.64 (brs, 16 H, Hβ-Cp). 31P
NMR (101.3 MHz, CDCl3, 298 K), δ(ppm): 33.6 (s). 19F
NMR (282.2 MHz, CDCl3, 298 K), δ(ppm): -136.1 (m,
16 F, FA), -141.3 (m, 16 F, FB).
3b: 1H NMR (250.1 MHz, CDCl3, 298 K), δ(ppm): 9.02 (brs,
12 H, HR-pyr), 7.94-7.59 (m, 60 H, Ph), 7.12 (d, J(H-H) =
5.0 Hz, 12 H, Hβ-pyr), 4.91 (brs, 12 H, HR-Cp), 4.64 (brs, 12 H,
Hβ-Cp). 31P NMR (101.3 MHz, CDCl3, 298 K), δ(ppm): 34.1 (s).
19F NMR (282.2 MHz, CDCl3, 298 K), δ(ppm): -136.3 (m, 12
F, FA), -141.5 (m, 12 F, FB).
Synthesis of Square [Pd(dppp)(L1)]4(OTf)8/Triangle [Pd(dppp)-
(L1)]3(OTf)6 (1a/1b). A solution of [Pd(H2O)2(dppp)](OTf)2
(17 mg, 0.02 mmol) in CH3NO2 (4 mL) was added to a suspension
of 4,40-bis(4-pyridyl)octafluorobiphenyl (9 mg, 0.02 mmol) in
CH3NO2 (2 mL). The resulting mixture was stirred at room
temperature for 1 h and then, 4 mL of diethylether were added to
precipitate 24 mg of 1a/1b as a pale yellow solid (93% yield).
1a: 1H NMR (400.1 MHz, acetone-d6, 298 K), δ(ppm): 9.27
(d, J(H-H) = 6.0 Hz, 16 H, HR-pyr), 7.85-7.43 (m, 96 H, Ph þ
Hβ-pyr), 3.44 (brs, 16 H, -P-CH2-CH2), 2.43 (brs, 8 H, -P-CH2-
CH2). 31P NMR (101.3 MHz, acetone-d6, 298 K), δ(ppm): 7.4
(s). 19F NMR (376.5 MHz, acetone-d6, 298 K), δ(ppm): -144.0
(m, 16 F, FA), -147.5 (m, 16 F, FB).
3a/3b: ES-MS(þ) m/z = 1966.0 ([3b - 2OTf]2þ, calcd: 1967.0),
1731.7 ([3a - 3OTf]3þ, calcd: 1732.0), 1263.1 ([Pd(dppf)(L1)-
(OTf)]þ, calcd: 1262.0). Anal. Calcd for (C58H36F14FeN2O6P2-
PdS2)n (1410.25 n): C, 49.35; H, 2.55; N, 1.99; S, 4.54. Found: C,
49.39; H, 2.57; N, 2.01; S, 4.56.
3
Synthesis of Square [Pt(dppf)(L1)]4(OTf)8/Triangle [Pt(dppf)-
(L1)]3(OTf)6 (4a/4b). [Pt(H2O)2(dppf)](OTf)2 (22 mg, 0.02
mmol) and 4,40-bis(4-pyridyl)octafluorobiphenyl (9 mg, 0.02
mmol) were reacted and worked up as described for 3a/3b to
yield 28 mg (95% yield) of an orange product.
1b: 1H NMR (400.1 MHz, acetone-d6, 298 K), δ(ppm): 9.15
(brs, 12 H, HR-pyr), 7.85-7.43 (m, 72 H, Ph þ Hβ-pyr), 3.44 (brs,
12 H, -P-CH2-CH2), 2.43 (brs, 6 H, -P-CH2-CH2). 31P NMR
(101.3 MHz, acetone-d6, 298 K), δ(ppm): 8.1 (s). 19F NMR
(376.5 MHz, acetone-d6, 298 K), δ(ppm): -144.2 (m, 12 F, FA),
-147.8 (m, 12 F, FB).
1
4a: H NMR (400.1 MHz, CDCl3, 298 K), δ(ppm): 9.19 (d,
J(H-H) = 5.0 Hz, 16 H, HR-pyr), 7.90-7.56 (m, 80 H, Ph), 7.20 (d,
J(H-H) = 5.0 Hz, 16 H, Hβ-pyr), 4.87 (brs, 16 H, HR-Cp), 4.61 (brs,
16 H, Hβ-Cp). 31P NMR (101.3 MHz, CDCl3, 298 K), δ(ppm): 3.9
(s, J(P-Pt) = 3417 Hz). 19F NMR (376.5 MHz, CDCl3, 298 K),
δ(ppm): -136.1 (m, 16 F, FA), -141.3 (m, 16 F, FB).
1a/1b: ES-MS(þ) m/z= 2389.1 ([1a - 2(OTf)]2þ,calcd:2389.1),
1754.1 ([1b - 2(OTf)]2þ, calcd: 1754.6), 1119.1 ([Pd(dppp)(L1)-
(OTf)]þ, calcd: 1119.1). Anal. Calcd for (C51H34F14N2O6P2PdS2)n
(1268.4 n): C, 48.25; H, 2.68; N, 2.20; S, 5.05. Found: C, 48.32; H,
2.66; N, 2.17; S, 5.07.
1
3
4b: H NMR (400.1 MHz, CDCl3, 298 K), δ(ppm): 9.08 (d,
J(H-H) = 5.0 Hz, 12 H, HR-pyr), 7.90-7.56 (m, 60 H, Ph), 7.17 (d,
J(H-H) = 5.0 Hz, 12 H, Hβ-pyr), 4.87 (brs, 12 H, HR-Cp), 4.61 (brs,
12 H, Hβ-Cp). 31P NMR (101.3 MHz, CDCl3, 298 K), δ(ppm): 4.2
(s, J(P-Pt) = 3417 Hz). 19F NMR (376.5 MHz, CDCl3, 298 K),
δ(ppm): -136.3 (m, 12 F, FA), -141.6 (m, 12 F, FB).
Synthesis of Square [Pt(dppp)(L1)]4(OTf)8/Triangle [Pt(dppp)-
(L1)]3(OTf)6 (2a/2b). A solution of [Pt(H2O)2(dppp)](OTf)2
(19 mg, 0.02 mmol) in CH3NO2 (4 mL) was added dropwise to a
4a/4b: ES-MS(þ) m/z = 1851.1 ([4a - 3OTf]3þ, calcd: 1850.4),
(53) Wu, D. H.; Chen, A. D.; Johnson, C. S. J. Magn. Reson., Ser. A 1995,
115, 260–264.
(54) 4-Bromopyridine hydrochloride was treated with NaOH in H2O.
Et2O was added, and the resulting 4-bromopyridine ethereal solution was
dried over MgSO4 and CaH2 and taken to dryness under vacuum.
1351.1([Pt(dppf)(L1)(OTf)]þ, [4a - 4OTf]4þ, [4b - 3OTf]3þ;calcd:
1350.7). Anal. Calcd for (C58H36F14FeN2O6P2PtS2)n (1498.94 n):
C, 46.43; H, 2.40; N, 1.87; S, 4.27. Found: C, 46.47; H, 2.42; N, 1.88;
S, 4.29.
3