D.A. Safin et al. / Inorganic Chemistry Communications 20 (2012) 162–166
165
Table 3
Hydrogen bond lengths (Å) and angles (°) for HLII and HLIII
.
D\H⋯A
d (D\H)
d (H⋯A)
d (D⋯A)
∠ (DHA)
HLII
Polymorph HLII{1}a
N(1)\H(1)⋯O(3)#1
C(16)\H(16)⋯O(3)#1
C(6)\H(6B)⋯S(1)#2
N(1)\H(1)⋯O(3)#1
N(1)\H(6)⋯O(1)#1
C(3)\H(1)⋯O(1)#1
C(11)\H(11B)⋯O(4)#2
N\H(1)⋯O(1)′
0.83 (4)
0.95
0.98
0.87 (2)
0.80 (3)
0.95
0.98
0.89 (6)
0.84 (6)
2.04 (4)
2.60
2.81
1.95 (2)
2.04 (3)
2.58
2.68
1.96 (8)
1.99 (6)
2.849 (4)
3.239 (4)
3.705 (6)
2.805 (2)
2.836 (2)
3.254 (2)
3.615
165 (3)
125
152
165 (2)
172 (3)
128
159
162 (5)
164 (6)
Polymorph HLII{2}b [13]
Polymorph HLIII{1}c
HLIII
Polymorph HLIII{2} [14]
2.837 (7)
2.811 (7)
N′\H(1)′⋯O(1)
a
Symmetry transformations used to generate equivalent atoms: #1 1/2−x, 1/2−y, 1−z; #2 x, −1+y, z.
Symmetry transformations used to generate equivalent atoms: #1 1−x, −y, −z.
Symmetry transformations used to generate equivalent atoms: #1 3/2−x, 3/2−y, 1−z; #2 x, –1+y, z.
b
c
In summary, the tetraphenylphosphonium salts PPh4LI,II have
[16] Physical measurements: IR spectra were recorded with Bruker IFS66νS or Specord
M-80 spectrometers in the range 400–3600 cm−1. NMR spectra (CDCl3) were
obtained on Bruker Avance 300 MHz or Varian Unity-300 NMR spectrometers
at 25 °C. 1H and 31P{1H} spectra were recorded at 299.948 and 121.420 MHz, re-
spectively. Chemical shifts are reported with reference to SiMe4 (1H) and 85%
been synthesized and characterized by means of IR, 1H, 31P{1H}
NMR spectroscopy, ES mass spectrometry and microanalysis. Recrys-
tallization of PPh4LI,II from an aqueous EtOH solution (1:1, v/v) leads
to the formation of HLII,III, respectively. The crystal structures of HLII,
III reveal to be polymorphs to the previously reported structures. Sin-
gle crystal X-ray diffraction studies showed that HLII,III form intermo-
lecular hydrogen bonds leading to the centrosymmetric dimer
formation.
H3PO4 (
31P{1H}). Electrospray ionization mass spectra were measured with a
Finnigan-Mat TCQ 700 mass spectrometer on a 10−6 M solution in CH3OH. The
speed of sample submission was 2 μL/min. The ionization energy was 4.5 kV.
The capillary temperature was 200 °C. Elemental analyses were performed on a
Perkin–Elmer 2400 CHN microanalyser. Synthesis of PPh4LI,II: A suspension of
HLI,II (0.317 or 0.301 g, respectively; 1.0 mmol), in 96% aqueous EtOH (10 mL)
was mixed with a 96% aqueous EtOH (10 mL) solution of sodium hydroxide
(0.044 g, 1.1 mmol, 10% excess).
A 96% aqueous EtOH (10 mL) solution of
PPh4Br (0.419 g, 1.0 mmol) was added dropwise under vigorous stirring to the
resulting sodium salt. The mixture was stirred at room temperature for a further
3 hours and left overnight. The white precipitate of NaBr was filtered off, and the
solvent was removed in vacuo. A yellow (PPh4LII) or colorless precipitate (PPh4-
LII) was isolated from a H2O/EtOH mixture (1:1, v/v). PPh4LI: Yield 0.525 g (80%).
IR ν (cm−1): 608 (P=S), 996 (POC), 1562 (S⋯C⋯N). 1H NMR δ (ppm): 1.14 (d, 3JH,
Acknowledgments
This work was partly funded by the Fonds National de la
Recherche Scientifique — FNRS (FRFC No. 2.4508.08, No. 2.4537.12,
IISN 4.4507.10) and the IAP-VI INANOMAT program. We thank the
F.R.S.-FNRS (Belgium) for a post-doctoral position allocated to D. A. S.
3
H =6.2 Hz, 6H, CH3, iPr), 1.18 (d, JH,H =6.1 Hz, 6H, CH3, iPr), 4.57 (d sept, 3J-
3
POCH =9.4 Hz, JH,H =6.2 Hz, 2H, OCH), 6.38–7.82 (m, overlapped with the sol-
vent signal, Ph). 31P{1H} NMR δ (ppm): 23.9 (1P, PPh4), 61.8 (1P, NPS). ES–MS
positive ion m/z (%): 339.4 (100) [PPh4]+, 657.1 (81.8) [PPh4Lig+H]+, 1013.4
(28.9) [PPh4Lig+H2O+PPh4]+
,
1041.7 (17.4) [PPh4Lig+EtOH+PPh4]+
,
Appendix A. Supplementary material
1330.8 (10.9) [(PPh4)2Lig2 +H2O+H]+
. ES–MS negative ion m/z (%): 316.2
(62.1) [Lig]−, 972.4 (85.3) [PPh4Lig+Lig]−, 1646.8 (38.6) [(PPh4)2Lig2 +H2O+
Lig]−. Anal. for C37H39NO2P2S2 (655.79): calcd. C 67.77, H 5.99, N 2.14; found C
67.64, H 6.04, N, 2.09. PPh4LII: Yield 0.569 g (89%). IR ν (cm−1): 1008 (POC),
CCDC 767460 (HLII) and 767909 (HLIII) contain the supplementa-
ry crystallographic data. These data can be obtained free of charge via
bridge Crystallographic Data Centre, 12 Union Road, Cambridge CB2
1EZ, UK; fax: (+44) 1223-336-033; or e-mail: deposit@ccdc.cam.ac.uk.
Supplementary data to this article can be found online at doi:10.1016/j.
1192 (P=O), 1557 (S⋯C⋯N). 1H NMR δ (ppm): 1.08 (d, JH,H =6.0 Hz, 6H, CH3,
3
3
3
3
iPr), 1.14 (d, JH,H =6.2 Hz, 6H, CH3, iPr), 4.74 (d sept, JPOCH =9.0 Hz, JH,
H =6.0 Hz, 2H, OCH), 6.21–7.76 (m, overlapping with the solvent signal, Ph).
31P{1H} NMR δ (ppm): 11.4 (1P, NPO), 22.3 (1P, PPh4). ES–MS positive ion m/z
(%): 339.1 (100) [PPh4]+, 641.3 (70.2) [PPh4Lig+H]+, 979.6 (44.1) [PPh4Lig+
PPh4]+
(%): 300.3 (48.2) [Lig]−
37H39NO3P2S (639.73): calcd. C 69.47, H 6.14, N 2.19; found: C 69.32, H 6.18, N
2.13.
[17] F. Ramirez, C.P. Smith, I.F. Pilot, J. Am. Chem. Soc. 90 (1968) 6726.
,
1312.0 (27.4) [(PPh4)2Lig2 +CH3OH+H]+
.
ES–MS negative ion m/z
,
972.7 (13.6) [PPh4Lig+CH3OH+Lig]−
.
Anal. for
C
References
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model on calculated positions and were refined as riding atoms. Figures were
generated using the program Mercury [28].
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