19.08 (5-O-THP), 23.02 (5-N-THP), 25.16 and 25.62
(4-N-THP and 4-O-THP), 29.77, 29.81 and 30.51 (3-N-THP
and 3-O-THP), 61.02 and 61.19 (5-N-THP), 61.62 and 61.77
(Pyr-CH2-OTHP), 68.62 (6-O-THP), 86.07 (2-N-THP), 98.11
and 98.33 (2-O-THP). 128.50 and 128.52 (2-Ph), 128.71 (4-Ph),
130.08 and 130.01 (5-pyr) 130.83 and 130.79 (2-Ph), 132.48,
135.81 and 147.79 (3/4-Pyr and 1-Ph), 181.29 (Pyr-CHO).
ESI(+) MS (m/z) CH3CN: calcd. for C21H26N2O4Na+
393.1785, found 393.1814.
N 14.35; found C 52.80, H 3.75, N 14.11. IR (ATR) cmꢁ1
:
3029 (w), 2919 (w), 1583 (w), 1530 (m), 1310 (s), 1046 (s),
1019 (s), 978 (s), 907 (s), 758 (s) 678 (s), 421 (m). ESI(+) MS
(m/z) MeCN: calcd for FeNi3C78H56N18BF4 1563.2360, found
1563.2210.
Acknowledgements
This work was supported by grants from the University of
Otago and the MacDiarmid Institute, including the award of a
MacDiarmid-funded PhD scholarship to JO. Mr J.E.M. Lewis
(Brooker group) is thanked for his help with proof reading,
repeating some of these syntheses, and the X-ray crystal
structure determination on 19. This invited paper is part of
the Molecular Materials thematic issue.
3-(Hydroxymethyl)-4-phenyl-5-pyrazolecarbaldehyde dimer (29)
5-Formyl-3-(20-tetrahydropyranyloxymethyl)-4-phenyl-1-(tetra-
hydropyran-2-yl)-1H-pyrazole (28, 0.47 g, 1.25 mmol) was
dissolved in a 0.1 M HCl solution in methanol (50 mL). The
solution was stirred for 1 h before the solvent was removed
in vacuo. Water was added (20 mL) to the brown oil residue.
The pH of the solution was adjusted to 7 using solid NaHCO3.
Then the aqueous phase was extracted with CH2Cl2 (2 ꢂ 50 mL)
and CHCl3 (2 ꢂ 50 mL). The combined organic phases were
dried over MgSO4 before the solvent was removed in vacuo.
Compound 29 was obtained as a light yellow solid (0.18 g,
0.44 mmol, 70% yield). Microanalysis (%) calcd. for
Notes and references
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C22H24N4O4ꢀ0.5H2O
C 64.62, H 5.05, N 13.70; found
1
C 64.99, H 5.64, N 13.16. H NMR 500 MHz (d6-DMSO @
7.26 ppm) d ppm: 4.44 (m, 4H, Pyr-CH2-OH), 5.20 (t J = 5.2 Hz,
2H, OH), 5.48 (m, 2H, OH), 6.54 (d, J = 6.9 Hz, 2H, NPyr-CH
(OH)-Cpyr), 7.47 (m, 4H, 3-Ph), 7.73 (m, 2H, 4-Ph), 7.91
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77.36 ppm) d ppm: 79.61 (Pyr-CH2-OH), 119.74 (1-Ph), 128.41
(2-Ph), 129.02 (3-Ph), 129.37, 130.21 and 135.19 (3/4/5-Pyr),
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Complex [FeII(NiIIL2)3](BF4)2ꢀ6H2O
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in 5 mL of HPLC methanol was added. No colour change was
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(87.53 mg, 0.78 mmol) caused an immediate colour change
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in an orange solid. According to microanalysis data this
product is contaminated with potassium tetrafluoroborate,
so it was recrystallised from a 1 : 1 MeOH/MeCN mixture
by diethyl ether vapour diffusion to give, after filtration and
drying under vacuum, [FeII(NiIIL2)3](BF4)2ꢀ6H2O as a red
solid (44.5 mg, 0.025 mmol, 19% yield). Microanalysis (%)
calcd. for {Fe[Ni(C26H18N6)3}(BF4)2ꢀ6H2O C 53.32, H 3.79,
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c
1252 New J. Chem., 2011, 35, 1242–1253
This journal is The Royal Society of Chemistry and the Centre National de la Recherche Scientifique 2011