O. Wichmann, H. Sopo, A. Lehtonen, R. Sillanpää
FULL PAPER
1
triethylamine (0.028 mL, 0.2 mmol) were added and the solution
was heated until all the solids had dissolved. The resulting dark red
solution was kept at room temperature and the solvent was allowed
to evaporate slowly for three days, which led to the formation of
crystals. The dark red crystals were filtered off, washed with aceto-
nitrile (2 mL) and air dried; yield 0.035 g (62%). 1H NMR: δ =
1.29, 1.52 [s, 18 H, Ar-C(CH3)3], 2.79 (t, 2 H, NCH2CH2), 3.47,
3.80 (d, 4 H, Ar-CH2-N), 4.85 (t, 2 H, CH2CH2O), 7.01, 7.26 (d,
and its subsequent H NMR spectrum consisted of the signals of
7 and 1 in a 1.6:1 ratio. A recrystallization by slow evaporation
from a mixture of acetonitrile and dichloromethane (9 mL, 5:4)
yielded dark, shiny crystals of 7, which were washed twice with
diethyl ether (1 mL) and air dried. To improve the poor yield
(8.6 mg) of the first recrystallization, the solvent was evaporated to
dryness, washed with diethyl ether (2ϫ1 mL), and a similar
recrystallization process was performed twice on the remains. Com-
4 H, Ar-H) ppm. 13C NMR (126 MHz, CDCl3): δ = 29.9, 31.6 plex 7 seemed to be practically insoluble to diethyl ether, which
[Ar-C(CH3)3], 34.5, 35.2 [Ar-C(CH3)3], 53.3 (NCH2CH2), 56.6 (Ar- helped to reduce the amount of 1 (soluble in small amounts) in the
1
CH2-N), 75.7 (CH2CH2O), 122.8, 124.7, 125.0, 136.0, 145.2, 165.1
(Ar) ppm. 51V NMR (132 MHz, CDCl3): δ = –392.7 ppm. IR:
νV=O, 951 cm–1. C32H48NO4V (561.68): calcd. C 68.3, H 8.4, N 2.4;
found C 68.4, H 8.6, N 2.5. A single-crystal X-ray analysis was
performed on one of the crystals.
precipitates; yield 22.3 mg (22%). H NMR (500 MHz, CDCl3): δ
= 1.87 [s, 6 H, Ar-C(26/29)H3], 2.25 [s, 6 H, Ar-C(27/28)H3], 2.91
(t, 2 H, NCH2CH2O), 3.34 (t, 2 H, CH2CH2O), 3.79, 4.86 (d, 2 H,
Ar-CH2-N), 4.57 (s, 2 H, Ar-CH2O), 6.78 [d, 2 H, Ar-H(5/11)], 6.92
[d, 2 H, Ar-H(3/13)], 6.92 [m, 2 H, Ar-H(22/23)], 7.01 (d, 1 H, Ar-
H24), 7.32 (t, 1 H, Ar-H21) ppm. 13C NMR (126 MHz, CDCl3): δ
= 15.7 [Ar-C(26/29)H3], 20.5 [Ar-C(27/28)H3], 53.9 (NCH2CH2),
66.4 (Ar-CH2-N), 68.7 (CH2CH2O), 72.8 (Ar-CH2O), 115.9 (C24),
119.6 (C6/C10), 122.3 (C23), 124.3 (C2/C14), 125.4 (C20), 126.5
(C5/C11), 128.2 (C4/C12), 128.7 (C21), 129.6 (C22), 131.6 (C3/
C13), 162.1 (C1/C15), 167.1 (C25) ppm. 51V NMR (132 MHz,
CDCl3): δ = –437.9 ppm. IR: νV=O, 943 cm–1. C27H30NO5V
(499.48): calcd. C 64.9, H 6.1, N 2.8; found C 65.4, H 5.8, N 3.1. A
single-crystal X-ray analysis was performed on one of the crystals.
[VO(L1)(CH3OH)]·0.5CH3OH (5): 0.265 g (1.0 mmol) of
[VO(acac)2] and 0.329 g (1.0 mmol) of H3L1·1/3toluene were mixed
with 10 mL of methanol. After the dark reaction mixture was kept
under open atmosphere for three hours, the reaction vessel was
sealed and the mixture was kept at room temperature for a week.
Dark, shiny crystals of the complex [VO(L1)(CH3OH)]·0.5CH3OH
1
were isolated and washed with methanol. Yield 280 mg (63%). H
NMR (500 MHz, CDCl3): δ = 2.25 [s, 6 H, Ar-C(19/20)H3], 2.35
[s, 6 H, Ar-C(18/21)H3], 2.70 (t, 2 H, NCH2CH2O), 3.43, 3.73 (d,
2 H, Ar-CH2-N), 3.49 (s, 6 H, CH3O), 4.81 (t, 2 H, NCH2CH2O),
6.76 [d, 2 H, Ar-H(5/11)], 6.90 [d, 2 H, Ar-H(3/13)] ppm. 13C NMR
(126 MHz, CDCl3): δ = 16.4 (C18/C21), 20.6 (C19/C20), 50.8
(CH3O) 53.0 (NCH2CH2O), 56.0 (Ar-CH2-N), 75.9 (NCH2CH2O),
124.4 (C6/C10), 124.8 (C4/C12), 127.9 (C5/C11), 130.3 (C3/C13),
132.0 (C2/C14), 164.2 (C1/C15) ppm. 51V NMR (132 MHz,
CDCl3): δ = –389.3 ppm. IR: νV=O, 952 cm–1. C21H25NO5V·
1/2CH3OH (438.39): calcd. C 58.9, H 6.2, N 3.2; found C 59.0, H
6.3, N 3.5. A single-crystal X-ray analysis was performed on one
of the crystals.
X-ray Crystallography: Crystals suitable for single-crystal X-ray
measurements were obtained directly from reaction tubes before
filtration. The crystal data for compounds 1–7 along with other
experimental details are summarized Tables S1–S2. The crystallo-
graphic data were collected at 123 or 173 K on an Enraf Nonius
Kappa CCD area detector diffractometer using graphite mono-
chromatized Mo-Kα radiation (λ = 0.71073 Å). The data were col-
lected with φ and ω scans and were processed using DENZO-SMN
v0.95.373.[41,42] An SADABS[43] absorption correction was applied
to the data sets. The structures were solved by direct methods using
the SHELXS-97[44] or SIR-97[45] programs and full-matrix least-
squares refinements on F2 were performed using the SHELXL-
97[46] program. The heavy atoms were refined anisotropically except
the disordered carbon atoms in the side chains of the aromatic
rings of 2, which were refined isotropically. The CH hydrogen
atoms were included at fixed distances using fixed displacement
parameters from their host atoms while other H atoms were refined
using fixed displacement parameters. Structure figures were drawn
using ORTEP-3 for Windows.[47]
[VO(L1C1)] (6): H3L1·1/3toluene (0.313 g, 0.87 mmol) was dis-
solved in ethanol (99.5%) (9 mL) and [VO(OCH2CH2CH3)3]
(0.092 mL, 0.4 mmol) was added to the solution and it was heated
until boiling. Water (1 mL) was added in five 200 μL portions and
the solution was refluxed for 18 h. The dark red crystals were fil-
tered off, washed twice with diethyl ether (1 mL) and air dried;
yield 0.069 g (33%). 1H NMR (500 MHz, CDCl3): δ = 1.86 [s, 6
H, Ar-C(28/31)H3], 2.26 [s, 6 H, Ar-C(29/30)H3], 2.29 [s, 3 H, Ar–
C(27)H3], 2.46 [s, 3 H, Ar-C(26)H3], 2.89 (t, 2 H, NCH2CH2O),
3.31 (t, 2 H, CH2CH2O), 3.76, 4.86 (d, 2 H, Ar-CH2-N), 4.52 (s, 2
H, Ar-CH2O), 6.67 (d, 1 H, Ar-H21), 6.77 [d, 2 H, Ar-H(5/11)],
6.90 [d, 2 H, Ar-H(3/13)], 7.01 (d, 1 H, Ar-H23) ppm. 13C NMR
(126 MHz, CDCl3): δ = 15.6 [Ar-C(26/29)H3], 16.5 [Ar-C(31)H3],
20.4 [Ar-C(27/28)H3], 20.6 [Ar-C(30)H3], 53.8 (NCH2CH2), 66.4
(Ar-CH2-N), 68.5 (CH2CH2O), 72.8 (Ar-CH2O), 119.6 (C6/C10),
123.9 (C24), 124.3 (C2/C14), 124.9 (C20), 126.5 (C5/C11), 126.8
(C21), 127.8 (C4/C12), 131.0 (C23), 131.4 (C3/C13), 131.9 (C22),
161.8 (C1/C15), 164.9 (C25) ppm. 51V NMR (132 MHz, CDCl3): δ
= –418.7 ppm. IR: νV=O, 954 cm–1. C29H34NO5V (527.53): calcd. C
66.0, H 6.5, N 2.7; found C 65.7, H 6.4, N 2.4. A single-crystal X-
ray analysis was performed on one of the crystals.
CCDC-802518 (for 1), -802519 (for 2), -802520 (for 3), -802521 (for
4), -802522 (for 5), -802523 (for 6), -802524 (for 7) contain the
supplementary crystallographic data for compounds 1–7 presented
in this paper. These data can be obtained free of charge from The
Cambridge Crystallographic Data Centre via www.ccdc.cam.ac.uk/
data_request/cif.
Supporting Information (see footnote on the first page of this arti-
cle): Figures S1 and S2 for compounds 2 and 4. Tables S1 and S2
(crystal data for compound 1–7). Tables S3–S4 (selected bond
lengths and angles for compounds 1–4).
Acknowledgments
[VO(L1C2)] (7): The complex was prepared by adding 1 (0.079 g,
0.20 mmol) and salicyl alcohol (0.40 mmol, 0.050 g) in dry acetoni-
trile. The solvent was dried beforehand with molecular sieves (4 Å)
and a CaCl2 tube was added to the experimental setup. The solu-
tion was refluxed for 20 h and cooled to 5 °C. Dark matter precipi-
tated on the bottom of the reaction vessel during two hours. The
precipitate (40.7 mg) was washed twice with diethyl ether (2 mL)
We thank Mr. Reijo Kauppinen for assistance of NMR experi-
ments and Mrs. Elina Hautakangas for performing the elemental
analyses.
[1] D. Rehder, Coord. Chem. Rev. 1999, 182, 297–322.
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Eur. J. Inorg. Chem. 2011, 1283–1291