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Russ.Chem.Bull., Int.Ed., Vol. 53, No. 4, April, 2004
Balashova et al.
scribed previously.4 Benzonitrile was distilled several times over
P2O5 and, immediately prior to use, treated with a minor amount
of NdI2 (1). The required amounts were withdrawn by vacuum
recondensation. Commercially available acrylonitrile was washed
with dilute H2SO4 and then with dilute alkali, dried with CaCl2,
and fractionated.
IR spectra were recorded on Specord Mꢀ80 and
Perkin—Elmer 577 instruments for suspensions in mineral oil,
and 1H and 13C NMR spectra were measured on a Bruker
DPXꢀ200 spectrometer. The chromatographic analysis was perꢀ
formed on a Milichrom 1A chromatograph using a 2×64 mm
stainlessꢀsteel column, and a hexane—THF or MeOH—H2O
mixture as the eluent. The molecular weight of polyacrylonitrile
was determined by viscosimetry at 25 °C in DMF. Xꢀray diffracꢀ
tion analysis of tetraphenylpyrazine was carried out on a Bruker
AXS Smart Apex diffractometer.
(1.88 mmol) of DyI3(C6H5CN)4, m.p. 202 °C. Found (%):
Dy, 16.98; I, 39.69. C28H20DyI3N4. Calculated (%): Dy, 17.0;
I, 39.84. IR (Nujol), ν/cm–1: 2250 s, 1590 w, 1290 w, 755 s,
685 s, 550 s. Tetrahydrofuran (15 mL) was added to the redꢀ
brown mother liquor. After 1 h, a bluish finely crystalline preꢀ
cipitate was formed. The solution was decanted and the residue
was washed with cold THF and dried in vacuo to give 1.94 g
(2.56 mmol) of DyI3(thf)3 (identified by elemental analysis and
IR spectroscopy). From the redꢀbrown decanted solution, THF
was completely removed and 10 mL of MeOH was added. The
crystalline precipitate of 2,4,6ꢀtriphenylꢀ1,3,5ꢀtriazine (0.17 g,
0.56 mmol) was collected on a filter, washed with MeOH,
and dried. The melting point of the product was 233 °C; its
IR spectrum was identical to the spectrum of triazine obtained
in the previous experiment. On storage of the mother liquor for
24 h at ~20 °C, colorless crystals of 3,5,6ꢀtetraphenylpyrazine
precipitated. The crystals were separated by filtration, washed
with MeOH, and dried to give 0.03 g (0.37 mmol) of
C4(C6H5)4N2, m.p. 252 °C. The IR and 1H and 13C NMR
spectra of the compound coincide with the corresponding charꢀ
acteristics of the pyrazine obtained in the experiment with
diiodide 1. Metanol was completely removed from the solution,
and 10 mL of H2O was added to the residue. The whiteꢀcolored
precipitate that formed was separated by centrifuging, washed
Reaction of diiodide 1 with benzonitrile. Benzonitrile (20 mL,
0.2 mol) was added with stirring to a powder of compound 1
(3.77 g, 9.5 mmol). Within 5 min, the solution acquired a redꢀ
brown color. The solution was concentrated to half its volume,
PhCN being removed by condensation in vacuo, and 15 mL of
THF was added. The finely crystalline bluishꢀcolored precipiꢀ
tate formed after 1 h was separated by decantation, washed with
cold THF, and dried in vacuo to give 2.56 g (3.45 mmol) of
NdI3(thf)3 (identified by elemental analysis and IR spectroꢀ
scopy). From the redꢀbrown mother liquor, THF was comꢀ
pletely removed and 10 mL of MeOH was added. The resulting
crystalline precipitate of 2,4,6ꢀtriphenylꢀ1,3,5ꢀtriazine was colꢀ
lected on a sintered funnel, washed with MeOH, and dried in air
to give 0.39 g (1.25 mmol) of C21H15N3, m.p. 233 °C (cf. Ref. 7:
m.p. 233 °C). The structure of the triazine was confirmed by a
structural study whose results coincided with published data.8
After 20 h at ~20 °C, crystals of 2,3,5,6ꢀtetraphenylpyrazine
precipitated from the mother liquor. The crystals were separated
by filtration, washed with MeOH, and dried to give 0.36 g
(0.92 mmol) of C28H20N2, m.p. 252 °C (cf. Ref. 9: m.p.
245—246 °C). The structure of the pyrazine was confirmed by a
structural study whose results coincided with published data.10
Methanol was completely removed from the solution and 10 mL
of H2O was added to give a white precipitate. The precipitate
was separated by centrifuging and dried to give 2.31 g (5.85 mmol)
of NdI(OH)2(H2O)5. Found (%): I, 31.78; Nd, 36.79. H12INdO7.
Calculated (%): I, 32.12; Nd, 36.50. After 20 h at ~20 °C,
crystalline 2,4,5ꢀtriphenylimidazole precipitated. The product
was collected on a filter, washed with ether, and dried to give
0.07 g (0.23 mmol) of C21H16N2, m.p. 275 °C (cf. Ref. 11: m.p.
277 °C). IR (Nujol), ν/cm–1: 1600 m, 1500 w, 1490 m, 1415 w,
1325 w, 1129 m, 1070 w, 1030 w, 969 m, 919 w, 840 w, 765 s,
with ether, and dried to give 3.25
g (6.71 mmol)
DyI(OH)2(H2O)11. Found (%): Dy, 31.14; I, 24.22. H24DyIO13.
Calculated (%): Dy, 31.17; I, 24.34. After 20 h, crystalline 2,4,5ꢀ
triphenylimidazole precipitated from the organic layer. The preꢀ
cipitate was collected on a filter, washed with ether, and dried to
give 0.07 g (0.23 mmol) of C21H16N2, m.p. 275 °C; the IR and
1H and 13C NMR spectra of the product were similar to those
described above. A poorly soluble polymeric product (0.3 g) was
isolated from the organic layer. This product could not be idenꢀ
tified.
Reaction of diiodide 3 with benzonitrile. The reaction and the
isolation and identification of the products were carried out as in
the experiment with compound 2. The reaction of TmI2(thf)5
(2.0 g, 2.56 mmol) and 15 mL of benzonitrile gave TmI3(PhCN)4
(0.71 g, 0.74 mmol), TmI3(thf)3 (0.52 g, 0.68 mmol), 2,4,6ꢀtriꢀ
phenylꢀ1,3,5ꢀtriazine (0.02 g, 0.05 mmol), 2,3,5,6ꢀtetraphenylꢀ
1,4ꢀpyrazine (0.02 g, 0.05 mmol), TmI(OH)2(H2O)5 (0.45 g,
1.07 mmol), and 2,4,5ꢀtriphenylimidazole (0.07 g, 0.23 mmol).
The complex TmI3(PhCN)4, m.p. 204 °C. Found (%):
Tm, 17.49; I, 39.68. C28H20I3N4Tm. Calculated (%): Tm, 17.56;
I, 39.57. IR (Nujol), ν/cm–1: 2250 s, 1590 w, 1290 w, 755 s,
685 s, 550 s.
The complex TmI(OH)2(H2O)5. Found (%): I, 30.74;
Tm, 40.19. H12IO7Tm. Calculated (%): I, 30.23; Tm, 40.23. As
in the reaction with diiodide 2, an unidentified polymer (0.2 g)
was isolated from the organic layer.
1
735 w, 697 s, 495 w. H NMR (200 MHz, THFꢀd8), 27 °C, δ:
7.02—7.42 (m, 11 H, PhH); 7.55 (d, 2 H, J = 7.1 Hz); 7.93 (d,
2 H, J = 7.3 Hz). 13C NMR (50 MHz, ТHFꢀd8, 27 °C), δ: 124.6;
125.6; 126.8; 127.0; 127.2; 127.3; 127.9; 128.0; 128.1; 130.7;
Synthesis of [{(HN=CMe)2MeCNH2}Dy(thf)3.5]I3. Tetraꢀ
hydrofuran (50 mL) was added to the lightꢀyellow crystals of
[{(HN=CMe)2MeCNH2}Dy(MeCN)6]I3 (0.91 g, 0.99 mmol)
and the mixture was heated for 1 h at 80 °C. The solid partially
dissolved and was converted into a white powder, which was
separated centrifugation followed by decantation, washed with
cold THF (2×10 mL), and dried in vacuo at ~20 °C to give 0.73 g
(79.36%) of [{(HN=CMe)2MeCNH2}Dy(thf)3.5]I3. Found (%):
Dy, 17.54; I, 36.05. C28H20DyI3N4. Calculated (%): Dy, 17.0;
I, 39.84. The IR spectrum (Nujol, ν/cm–1) exhibits bands for
the (HN=CMe)2MeCNH2 ligand (3210, 3180, 1660, 1580, 1470,
1
131.8; 135.4; 137.5; 145.4. The H and 13C NMR signals were
assigned using a database.12
Reaction of diiodide 2 with benzonitrile. Under conditions of
the previous experiment, benzonitrile (20 mL, 200 mmol) was
added to a powder of compound 2 (4.57 g, 11 mmol). The
resulting redꢀbrown solution was concentrated to half its volꢀ
ume, benzonitrile being removed in vacuo. After 24 h, colorless
rectangular crystals precipitated. These were separated by deꢀ
cantation, washed with benzonitrile, and dried to give 1.8 g