8360 Inorganic Chemistry, Vol. 49, No. 18, 2010
Kajiwara et al.
N-oxide and trimethylsilylcyanide according to the reported
procedure.15 This cyanopyridine (3.0 g, 25 mmol) was heated
at 125 °C for 24 h in the presence of a catalytic amount of sodium
hydride (60% dispersion in mineral oil, 0.1 g) to afford 1,3,5-
tris(4-methyl-2-pyridyl)triazine. The crude product was dis-
solved in 100 mL of dichloromethane, and then 70 mL of
n-heptane was added. The black precipitate was removed by
filtration, and the resulting yellow solution was slowly concen-
trated to about 1/3 of the volume in air. The triazine was
obtained as yellow crystalline compound (2.14 g, yield =71%).
1H NMR (CDCl3): δ = 8.81 (1H, d, J = 4.8 Hz), 8.68 (1H, s),
7.35 (1H, d, J = 4.9 Hz), 2.54 (3H, s) ppm.
Bis(4-tert-butyl-2-pyridylcarbonyl)amine (10, HBuL). An aque-
ous suspension (6 mL) of 6 (1.44 g, 3 mmol) and an aqueous
solution (24 mL) of copper(II) sulfate (1.50 g, 6 mmol) were
mixed, and the resulting deep green solution was refluxed for 4 h,
during which the color changed to deep blue. This solution was
cooled to room temperature, and a blue powder of {CuII(PhL)}þ
compound precipitated, which was collected by filtration and
dried. This powder was used for the next reaction without further
purification. Yield 0.90 g. IR (cm-1): ν (CO) 1711 (s).
The blue powder (0.90 g) and excess Na2H2edta (2.0 g, 5.4 mmol)
were suspended in a H2O (80 mL)/CHCl3 (50 mL) mixture, and the
suspension was vigorously stirred for 1 h. The resulting clear
solution was separated, and the pale green organic layer was
dried with sodium sulfate and evaporated under reduced pressure.
10 was obtained as pale green crystals in a yield of 0.18 g (18%
based on 6).
1,3,5-Tris(4-tert-butyl-2-pyridyl)triazine (6)14. 4-tert-Butyl-2-
cyanopyridine was obtained using the same procedure to pre-
pare
5 with 4-tert-butylpridine N-oxide as the starting
material.15 The mixture of 4-tert-butylcyanopyridine (4.0 g,
25 mmol) and NaH (0.12 g, obtained from the 60% sodium
hydride dispersed in mineral oil by washing with n-hexane) was
heated at 125 °C for 24 h to give a black solid. The crude product
was purified by column chromatography on alumina with
chloroform as the eluent. The triazine was obtained as pale
yellow crystals. Yield 1.59 g (40%).
Elemental analysis calcd for C20H25.67N3O2.33 (10 1/3H2O):
3
C 69.54, H 7.49, N 12.16; Found: C 69.39, H 7.27, N 12.31. IR
1
(cm-1): v(CO) 1758 (s) H NMR (CDCl3): δ = 1.38 (s, 18H),
7.53 (d, 1H), 7.54 (d, 1H), 8.34 (d, 1H), 8.35 (d, 1H), 8.64 (d, 1H),
8.65 (d, 1H) ppm.
Bis(4-phenyl-2-pyridylcarbonyl)amine (11, HPhL). An ethano-
lic suspension (60 mL) of 7 (1.08 g, 2 mmol) and an aqueous
solution (20 mL) of copper(II) perchlorate (2.22 g, 6 mmol) were
mixed, and the resulting deep brown solution was refluxed for
4 h, during which the color changed to deep blue. The solution
was cooled to room temperature, and the blue powder that
precipitated was collected by filtration and dried. Yield 0.92 g.
The composition of this compound was confirmed to be
[CuII(PhL)(H2O)2]ClO4 (12) by using X-ray analysis (see Sup-
porting Information, Figure S2). This powder was used for the
next reaction without further purification. IR (cm-1): ν (CO)
1711 (s).
1H NMR (CDCl3): δ = 8.47 (1H, d, J = 5.1 Hz), 8.23 (1H, d,
J = 1.9 Hz), 7.43 (1H, dd, J = 5.2, 2.0 Hz), 1.35 (9H, s) ppm.
1,3,5-Tris(4-phenyl-2-pyridyl)triazine (7)14,15. 4-Phenyl-2-cy-
anopydine was obtained using the same procedure to prepare 5
with 4-phenylpridine N-oxide as the starting material. The
cyanopyridine (3.3 g, 18 mmol) was heated at 125 °C for 24 h
in the presence of a catalytic amount of sodium hydride (60%
dispersion in mineral oil, 0.17 g) to afford 1,3,5-tris(4-phenyl-2-
pyridyl)triazine. The crude product was first purified by column
chromatography on alumina with chloroform as the eluent, and
from the main fraction, a brown oily product was obtained. This
oily product was dissolved in 50 mL of dichloromethane, and
then 150 mL of n-heptane was added. The black precipitate was
collected by filtration and was again purified by column chro-
matography on alumina using chloroform as the eluent. The
triazine was obtained as a yellow solid. Yield 2.17 g (66%).
1H NMR (CDCl3): δ = 9.05 (1H, d, J = 1.7 Hz), 9.00 (1H,
dd, J = 5.1, 0.9 Hz), 7.81 (2H, dd, J = 6.8, 9.8 Hz), 7.76 (1H, d,
J = 5.1, 1.7 Hz), 7.57-7.54 (2H, br m), 7.51-7.49 (1H, br m)
ppm.
The blue powder (0.90 g) and excess Na2H2edta (2.0 g, 5.4
mmol) were suspended in a H2O (80 mL)/CHCl3 (50 mL)
mixture, and the suspension was vigorously stirred for 7 days.
The resulting clear solution was separated, and the pale green
organic layer was dried over sodium sulfate and evaporated
under reduced pressure to give pale green crystals of 11 in a yield
of 0.15 g (19% based on 7).
Elemental analysis (%) calcd for C24H19N3O3 (11 H2O): C
3
72.53, H 4.81, N 10.57; found: C 72.28, H 4.73, N 10.81. IR
(cm-1): v(CO) 1758 (s) 1H NMR (CDCl3): δ = 7.51 (t, 3H), 7.76
(d, 2H), 7.78 (d, 1H), 8.60 (s, 1H), 8.81 (d, 1H) ppm.
Bis(4-methyl-2-pyridylcarbonyl)amine (8, HMeL). An ethano-
lic solution (50 mL) of 5 (1.77 g, 5 mmol) and an aqueous
solution (60 mL) of copper(II) nitrate (1.21 g, 5 mmol) were
mixed, and the resulting deep brown solution was refluxed for
4 h. The resulting green solution was slowly evaporated to about
1/10 volume in the air, and blue plate crystals were obtained in a
yield of 0.95 g, of which the composition was confirmed to be
[CuII(MeL)(H2O)2]NO3 3H2O (9 3H2O) by using X-ray ana-
Synthesis of [Fe ( L
III MeL)2]ClO4 (12). To a solution of HMe
(351 mg, 1.37 mmol) in 20 mL of acetone was added an aqueous
solution (10 mL) of iron(III) nitrate (284 mg, 0.81 mmol). To the
mixture was added excess Et4NClO4 (987 mg, 4.3 mmol), and
the resulting dark green solution was allowed to stand for 4-5
days to afford 12 as dark brown crystals. They were collected by
suction filtration, washed with a minimum amount of acetone,
and dried in vacuo. Yield 310 mg (66%)
3
3
lysis (see Supporting Information, Figure S1). IR (cm-1): ν (CO)
1714 (s).
9 3H2O (0.95 g) and an excess of Na2H2edta (2.0 g, 5.4 mmol)
Elemental analysis (%) calcd for FeC28H26N6O9Cl (12 H2O):
3
3
were suspended in a H2O (80 mL)/CHCl3 (50 mL) mixture, and
the suspension was vigorously stirred for 1 h. The resulting clear
solution was separated, and the yellow organic layer was dried
with sodium sulfate and evaporated under reduced pressure.
8 was obtained as yellow crystals with a yield of 0.28 g (22%
based on 5).
C 49.32, H 3.85, N 12.32; found: C 49.23, H 4.24, N 12.15. IR
(cm-1): v(CO) 1758 (s); v(ClO4) 1095 (s).
Synthesis of [Fe ( L
III BuL)2]ClO4 (13). To a solution of HBu
(500 mg, 1.4 mmol) in 70 mL of acetone was added an aqueous
solution (20 mL) of iron(III) perchlorate (384 mg, 0.83 mmol).
The brown suspension was stirred at room temperature for 5 h,
and the resulting orange solution was allowed to stand for 1-2
days to afford 13 as orange crystals. They were collected by
suction filtration, washed with a minimum amount of acetone,
and dried in vacuo. Yield 350 mg (56%)
Elemental anal.; Found: C, 65.50; H, 5.40; N, 16.67. Calcd. for
C14H13N3O2 (HMeL): C, 65.87 ; H, 5.13; N, 16.46. IR (cm-1):
v(CO) 1758 (s) 1H NMR (CDCl3): δ = 2.45 (s, 6H), 7.26 (d, 1H),
7.37 (d, 1H), 8.04 (s, 1H), 8.17 (s, 1H), 8.42 (d, 1H), 8.60
(d, 1H) ppm.
Elemental analysis (%) calcd for FeC40H54N6O11Cl (13 3H2O):
3
C 54.21, H 6.14, N 9.48; found: C 54.27, H 6.02, N 9.61. IR (cm-1):
v(CO) 1758 (s); v(ClO4) 1758 (s).
(15) (a) Shuman, R. T.; Ornstein, P. L.; Paschal, J. W.; Gesellchen, P. D.
J. Org. Chem. 1990, 55, 738. (b) Bell, Z. R.; Motson, G. R.; Jeffery, J. C.;
McCleverty, J. A.; Ward, M. D. Polyhedron 2001, 20, 2045. (c) Hoyle, W. C.;
Benga, J. Talanta 1980, 27, 963.
Synthesis of [Fe ( L
III PhL)2]ClO4 (14). To a solution of HPh
(530 mg, 1.3 mmol) in 140 mL of acetone and 15 mL of methanol
was added an aqueous solution (20 mL) of iron(III) perchlorate