1636 Inorganic Chemistry, Vol. 50, No. 5, 2011
Tabuchi et al.
N-[6-(4-Methoxyphenyl)pyridin-2-ylmethyl]-N-(6-phenylpyri-
din-2-ylmethyl)benzylamine (3p). This compound was prepared
in a similar manner for the synthesis of 3m, using 6-(4-methox-
yphenyl)pyridin-2-ylcarboxyaldehyde (2p), instead of 2m (70%
(hexane and ethyl acetate eluent) converted some of compound
4 to compound 5H. Thus, the isolated yield of 4 was 6% and that
of 5H was 25%, based on the starting copper(II) complex
CuIILmH after the SiO2 column chromatography.
1
4. 1H NMR (400 MHz, CDCl3): δ 3.71 (3 H, s, -CH3), 3.77
(2 H, s, -CH2-), 3.91(2H, s, -CH2-), 3.91 (2 H, s, -CH2-), 6.74
(1 H, d, J = 10.0 Hz), 6.77 (1 H. d, J = 10.4 Hz), 7.16 (1 H, dd,
J = 7.4 and 1.6 Hz), 7.22-7.25 (1 H, m), 7.33 (2 H, t, J = 7.4
Hz), 7.39 (1 H, t, J = 7.2 Hz), 7.44-7.47 (4 H, m), 7.51 (1 H, d,
J = 7.2 Hz), 7.59 (1 H, d, J = 7.6 Hz), 7.70-7.77 (3 H, m), 7.99
(2 H, d, J = 6.8 Hz); FT-IR (NaCl) 1672 and 1727 cm-1 (CdO);
isolated yield). H NMR (400 MHz, CDCl3): δ 3.82 (2 H, s,
-CH2-), 3.86 (3 H, s, -OCH3), 3.95 (2 H, s, -CH2-), 3.97
(2 H, s, -CH2-), 6.98 (2 H, d, J = 8.8 Hz), 7.23-7.27 (1 H. m),
7.34 (2 H, t, J = 7.4 Hz), 7.41 (1 H, d, J = 7.2 Hz), 7.44-7.54
(6 H, m), 7.59 (2 H, t, J = 7.8 Hz), 7.68-7.76 (2 H, m), 7.97 (2 H,
d, J = 8.8 Hz), 8.01 (2 H, d, J = 6.8 Hz); HRMS (FABþ): m/z =
472.2385. Calcd for (C32H30N3O)þ 472.2389.
þ
N-[(6-(3-Hydroxylphenyl)pyridin-2-ylmethyl)-N-(6-phenyl-
pyridin-2-ylmethyl)benzylamine (LpH). This compound was pre-
pared in a similar manner for the synthesis of LmH, using 3p
instead of 3m (41% isolated yield). 1H NMR (400 MHz, CDCl3):
δ 3.79 (2 H, s, -CH2-), 3.95 (2 H, s, -CH2-), 3.97 (2 H, s,
-CH2-), 6.75 (2 H, d, J = 9.2), 7.23 (1 H, t, J = 7.4), 7.32 (2 H,
t, J = 7.6 Hz), 7.52-7.39 (1 H, m), 7.42-7.48 (5 H, m),
7.52-7.59 (3 H, m), 7.66-7.40 (2 H, m), 7.78 (2 H, d, J =
9.2 Hz), 7.96 (2 H, d, J = 6.8 Hz); HRMS (FABþ): m/z =
458.2220. Calcd for (C31H27N3O)þ 458.2232.
HRMS (FABþ) m/z = 502.2159; Calcd for C32H28N3O3
502.2131.
5H. 1H NMR (400 MHz, CDCl3): 3.89 (2 H, s, H23), 3.96 (2
H, s, H1), 4.03 (2 H, s, H13), 6.71 (1 H, d, J = 10.2 Hz, H10), 6.83
(1 H. d, J = 10.2 Hz, H9), 7.00 (1 H, d, J = 7.6 Hz, H3),
7.22-7.26 (1 H, m, H27), 7.31 (2 H, t, J = 7.6 Hz, H26), 7.39 (1 H,
t, J = 7.2 Hz, H22), 7.43-7.47 (2 H, m, H21), 7.52 (2 H, d, J = 7.2
Hz, H25), 7.56 (1 H, d, J = 7.6 Hz, H17), 7.61 (1 H, d, J = 7.2 Hz,
H15), 7.71 (1 H, t, J = 7.6 Hz, H16), 7.77 (2 H, t, J = 8.2 Hz, H4),
7.94 (2 H, d, J = 7.2 Hz, H20), 9.04 (1 H, d, J = 9.2 Hz, H5); 13
C
Synthesis of Copper(II) Complexes. [CuII(LmH)(CH3CN)]-
NMR (100 MHz, CDCl3): 55.26 (C23), 60.02 (C1), 61.12 (C13),
104.28 (C7), 117.99 (C3), 119.05 (C17), 121.81 (C5), 122.21 (C15),
126.81 (C20), 127.68 (C27), 128.54 (C26), 128.70 (C21), 128.93
(C22), 129.38 (C25), 132.74 (C9), 137.14 (C24), 137.37 (C16),
139.15 (C19), 141.90 (C4), 143.56 (C10), 148.71 (C2), 152.88
(C6), 156.52 (C18), 157.45 (C14), 173.90 (C12), 183.52 (C8),
184.38 (C11); FT-IR (NaCl, cm-1) 1686 and 1731 (CdO), 347þ4
(OH); HRMS (FABþ) m/z = 488.1990; Calcd for C32H28N3O3
488.1974.
[CuII(6)](ClO4) (CuII6). CuIILpH (50 mg, 0.066 mmol) was
dissolved in methanol (30 mL) and Et3N (2 equiv) was added to
the solution. The resulting solution was stirred for 3 days at 60
ꢀC, and then the solvent was reduced under reduced pressure to
give a brown residue. The addition of ether (100 mL) to the
residue gave a brown powder, which precipitated by allowing
the mixture to stand for several minutes. The supernatant was
then removed by decantation, and the remaining brown solid
was washed with ether three times and dried to give complex
CuII6 in 80%. FT-IR (KBr, cm-1): 1192 and 621 (ClO4-), 1665
(CdO); MS (ESIþ) m/z = 535.1; Calcd for C31H26N3O2Cu
535.1.
(ClO4)2 (CuIILmH). CuII(ClO4)2 6H2O (74 mg, 0.20 mmol) was
3
added to an acetonitrile solution (5 mL) of ligand LmH (92 mg,
0.20 mmol) and stirred for 15 min at room temperature. The
addition of ether (100 mL) to the solution gave a green powder
that was precipitated by allowing the mixture to stand for 30
min. The supernatant was then removed by decantation, and the
remained green solid was washed with ether three times and
dried to give complex CuIILmH in 75%. Single crystals of
CuIILmH were obtained by vapor diffusion of ether into an
acetone:CH3CN (5:1) solution of the complex. FT-IR (KBr,
cm-1): 1114 and 623 (ClO4-), 3374 (OH); HRMS (FABþ) m/z
= 520.1445; Calcd for C31H27N3OCu 520.1450; Anal. Calcd
for: [CuII(Lm)(CH3CN)](ClO4)2 H2O: C, 50.87; H, 4.14; N,
3
7.19. Found: C, 50.71; H, 3.92; N, 7.00.
[CuII(LpH)(CH3CN)](ClO4)2 (CuIILpH). This compound was
synthesized by following the same procedure as that described
for the preparation of CuIILmH, using LpH (92 mg, 0.20 mmol)
instead of LmH as a green powder in a 82% yield. Single crystals
of CuIILpH were obtained by vapor diffusion of ether into an
acetone:CH3CN (5:1) solution of the complex. FT-IR (KBr,
cm-1): 1094 and 626 (ClO4-), 3371 (OH); HRMS (FABþ) m/z
= 520.1474; Calcd for C31H27N3Ocu 520.1450; Anal. Calcd for
[CuII(LpH)(CH3CN)](ClO4)2 H2O 1/2CH3CN: C, 50.67; H,
Isolation and Structure Determination of Modified Ligand 6H.
After the reaction described above, the reaction mixture was
dissolved in CH2Cl2 (20 mL) and 25% NH3 aqueous solution
(10 mL) was added to the solution. The aqueous solution was
then extracted with CH2Cl2 (30 mL ꢀ 3), and the combined
organic layer was dried over Na2SO4. After the removal of
Na2SO4 by filtration, evaporation of the solvent gave a brown
3
3
4.05; N, 6.46. Found: C, 50.87; H, 4.24; N, 6.66.
[CuII(4)(OCH3)](ClO4) (CuII4). CuIILmH (50 mg, 0.066
mmol) was dissolved in methanol (30 mL), and then Et3N
(2 equiv) was added to the solution. The resulting solution was
stirred for 3 days at room temperature. After the reaction, the
solvent was removed under reduced pressure to give a brown
residue, to which ether (100 mL) was added. Brown powder was
gradually precipitated by allowing the mixture to stand for
several minutes. The supernatant was then removed by decanta-
tion, and the remaining brown solid was washed with ether three
times and dried to give complex CuII4 in 94%. FT-IR (KBr,
cm-1): 1108 and 622 (ClO4-); HRMS (FABþ) m/z = 595.1514;
Calcd for C33H30N3O4Cu 595.1532.
1
material. The H NMR spectrum of the resulting brown ma-
terial indicated that compound 6H was produced in 56% (NMR
yield based on CuIILpH using CH2Br2 as an internal standard).
1H NMR (400 MHz, CDCl3): δ 3.79 (2 H, s, H21), 3.93 (2 H, s,
H11), 3.94 (2 H, s, H1), 6.26 (2 H, d, J = 8.8 Hz, H8), 6.48 (1 H, s,
OH26), 6.72 (2 H. d, J = 8.8 Hz, H9), 7.09 (1 H, d, J = 7.6 Hz,
H5), 7.26-7.31 (1 H, m, H25), 7.36 (2 H, t, J = 8.4 Hz, H24),
7.40-7.42 (1 H, m, H20), 7.46 (2 H, d, J = 7.2 Hz, H23),
7.49-7.54 (3 H, m, H13 and H19), 7.59-7.64 (2 H, m, H3 and
H15), 7.68 (1 H, t, J = 7.6 Hz, H4), 7.74 (1 H, t, J = 7.8 Hz, H14),
8.00 (2 H, d, J = 8.4 Hz, H18); 13C NMR (100 MHz, CDCl3):
58.82 (C21), 59.30 (C1), 60.19 (C11), 70.78 (C7), 118.73 (C5
and C15), 120.95 (C13), 122.65 (C3), 126.87 (C18), 127.19
(C25), 127.85 (C8), 128.38 (C24), 128.67 (C19 and C23), 128.87
(C20), 137.13 (C14), 138.25 (C4), 138.88 (C22), 139.32 (C17),
150.81 (C9), 154.19 (C6), 156.65 (C16), 159.14 (C2 or C12),
159.25 (C2 or C12), 185.74 (C10). FT-IR (NaCl, cm-1) 1688
and 1733 (CdO), 3465 (OH); HRMS (FABþ) m/z = 488.1990;
Isolation and Structure Determination of Modified Ligands 4
and 5H. After the reaction described above, the mixture was
dissolved in CH2Cl2 (20 mL) and a 25% NH3 aqueous solution
(10 mL) was added to the solution. The aqueous solution was
then extracted with CH2Cl2 (30 mL ꢀ 3), and the combined
organic layer was dried over Na2SO4. After removal of Na2SO4
by filtration, evaporation of the solvent gave a brown material.
1
The H NMR spectrum of the resulting brown material indi-
cated that compound 4 was produced in 51% (NMR yield based
on CuIILmH, using CH2Br2 as an internal standard). A SiO2
column chromatographic treatment of the brown material
þ
Calcd for C32H28N3O3 488.1974. FT-IR (NaCl, cm-1) 1671