C≡CCH2, 3JH–H = 6.2 Hz), 1.59–1.54 (m, 4H, CH2), 1.48 (m, 4H,
ArH, 4JH–H = 2.3 Hz), 7.34–7.29 (m, 5H, thiophene + ArH), 7.16
(m, 2H, thiophene), 6.99–6.97 (m, 1H, thiophene), 6.69 (s, 1H,
ArH), 6.67 (d, 1H, ArH). 13C NMR (d8-THF): 174.4 (Ph), 173.8
CH2), 1.33–1.31 (m, 24H, CH2), 0.89 (t, 6H, CH3, 3JH–H = 6.7 Hz).
13
=
C NMR (d8-THF): d 174.0 (Ph), 173.4 (Ph), 164.0 (C N), 163.1
=
=
=
(C N), 153.7, 147.0, 141.3, 140.5, 139.1, 138.8, 137.9 124.9, 124.8,
(Ph), 163.9 (C N), 163.1 (C N), 153.5, 147.2, 141.9, 141.0, 138.4,
138.1, 137.9, 131.3, 131.2, 127.8, 127.0, 126.9, 126.0, 125.6, 125.1,
125.0, 124.7, 123.3, 122.4, 122.1, 107.1, 106.8, 95.1 (C≡C), 95.0
124.6, 123.2, 122.0, 121.7, 108.9, 108.6, 86.6 (C≡C), 86.5 (C≡C),
82.1 (C≡C), 33.1 (C≡CCH2), 30.8, 30.5, 30.4, 30.0, 26.5, 23.7,
20.2 (CH2), 14.6 (CH3). IR (cm−1 KBr): 2952 (sh), 2925, 2853
(C≡C), 80.2 (C≡C), 80.1 (C≡C). MS (FAB): m/z 552.1 (M+
+
=
=
m(N C–H), 2190 m(C≡C), 1593 m(C N). MS (FAB): m/z 668.4
(M+). Anal. Calcd for C43H53MgN3O2·2H2O: C, 73.34; H, 8.16; N,
5.97. Found: C, 73.62; H, 8.30; N, 5.78%.
1). Anal. Calcd for C31H17MgN3O2S2·2H2O: C, 63.33; H, 3.60; N,
7.15; S, 10.91. Found: C, 63.61; H, 3.60; N, 6.78; S, 10.90%.
Synthesis of complex 8a. To compound 6a (16.6 mg,
0.044 mmol) in MeOH–THF (10 mL/10 mL) was added
Zn(OAc)2·2H2O (9.7 mg, 0.044 mmol) and compound 1f (13.8 mg,
0.044 mmol). The mixture was stirred for 20 h, and then the
solvent was removed under vacuum. The residue was washed with
methanol and the precipitate was collected by filtration. The yellow
solid (62% yield, 20 mg) was identified as 8a. Melting point of
Synthesis of monoimine 6b and Mg(II) Schiff base complex 7b.
Monoimine 6b (yellow solid, 20% yield) was prepared using the
same synthetic procedure as that for 6a. Spectroscopic data of 6b:
1
=
H NMR (CDCl3): d 12.75 (s, 1H, OH), 8.57 (s, 1H, N CH), 8.02
(d, 1H, PyrH,3JH–H = 4.8 Hz), 7.58 (d, 1H, ArH, 4JH–H = 1.9 Hz),
7.54 (dd, 1H, ArH, 3JH–H = 8.5 Hz, 4JH–H = 2.4 Hz), 7.41 (d, 2H,
ArH, 3JH–H = 8.2 Hz), 7.21 (d, 1H, PyrH, 3JH–H = 7.6 Hz), 7.14 (d,
2H, ArH, 3JH–H = 8.2 Hz), 7.00 (d, 1H, ArH, 3JH–H = 8.5 Hz), 6.73
(dd, 1H, PyrH, 3JH–H = 7.6 Hz, 3JH–H = 4.8 Hz), 4.81 (s, 2H, NH2),
2.59 (t, 2H, CH2, 3JH–H = 7.4 Hz), 1.63 − 1.58 (m, 2H, CH2), 1.31 −
1.29 (m, 4H, CH2), 0.87 (t, 3H, CH3, 3JH–H = 6.4 Hz). 13C NMR
◦
1
=
8a: >350 C. H NMR (d8-THF): d 9.63 (s, 1H, N CH), 8.96
3
4
=
(s, 1H, N CH), 8.37 (dd, 1H, PyrH, JH–H = 4.6 Hz, JH–H
=
3
4
1.5 Hz), 8.22 (dd, 1H, PyrH, JH–H = 8.3 Hz, JH–H = 1.5 Hz),
4
3
7.76 (d, 1H, ArH, JH–H = 2.4 Hz), 7.42 (dd, 1H, ArH, JH–H
=
4
8.9 Hz, JH–H = 2.4 Hz), 7.38–7.35 (m, 2H, ArH), 7.21 (dd, 1H,
=
(CDCl3) 163.0 (Ph), 160.7 (C N), 153.2, 147.1, 143.4, 136.7, 135.5,
ArH, 3JH–H = 8.9 Hz, 4JH–H = 2.3 Hz), 6.63 (d, 1H, ArH, 3JH–H
=
131.4, 130.1, 128.5, 125.1, 120.3, 119.2, 117.7, 114.8, 114.5 (Ph),
89.3 (C≡C), 79.3 (C≡C), 35.9, 31.4, 30.9, 22.5 (CH2), 14.0 (CH3).
MS (FAB): m/z 384.2 (M+ + 1). Anal. Calcd for C25H25N3O: C,
78.30; H, 6.57; N, 10.96. Found: C, 78.37; H, 6.51; N, 10.86%.
8.9 Hz), 6.73 (d, 1H, ArH, 3JH–H = 8.9 Hz), 2.37 (t, 2H, C≡CCH2,
3JH–H = 6.8 Hz), 1.60–1.57 (m, 2H, CH2), 1.50–1.45 (m, 2H, CH2),
3
1.34–1.29 (m, 12H, CH2), 0.89 (t, 3H, CH3, JH–H = 7.2 Hz).
IR (cm−1 KBr): 2959 (sh), 2926, 2854 m(N C–H), 2209 m(C≡C),
=
Complex 7b: Light yellow solid with 62% yield. Spectroscopic
+
=
1618 m(C N). MS (FAB): m/z 734.1 (M + 1). Anal. Calcd for
1
=
data of 7b: H NMR (d8-THF): d 9.57 (s, 1H, N CH), 8.91 (s,
C39H32F5N3O2Zn·H2O: C, 62.20; H, 4.55; N, 5.58. Found: C, 62.58;
3
=
1H, N CH), 8.33 (d, 1H, PyrH, JH–H = 4.5 Hz), 8.19 (d, 1H,
H, 4.71; N, 5.38%.
3
4
PyrH, JH–H = 8.4 Hz), 7.59 (d, 1H, ArH, JH–H = 2.3 Hz), 7.52
4
(d, 1H, ArH, JH–H = 2.3 Hz), 7.36–7.29 (m, 7H, ArH), 7.14 (d,
Synthesis of complex 8b. Complex 8b (yellow solid, 49% yield)
was prepared using the same synthetic procedure as that for 8a.
3
3
4H, ArH, JH–H = 8.0 Hz), 6.68 (d, 2H, ArH, JH–H = 8.0 Hz),
2.61 (t, 4H, PhCH2, 3JH–H = 6.4 Hz), 1.61 (m, 4H, CH2), 1.35–1.33
1
=
=
H NMR (d8-THF): d 9.59 (s, 1H, N CH), 8.95 (s, 1H, N CH),
(m, 8H, CH2), 0.91 (t, 6H, CH3, JH–H = 6.6 Hz). 13C NMR (d8-
3
3
4
8.36 (dd, 1H, PyrH, JH–H = 4.73 Hz, JH–H = 1.2 Hz), 8.19 (dd,
=
=
THF): d 174.3 (Ph), 173.7 (Ph), 163.9 (C N), 163.1 (C N), 153.5,
147.1, 143.1, 143.0, 141.7, 140.9, 138.7, 138.4, 137.9, 131.8, 129.2,
125.9, 125.0, 124.7, 123.2, 122.9, 122.2, 121.9, 107.8, 107.5, 90.8
(C≡C), 87.2 (C≡C), 87.1 (C≡C), 36.6 (CH2), 32.5, 32.0, 30.8, 23.5
(CH2), 14.4 (CH3). MS (FAB): m/z 680.4 (M+ + 1). Anal. Calcd
for C45H41MgN3O2·2H2O: C, 75.47; H, 6.33; N, 5.87. Found: C,
75.79; H, 6.51; N, 5.94%.
3
4
1H, PyrH, JH–H = 8.3 Hz, JH–H = 1.2 Hz), 7.56 (d, 1H, ArH,
4JH–H = 2.2 Hz), 7.37–7.29 (m, 3H, ArH), 7.21 (d, 1H, ArH, 3JH–H
=
3
8.8 Hz), 6.77 (d, 1H, ArH, JH–H = 8.8 Hz), 6.73 (d, 1H, ArH,
3JH–H = 8.8 Hz), 4.43–4.42 (m, 2H, CpFe), 4.21–4.19 (m, 7H,
CpFe), 2.37 (t, 2H, C≡CCH2, 3JH–H = 6.8 Hz), 1.60–1.58 (m, 2H,
CH2), 1.50–1.48 (m, 2H, CH2), 1.34–1.29 (m, 12H, CH2), 0.89
(t, 3H, CH3, JH–H = 6.8 Hz). MS (FAB): m/z 751.1 (M+ + 1).
3
Synthesis of monoimine 6g and Mg(II) Schiff base complex 7g.
Anal. Calcd for C43H42FeN3O2Zn·H2O: C, 66.89; H, 5.74; N, 5.44.
Complex 6g (yellow solid, 12% yield) was prepared using the same
Found: C, 66.88; H, 5.74; N, 5.64%.
1
synthetic procedure as that for 6a. Spectroscopic data of 6g: H
=
NMR (CDCl3): 12.82 (s, 1H, OH), 8.56 (s, 1H, N CH), 8.03
Synthesis of complex 8c. Complex 8c (yellow solid, 61% yield)
was prepared using the same synthetic procedure as that for 8a.
(dd, 1H, PyrH,3JH–H = 5.0 Hz,4JH–H = 1.6 Hz), 7.58 (d, 1H, ArH,
4JH–H = 2.1 Hz), 7.53 (dd, 1H, ArH, JH–H = 8.6 Hz, JH–H
=
Melting point of 8c: >350 ◦C. 1H NMR (d8-THF): d 9.55 (s, 1H,
3
4
3
=
=
2.1 Hz), 7.28–7.23 (m, 3H, thiophene + PyrH), 7.02–6.99 (m, 2H,
N CH), 8.99 (s, 1H, N CH), 8.36 (d, 1H, PyrH, JH–H = 4.6 Hz),
3
3
3
4
thiophene +ArH), 6.72 (dd, 1H, PyrH, JH–H = 7.6 Hz, JH–H
=
8.20 (d, 1H, PyrH, JH–H = 8.3 Hz), 7.47 (d, 1H, ArH, JH–H
=
5.0 Hz), 4.79 (s, 2H, NH2). 13C NMR (CDCl3): 162.8 (Ph), 160.9
2.3 Hz), 7.43 (d, 1H, ArH, JH–H = 2.3 Hz), 7.35–7.28 (m, 2H,
4
3
4
=
(C N), 153.2, 147.2, 136.5, 135.5, 131.7, 130.0, 127.2, 127.1, 125.1,
ArH), 7.22 (dd, 1H, ArH, JH–H = 8.8 Hz, JH–H = 1.7 Hz), 6.77
(d, 1H, ArH, 3JH–H = 8.8 Hz), 6.73 (d, 1H, ArH, 3JH–H = 8.8 Hz),
4.43–4.41 (m, 2H, CpFe), 4.21–4.19 (m, 7H, CpFe), 2.37 (t, 2H,
123.3, 119.2, 117.7, 114.5, 114.2, 91.9 (C≡C), 81.7 (C≡C). MS
(FAB): m/z 320.0 (M+ + 1). Anal. Calcd for C18H13N3OS: C,
67.69; H, 4.10; N, 13.16. Found: C, 67.76; H, 4.18; N, 13.26%.
Complex 7g: Dark brown solid with 51% yield. Spectroscopic
data of 7g: H NMR (d8-THF): 9.57 (s, 1H, N CH), 8.91 (s, 1H,
C≡CCH2, 3JH–H = 6.9 Hz), 1.60–1.55 (m, 2H, CH2), 1.50–1.48 (m,
3
2H, CH2), 1.34–1.31 (m, 12H, CH2), 0.89 (t, 3H, CH3, JH–H
=
1
6.2 Hz). IR (cm−1 KBr): 2959 (sh), 2924, 2852 m(N C–H), 2210
=
=
3
=
=
N CH), 8.34 (d, 1H, PyrH, JH–H = 3.8 Hz), 8.19 (d, 1H, PyrH,
m(C≡C), 1614m(C N) Anal. Calcd for C43H42FeN3O2Zn·H2O: C,
3JH–H = 8.7 Hz), 7.61 (d, 1H, ArH, 4JH–H = 2.3 Hz), 7.54 (d, 1H,
66.89; H, 5.74; N, 5.44. Found: C, 66.93; H, 5.77; N, 5.66%.
This journal is
The Royal Society of Chemistry 2007
Dalton Trans., 2007, 781–791 | 789
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