J IRAN CHEM SOC (2017) 14:2567–2578
2569
13C{1H} NMR (ppm): 146.9 (CH=N), 168.8 (NCO), 34.2,
25.1 (–CH2CH2), 157.8, 131.6 129.9, 120.5, 119.7, 116.5
(Ar–C).
2CH2), 6. 77 (d, 2H, Ar–H, 3JH–H = 8.4), 7.32 (t, 2H, Ar–H,
3JH–H = 7.8), 6.71 (t, 2H, Ar–H, 3JH–H = 7.4), 7.13 (dd, 2H,
3
3
Ar–H, JH–H = 7.8), 1.46 (q, 4H, Hα–SnEt, JH–H = 7.5),
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1.27 (t, 6H, Hβ–SnEt, JH–H = 7.2) 13C{1H} NMR (ppm):
Bis[dimethyltin(IV)] [N1′, N6′‑bis(2‑oxidobenzylidene)
a di p o d i hy d ra z i d e ] ( 1 ) T h e l i ga n d N1 ′ ,
N6′-bis(2-hydroxybenzylidene)adipodihydrazide (0.57 g,
1.5 mmol) H4L and triethylamine (0.84 mL, 6.0 mmol)
were dissolved in chloroform (50 mL), and the mixture
was stirred for 30 min at 298 K. Dimethytin(IV) dichloride
(0.66 g, 3.0 mmol) in chloroform (25 mL) was added drop
wise and reaction mixture further stirred for 3 h. The solu-
tion turned dark yellow and white precipitates of Et3NHCl
formed. The precipitates were fltered, and fltrate was con-
centrated by rotary evaporator to obtain yellow solid. The
product was recrystallized from CHCl3/n-hexane (4:1) mix-
160.9 (CH=N), 176.0 (NCO), 34.3, 26.2 (–CH2CH2), 167.0,
135.1, 134.2, 121.5, 116.9, 116.4 (Ar–C), 14.2 (Cα–SnEt,
1J[119/117Sn–13C] = 618, 590 Hz), 9,6 (Cβ–SnEt, 2J[119Sn–
13C] = 43 Hz), 119Sn NMR: δ (ppm) = −192.5.
Bis[di‑n‑butyltin(IV)] [N1′, N6′‑bis(2‑oxidobenzylidene)
adipodihydrazide] (3) Compound 3 was prepared in the
same way as 1, using following precursors quantities: N1′,
N6′-bis(2-hydroxybenzylidene)adipodihydrazide (0.57 g,
1.5 mmol), dibutyltin(IV) dichloride (0.91 g, 3.0 mmol) and
triethylamine (0.84 mL, 6.0 mmol) were reacted in a 1:2:4
ratio. Solid product was recrystallized from a chloroform
and n-hexane (4:1) mixture.
C24H30N4O4Sn2 (M = 678): C, 42.65; H, 4.47; N, 8.29
Found: C, 42.61; H, 4.45; N, 8.31% EI-MS, m/z(%):
[(C8H5N2O2)2C4H8Sn2(CH3)4]+ 678(3.5), [(C8H5N2O2)2
C4H8Sn2(CH3)3]+ 663(85.2), [(C8H5N2O2)2C4H8Sn2(CH3)2]+
648(4.3), [(C8H5N2O2) CNC4H8Sn(CH3)2]+ 393(8.8),
[(C8H5N2O2)C4H8Sn(CH3)2]+ 367(4.6), [(C8H5N2O2)
CH2Sn(CH3)2]+ 325(23.6), [(C8H6N2O2)Sn(CH3)2]+
312(4.5), [(C8H5N2O2)Sn(CH3)2]+ 311 (16.1), [(C8H6N2O2)
Sn]+ 282(100.0), [C7H4NOSn]+ 238(46.3), [(CH3)2HSn]+
151 (4.0), [CH3Sn]+ 135(25.4), [Sn]+ 120(9.6) FT-IR
Yield 75%. mp 88–90 °C. Anal. Calc. for
C36H54N4O4Sn2(M = 846): C, 51.21; H, 6.45; N,
6.64 Found: C, 51.19; H, 6.41; N, 6.60% EI-MS,
m/z(%): [(C8H5N2O2)2C4H8Sn2(C4H9)4]+ 846(5.5),
[(C8H5N2O2)2 C4H8Sn2 (C4H9)3]+ 789(100.0),
[(C8H5N2O2)2C4H8Sn2(C4H9)2]+ 732(4.3), [(C8H5 N2O2)
Sn]+ 281(5.5), [C7H4NOSn]+ 238(30.2), [(C4H9)2Sn]+
234(7.6), [C4H9Sn]+ 177 (4.2), [Sn]+ 120(4.3) FT-IR
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(cm−1): 1608 νC=N, 1076 νN–N, 568 νSn–O, 472 νSn–N, H
NMR (ppm): 8.58 (s, 2H, CH=N, 3J(119Sn–1H) = 43 Hz)],
2.35 (bs, 4H, 2CH2), 1.75 (bs, 4H, 2CH2), 6. 76 (d, 2H,
Ar–H, 3JH–H = 8.7), 7.31 (t, 2H, Ar–H, 3JH–H = 7.8), 6.71 (t,
2H, Ar–H, 3JH–H = 7.5), 7.12 (dd, 2H, Ar–H, 3JH–H = 7.8),
1.58–1.65 (m, 4H, Hα–SnBu), 1.44–1.49 (m, 4H, Hβ–SnBu),
1.34 (q, 4H, Hγ–SnBu, 3JH–H = 7.4), 0.88 (t, 6H, Hδ–SnBu,
3JH–H = 7.5) 13C{1H} NMR (ppm): 160.8 (CH=N), 175.8
(NCO), 34.3, 26.0 (–CH2CH2), 166.9, 135.0, 134.2,
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(cm−1): 1612 νC=N, 1084 νN–N, 576 νSn–O, 468 νSn–N, H
NMR (ppm): 8.59 (s, 2H, CH=N, 3J(119Sn–1H) = 47 Hz)],
2.35 (bs, 4H, 2CH2), 1.73 (bs, 4H, 2CH2), 6. 77 (d, 2H,
Ar–H, 3JH–H = 8.4), 7.33 (t, 2H, Ar–H, 3JH–H = 7.8), 6.74 (t,
2H, Ar–H, 3JH–H = 7.5), 7.13 (dd, 2H, Ar–H, 3JH–H = 7.8),
0.79 (s, 6H, Hα, SnCH3, 2J (119/117Sn–1H) = 75, 79. 13C{1H}
NMR (ppm): 161.0 (CH=N), 175.5 (NCO), 34.2, 26.0 (–
CH2CH2), 166.3, 135.2, 134.2, 121.6, 117.2, 116.5 (Ar–C),
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121.6, 116.8, 116.5(Ar–C), 22.0 (Cα–SnBu, J[119/117Sn–
13C] = 604, 577 Hz), 26.9 (Cβ–SnBu, 2J[119/117Sn–
13C] = 36 Hz), 26.5 (Cγ–SnBu, 3J[119/117Sn–13C] = 94 Hz),
13.6 (Cδ–SnBu), 119Sn NMR: δ (ppm) = −192.4.
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1.3 (Cα–SnCH3, J[119/117Sn–13C] = 648, 621 Hz), 119Sn
NMR: δ (ppm) = −154.8.
Bis[diethyltin(IV)] [N1′, N6′‑bis(2‑oxidobenzylidene)adi‑
podihydrazide] (2) Compound 2 was prepared in the same
way as 1, using N1′, N6′-bis(2-hydroxybenzylidene)adipo-
dihydrazide (0.57 g, 1.5 mmol), triethylamine (0.84 mL,
6.0 mmol) and diethyltin(IV) dichloride (0.74 g, 3.0 mmol)
in a 1:2:4 ratio. The solid product was recrystallized from a
chloroform and n-hexane (4:1) mixture.
Bis[diphenyltin(IV)] [N1′, N6′‑bis(2‑oxidobenzylidene)
adipodihydrazide] (4) Compound 4 was prepared in the
same way as 1, using following precursors quantities: N1′,
N6′-bis(2-hydroxybenzylidene)adipodihydrazide (0.57 g,
1.5 mmol), diphenyltin(IV) dichloride (1.03 g, 3.0 mmol)
and triethylamine (0.84 mL, 6.0 mmol) were reacted in a
1:2:4 ratio. The solid product was recrystallized from a chlo-
roform and n-hexane (4:1) mixture.
Yield 72%. mp 144–145 °C. Anal. Calc. for
C28H38N4O4Sn2 (M = 734):C, 45.94; H, 5.23; N, 7.65 Found:
C, 45.91; H, 5.22; N, 7.69% EI-MS, m/z(%):[(C8H5N2O2)2
C4H8Sn2(C2H5)3]+ 705(100.0), [C7H4NOSn]+ 238(11.0),
[Sn]+ 120(5.4) FT-IR (cm−1): 1610 νC=N, 1088 νN–N, 570
Yield 76%. mp 186–188 °C. Anal. Calc. for
C44H38N4O4Sn2 (M = 926): C, 57.18; H, 4.14; N,
6.06 Found: C, 57.21; H, 4.09; N, 6.08% EI-MS,
m/z(%): [(C8H5N2O2)2C4H8Sn2(C6H5)4]+ 926(5.6),
[(C8H5N2O2)2 C4H8Sn2(C6H5)3]+ 849(100.0),
[(C8H5N2O2)2C4H8Sn2(C6H5)2]+ 772(3.4), [(C8H5N2O2)
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νSn–O, 460 νSn–N, H NMR (ppm): 8.61 (s, 2H, CH=N,
3J(119Sn–1H) = 43 Hz)], 2.36 (bs, 4H, 2CH2), 1.75 (bs, 4H,
1 3