Organotin(IV) complexes with thiosemicarbazones
5
(m, NH), 1583(m, C=N–N=C), 1520 (s, Caro–O), 1025 (w, N–N), 1322, 837 (m, C–S), 599
1
(w, Sn–C), 550 (w, Sn–O), 464 (w, Sn–N). H NMR (DMSO-d6, ppm): 10.08 (s,1H, OH),
9.82 (m, 1H, N3–H), 8.34 (s, 1H, C7–H), 7.45 (d, 1H, J = 7.1, aroC4–H), 7.30 (d, 1H,
J = 7.6, aroC6–H), 7.06 (t, 1H, aroC5–H), 3.11 (d, 3H, C9–H), 1.50–1.54 (t, 2H, Sn–CH2–
CH2–CH2–CH3), 1.45–1.49 (m, 2H, Sn–CH2–CH2–CH2–CH3), 1.38–1.41 (m, 2H,
Sn–CH2–CH2–CH2–CH3), 0.96–0.99 (t, 3H, Sn–CH2–CH2–CH2–CH3). 13C NMR (DMSO-
d6, ppm): 178.45 (C=S), 163.20 (C=N), 151.35–131.23 (aromatic–C), 30.88 (CH3), 24.11,
22.80, 20.75, 18.54 (Sn–CH2–CH2–CH2–CH3). 119Sn NMR (DMSO-d6) δ: −168.45. Anal.
Calcd for C13H18ClN3O2SSn: C, 35.93; H, 4.18; N, 9.67. Found: C, 35.99; H, 4.25; N,
9.75%.
2.6. Synthesis of [PhSnCl(DDMT)] (5)
M.p.: 239–241 °C, (0.54 g, 79%). Molar conductance (DMSO) Ω−1cm2 mol−1: 12.11:
UV–Vis (DMSO) λmax/nm: 239, 335, 381, 427: FT-IR (KBr, cm−1) νmax: 3355 (m, OH), 3135
(m, NH), 1585 (m, C=N–N=C), 1505 (s, Caro–O), 1020 (w, N–N), 1333, 841 (m, C–S), 593
1
(w, Sn–C), 543 (w, Sn–O), 464 (w, Sn–N). H NMR (DMSO-d6, ppm): 10.10 (s, 1H, OH),
9.81 (m, 1H, N3–H), 8.30 (s, 1H, C7–H), 7.51–7.07(m, 8H, aro–H), 3.09 (d, 3H, C9–H).
13C NMR (DMSO-d6, ppm): 177.88 (C=S), 160.22 (C=N), 152.45–133.45 (aromatic–C),
30.98 (CH3). 119Sn NMR (DMSO-d6) δ: −178.15. Anal. Calcd for C15H14ClN3O2SSn: C,
39.64; H, 3.10; N, 9.25. Found: C, 39.55; H, 3.15; N, 9.36%.
2.7. Synthesis of [MeSnCl(DMMT)] (6)
H2DMMT (2) (0.223 g, 1.0 mmol) was dissolved in absolute methanol (10 mL) under a
nitrogen atmosphere in a round-bottomed reaction flask. Then, a methanolic solution of
methyltin(IV) trichloride (0.24 g, 1.0 mmol) was added dropwise and resulted in a yellow
solution. The resulting reaction mixture was refluxed for 4 h (scheme 2) and cooled to room
temperature. The yellow microcrystals were filtered off, washed with a small amount of
cold methanol, and dried in vacuo over silica gel. M.p.: 265–267 °C, (0.35 g, 76%). Molar
conductance (DMSO) Ω−1cm2 mol−1: 8.33: UV–Vis (DMSO)λmax/nm: 273, 325, 371, 508:
FT-IR (KBr, cm−1) νmax: 3215 (s, NH), 1575 (m, C=N–N=C), 1515 (s, Caro–O), 1035 (w,
1
N–N), 1320, 830 (m, C–S), 587 (w, Sn–C), 551 (w, Sn–O), 447 (w, Sn–N). H NMR
2
1
(DMSO-d6, ppm, J[119Sn, H]): 9.45 (m, 1H, N3–H), 8.25 (s, 1H, C7–H), 7.80 (d, 1H,
J = 7.2, aroC3–H), 7.11 (s, 1H, aroC6–H), 6.85 (d, 1H, J = 7.8, aroC4–H), 3.08 (d, 3H,
C9–H), 2.25 (s, 3H, H3C–Ph), 1.18 (s, 3H, Sn–CH3, [78.42 Hz]). 13C NMR (DMSO-d6,
ppm): 175.72 (C=S), 168.23 (C=N), 150.33–135.18 (aromatic–C), 31.89 (CH3), 21.12
(CH3–Ph), 17.11 (Sn–CH3). 119Sn NMR (DMSO-d6,) δ: −174.22. Anal. Calcd for
C11H14ClN3OSSn: C, 33.84; H, 3.61; N, 10.76. Found: C, 33.95; H, 3.71; N, 10.84%.
Complexes 7 and 8 were synthesized using a similar procedure to 6 using corresponding
organotin(IV) chloride(s) (scheme 2).
2.8. Synthesis of [BuSnCl(DMMT)] (7)
M.p.: 260–262 °C, (0.41 g, 81%). Molar conductance (DMSO) Ω−1cm2 mol−1: 11.38:
UV–Vis (DMSO) λmax/nm: 270, 327, 375, 405: FT-IR (KBr, cm−1) νmax: 3201 (s, NH), 1578
(m, C=N–N=C), 1518 (s, Caro–O), 1030 (w, N–N), 11,315, 832 (m, C–S), 589 (w, Sn–C),