ACCEPTED MANUSCRIPT
The procedure of C2 is same as C1 except that Ga(NO3)3 (0.5 mmol) was replaced by GaCl3 (1 mmol).
Yield 78%. Anal. Calcd for C9H11Cl2GaN4S: C, 31.07; H, 3.19; N, 16.10. Found: C, 31.10; H, 3.17; N,
16.11. IR (main peaks): 2929 (vs, amide), 1603m, 1514 (vs, pyridine), 1368 (s, C=N), 1305s, 1248s,
1136s, 1054s, 903 (s, C=S), 775vs, 666m, 624m. MS m/z (%) 275.00. (M − 2Cl, 100). 1H NMR (400
MHz, DMSO-d6) δ 9.04 (s, 1H, Py-H), 8.20 (d, J = 1.4 Hz, 1H, N=CH), 7.99 (t, J = 6.6 Hz, 2H, Py-H),
7.57 (s, 1H, Py-H), 3.31 – 3.21 (m, 6H, N(CH3)2). 13C NMR (101 MHz, DMSO-d6) δ 177.30 (s, C=S),
145.27 (s, C=N), 144.95 (s, Py–C), 142.81 (s, Py–C), 138.23 (s, Py–C), 127.61 (s, Py–C), 126.44 (s,
Py–C), 40.58 (s, CH3).
4.2.4
Synthesis
and
characterization
of
[bis(1-pyrrolidinecarbothioic
acid
2-(2-pyridinylmethylene)hydrazide) -N,N,S-gallium(III)] hydroxide (C3).
The procedure of C3 is same as C1 except that L1 was replaced by L2. Yield 82%. Anal. Calcd for
C22H24GaN8OS2: C, 47.75; H, 4.92; N, 20.25; O, 2.89. Found: C, 47.73; H, 4.95; N, 20.22 O, 2.32. IR
(main peaks): 2963 (vs, amide), 1605 (vs, pyridine), 1450 (s, C=N), 1368 s, 1242s, 1164s, 913 (vs, C=S),
1
776vs, 650m, 516m. MS m/z (%) 534.09 (M−, 100). H NMR (400 MHz, DMSO-d6) δ 9.04 (s, 1H,
Py-H), 8.84 (d, J = 5.2 Hz, 1H, Py-H), 8.47 (s, 1H, Py-H), 8.27 – 8.17 (m, 2H, N=CH), 7.99 (t, J = 6.8
Hz, 2H, Py-H), 7.87 (d, J = 7.8 Hz, 1H, Py-H), 7.77 – 7.73 (m, 1H, Py-H), 7.61 – 7.51 (m, 1H, Py-H),
3.81 – 3.55 (m, 8H, Pyrrolidine-H), 1.98 – 1.88 (m, 8H, Pyrrolidine-H). 13C NMR (101 MHz,
DMSO-d6) δ 174.13 (s, C=S), 145.36 (s, C=N), 144.89 (s, C=N), 142.76 (s, Py–C), 137.63 (s, Py–C),
127.50 (s, Py–C), 126.31 (s, Py–C), 50.78 (s, Pyrrolidine-C), 49.06 (s, Pyrrolidine-C), 25.05 (s,
Pyrrolidine-C), 24.51 (s, Pyrrolidine-C).
4.2.5
Synthesis
and
characterization
of
[1-pyrrolidinecarbothioic
acid
2-(2-pyridinylmethylene)hydrazide-N,N,S-gallium(III)] bis(Chloride) (C4).
The procedure of C4 is same as C3 except that Ga(NO3)3 (0.5 mmol) was replaced by GaCl3 (1 mmol).
Yield 83%. Anal. Calcd for C11H13Cl2GaN4S: C, 35.33; H, 3.50; N, 14.98. Found: C, 35.30; H, 3.53; N,
14.96. IR (main peaks): 2958 (vs, amide), 2866vs, 1604 (vs, pyridine), 1457 (s, C=N), 1282s, 1179s,
1118s, 907 (vs, C=S), 774vs, 647vs, 577m. MS m/z (%) 301.00 (M − 2Cl, 100). 1H NMR (400 MHz,
DMSO-d6) δ 9.02 (s, 1H, Py-H), 8.20 (td, J = 7.8, 1.4 Hz, 1H, N=CH), 7.98 (dd, J = 15.8, 6.5 Hz, 2H,
Py-H), 7.61 – 7.51 (m, 1H, Py-H), 3.68 (dd, J = 28.5, 21.6 Hz, 4H, Pyrrolidine-H), 1.96 – 1.84 (m, 4H,
Pyrrolidine-H). 13C NMR (101 MHz, DMSO-d6) δ 174.15 (s, C=S), 145.97 (d, J = 18.1 Hz, C=N),
144.88 (s, Py–C), 142.75 (s, Py–C), 137.63 (s, Py–C), 127.50 (s, Py–C), 126.34 (s, Py–C), 48.59 (s,
Pyrrolidine-C), 25.02 (d, J = 6.9 Hz, Pyrrolidine-C).
4.3 Determination of structure of Ga(III) complexes
X-ray crystallographic data of Ga(III) complexes (C1-C4) were collected by a Bruker SMART Apex II
CCD diffractometer using graphite-monochromated Mo-Kα (λ = 0.71073 Å) radiation. The SADABS
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