1012
T. KIMURA ET AL.
Octakis(methylthio)octaethylphthalocyaninato Titanium (IV)
Benzenedithiolate (4a)
The solution of 3a, prepared as described above, was transferred by syringe to
the reactor containing PcSMeTiO (97.4 mg, 0.0845 mmol) under Ar. The solution was
stirred for 24 h, and the solvent was evaporated. The residue was purified by column
chromatography (Wakogel C-300HG, n-hexane:CHCl3 = 1:1 and CHCl3) and (Bio-beads,
CHCl3) to produce 4a in 51% yield (65.2 mg); dark green powder, mp > 300◦C; 1H NMR
(400 MHz, CDCl3) δ = 0.23 (t, J = 7.2 Hz, 6H, CH3), 1.60 (t, J = 7.2 Hz, 24H, CH3), 1.81
(q, 4H, CH2), 2.72 (s, 24H, SCH3), 4.68–5.00 (m, 16H, CH2) ppm; 13C NMR (101 MHz,
CDCl3) δ = 11.5, 16.4, 22.7, 25.4, 30.0, 124.9, 132.9, 136.4, 146.7, 146.8, 147.9, 151.4
ppm; UV-vis (CHCl3) λmax = 763.5 nm; FAB MS (m/z) 1504.13 [M+]; Anal. Calcd for
C66H74Br2N8S10Ti: C, 52.58; H, 4.95; N, 7.43. Found: C, 52.36; H, 5.09; N, 6.53.
Octakis(methylthio)octaethylphthalocyaninato Titanium (IV)
Benzenediselenoolate (4b)
Compound (4b) was prepared in 33% yield by the procedure as described above;
dark green powder, mp 225◦C; 1H NMR (400 MHz, CDCl3) δ = 0.29 (t, J = 7.4 Hz, 6H,
CH3), 1.59 (t, J = 7.2 Hz, 24H, CH3), 1.93 (q, 4H, CH2), 2.74 (s, 24H, SCH3), 4.60–4.99
(m, 16H, CH2) ppm; 13C NMR (101 MHz, CDCl3) δ = 11.7, 16.4, 22.7, 25.4, 29.7, 125.2,
132.9, 139.5, 146.6, 146.8, 148.5, 151.2 ppm; 77Se NMR (76 MHz, CDCl3) δ = 448.5 ppm;
UV-vis (CHCl3) λmax = 765.5 nm; FAB MS (m/z) 1600.13 [M+].
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