SYNTHESIS AND SPECTRAL PROPERTIES
683
M = Cd(II) (2),
M = Ni(II) (3),
M = Pd(II) (4),
M = Pt(II) (5),
M = Pt(IV) (6)
NH
N
N
N
N
N
N
M
HN
(1)
(2)
4- and 5-positions). MS (m/z (Irel, %)): 870 (83) [M]+,
5,10,15,20-Tetraphenyltetrabenzoporphyrin
(1)
was obtained by procedure reported in [13, 14]. Cad-
mium(II) 5,10,15,20-tetraphenyltetrabenzoporphyri-
nate (2) was obtained by the complexation of porphy-
rin 1 with cadmium acetate in dimethylformamide.
Synthesis procedure for complex 2 was reported in the
work [12].
calcd. for C60H36N4Ni: 871.
Palladium(II) 5,10,15,20-tetraphenyltetrabenzo-
porphyrinate (4). A mixture of 0.02 g (0.0216 mmol) of
complex 2 and 0.038 g (0.216 mmol) of PdCl2 was dis-
solved in 4 mL of DMF, heated to reflux, and refluxed
for 30 s. The mixture was treated similarly to complex 3.
Yield 0.016 g (0.0174 mmol, 80%).
1H NMR (CDCl3, δ, ppm): 8.26 (d, 8H, ortho-
C6H5), 7.92 (t, 4H, para-C6H5), 7.85 (d, 8Н, meta-
C6H5), 7.23–7.20 (m, 8H, benzene rings in the 3- and
6-positions), 7.13–7.09 (m, 8H, benzene rings in the
4- and 5-positions). MS (m/z (Irel, %)): 918 (98) [M]+,
calcd. for C60H36N4Pd: 919.
1H NMR (C6D6, δ, ppm): 8.37 (d, 8H, ortho-
C6H5), 7.73 t, (4H, para-C6H5), 7.63 (d, 8H, meta-
C6H5), 7.16–7.13 (m, 8H, benzene rings in the 3- and
6-positions), 7.10–7.07 (m, 8H, benzene rings in the
4- and 5-positions).
For C60H36N4Cd anal. calcd. (%): C 77.88; N 6.05;
H 3.92.
Found (%): C 77.65; N 6.15; H 3.99.
Platinum(II)
5,10,15,20-tetraphenyltetrabenzo-
porphyrinate (5). A mixture of 0.02 g (0.0216 mmol) of
complex 2 and 0.057 g (0.216 mmol) of PtCl2 was dis-
solved in 6 g of phenol, the mixture was heated to
reflux for 1 min, refluxed for 2 min, cooled, DMF and
distilled water were added, the resultant precipitate was
separated by filtration, washed with water, dried, and
chromatographed on aluminum oxide using chloro-
form as an eluent. Yield 0.0165 g (0.0164 mmol, 75%).
The course of complexation and metal exchange
reactions was monitored by spectrophotometry by
sampling. Electronic absorption spectra were
recorded on a Cary-100 spectrophotometer at ambient
temperature.
Nickel(II) 5,10,15,20-tetraphenyltetrabenzopor-
phyrinate (3). (a) A mixture of 0.02 g (0.0246 mmol) of
porphyrin 1 and 0.044 g (0.246 mmol) of Ni(OAc)2
was dissolved in 4 mL of DMF, heated to reflux,
refluxed for 40 s, and cooled, water was added, the
1H NMR (CDCl3, δ, ppm): 8.28 (d, 8H, ortho-
C6H5), 7.92 (t, 4H, para-C6H5), 7.85 (d, 8Н, meta-
resultant precipitate was separated by filtration, C6H5), 7.20–7.16 (m, 8H, benzene rings in the 3- and
washed with water, dried, and chromatographed on
aluminum oxide (using chloroform as an eluent).
Yield 0.017 g (0.0195 mmol, 79%). (b) A mixture of
0.02 g (0.0216 mmol) of complex 2 and 0.028 g (0.216
mmol) of NiСl2 was dissolved in 4 mL of DMF and
heated to reflux for 30 s. The mixture was treated sim-
ilarly to method (a). Yield 0.017 g (0.0195 mmol,
90%).
1H NMR (CDCl3, δ, ppm): 8.04 (d, 8H, ortho-
C6H5), 7.83 (t, 4H, para-C6H5), 7.75 (d, 8Н, meta-
C6H5), 7.16–7.13 (m, 8H, benzene rings in the 3- and
6-positions), 7.13–7.09 (m, 8H, benzene rings in the
4- and 5-positions). MS (m/z (Irel, %)): 1007 (48)
[M]+, calcd. for С60Н36N4Pt 1008.
Platinum(IV)(Br)2 5,10,15,20-tetraphenyltetraben-
zoporphyrinate (6). Complex 5 (0.02 g, 0.0198 mmol) was
dissolved in 10 mL of CHCl3. Twelve drops (0.11 mL)
of bromine was dissolved in 5 mL of chloroform,
25 drops of the resultant solution was added to the
solution of the complex with stirring. The mixture was
kept at ambient temperature for 20 min, water was
added, the organic layer was separated, and the solvent
6-positions), 7.10–7.07 (m, 8H, benzene rings in the was evaporated. Yield 0.019 g (0.0163 mmol, 83%).
RUSSIAN JOURNAL OF INORGANIC CHEMISTRY Vol. 63 No. 5 2018