Synthesis and spectral properties of β-bromo-substituted nickel(II) tetraphenylporphyrins

Article abstract of DOI:10.1134/S1070428017070235

Bromination of (5,10,15,20-tetraphenylporphyrinato)nickel(II) with N-bromosuccinimide in chloroform and chloroform–dimethylformamide mixture and complexation of 2-bromo-5,10,15,20-tetraphenylporphyrin and 2,3,12,13-tetrabromo-5,10,15,20-tetraphenylporphyr

Full text of DOI:10.1134/S1070428017070235

ISSN 1070-4280, Russian Journal of Organic Chemistry, 2017, Vol. 53, No. 7, pp. 1094–1098. © Pleiades Publishing, Ltd., 2017.
Original Russian Text © N.V. Chizhova, A.V. Konakova, O.V. Mal’tseva, N.Zh. Mamardashvili, O.I. Koifman, 2017, published in Zhurnal Organicheskoi
Khimii, 2017, Vol. 53, No. 7, pp. 1080–1083.
Synthesis and Spectral Properties of β-Bromo-Substituted
Nickel(II) Tetraphenylporphyrins
N. V. Chizhovaa,* A. V. Konakovab, O. V. Mal’tsevaa,
N. Zh. Mamardashvilia, and O. I. Koifmana–c
a Krestov Institute of Solution Chemistry, Russian Academy of Sciences, ul. Akademicheskaya 1, Ivanovo, 153040 Russia
*e-mail: nvc@isc-ras.ru
b Ivanovo State University of Chemistry and Technology, Sheremetevskii pr. 7, Ivanovo, 153000 Russia
c Research Institute of Macroheterocyclic Compounds, Ivanovo State University of Chemistry and Technology,
Sheremetevskii pr. 7, Ivanovo, 153000 Russia
Received April 26, 2017
Abstract—Bromination of (5,10,15,20-tetraphenylporphyrinato)nickel(II) with N-bromosuccinimide in chloro-
form and chloroform–dimethylformamide mixture and complexation of 2-bromo-5,10,15,20-tetraphenylpor-
phyrin and 2,3,12,13-tetrabromo-5,10,15,20-tetraphenylporphyrin with nickel(II) acetate in dimethylformamide
have been studied. The resulting nickel(II) complexes with mono-, tetra-, and octabromo-5,10,15,20-tetra-
phenylporphyrins have been identified by electronic absorption, IR, 1H NMR, and mass spectra.
DOI: 10.1134/S1070428017070235
Introduction of bromine atoms into porphyrin mole-
cules gives rise to compounds that are readily soluble
in organic solvents and form metal complexes highly
stable in various media. Bromo-substituted porphyrins
are convenient substrates for further chemical trans-
formations, e.g., for replacement of bromine atoms by
CN, NH2, and other groups. Bromination of porphyrins
may be regarded as protection of the β-pyrrole posi-
tions since the β-bromine atom can readily be removed
afterwards [1].
The reaction of 5,10,15,20-tetraphenylporphyrin (1)
with N-bromosuccinimide (NBS) in boiling chloro-
form was reported to produce 2-bromo-5,10,15,20-
tetraphenylporphyrin (2) [6] and 2,3,12,13-tetrabromo-
5,10,15,20-tetraphenylporphyrin (3) [7]. The copper
complex of tetraphenylporphyrin reacted with molec-
ular bromine in a mixture of chloroform with carbon
tetrachloride and pyridine to give octabromo-sub-
stituted copper(II) porphyrin [8]. Treatment of the
copper complex with perchloric acid afforded
2,3,7,8,12,13,17,18-octabromo-5,10,15,20-tetraphenyl-
porphyrin (4) which reacted with nickel(II) acetate in
chloroform–methanol, yielding nickel(II) octabromo-
tetraphenylporphyrin [8]. Cobalt(II), cobalt(III), man-
Interest in the synthesis and properties of porphyrin
complexes with nickel is determined by their potential
application as optical materials, molecular thermom-
eters, sensors, and molecular switches [2–5].
R3
R3
Ph
R1
Ph
R1
R2
Ph
R3
R2
Ph
R3
R3
R3
NH
N
N
N
N
N
N
Ni
Ph
R2
Ph
R2
HN
R3
R3
R2
Ph
1–4
R2
Ph
5–8
1, 5, R1 = R2 = R3 = H; 2, 6, R1 = Br, R2 = R3 = H; 3, 7, R1 = R2 = Br, R3 = H; 4, 8, R1 = R2 = R3 = Br.
1094

SYNTHESIS AND SPECTRAL PROPERTIES OF β-BROMO-SUBSTITUTED
1095
Electronic absorption spectra of nickel(II) tetraphenylpor-
phyrins 5–8
ganese(III), platinum(II), and platinum(IV) porphyrins
were synthesized from β-bromo-substituted tetra-
phenylporphyrins and cobalt(II) acetate, manganese(II)
chloride, and platinum(II) chloride [9–11].
λmax, nm (logε)
Comp.
Solvent
no.
I
II
Soret
With the goal of obtaining nickel(II) porphyrin
complexes containing bromine atoms in the β-pyrrole
positions, (5,10,15,20-tetraphenylporpyrinato)nickel(II)
(5) was treated with NBS in chloroform and in a mix-
ture of chloroform with dimethylformamide, and por-
phyrins 2 and 3 were reacted with nickel(II) acetate in
dimethylformamide.
5
5
DMF
560 sh 527 (4.46) 414 (5.56)
562 sh 528 (4.47) 415 (5.59)
572 sh 534 (4.32) 419 (5.39)
572 sh 535 (4.33) 420 (5.38)
588 sh 546 (4.24) 431 (5.30)
587 sh 546 (4.27) 431 (5.28)
CHCl3
DMF
6
6
CHCl3
DMF
7
The bromination of 5 with NBS at a molar ratio of
1:2.5 in boiling chloroform for 6 min gave (2-bromo-
5,10,15,20-tetraphenylporphyrinato)nickel(II) (6). The
electronic absorption spectrum of a solution of com-
plex 6 in chloroform showed bands with their maxima
at λ 535 and 420 nm, which appeared ~5–7 nm red
relative to those of initial complex 5 (see table). The
mass spectrum of 6 contained the molecular ion peak
with m/z 749 (C44H27BrN4Ni; Mcalc 750). Nickel com-
plex 6 was also formed in the reaction of 5 with NBS
(1:1.5) in chloroform–DMF (10:1) at room tempera-
ture (40 min). As shown in [6], the bromination of
tetraphenylporphyrin 1 with 2 equiv of NBS in chloro-
form afforded 2-bromo-5,10,15,20-tetraphenylporphy-
rin (2). The complexation of 2 with excess nickel(II)
acetate (1:10) in boiling DMF (4 min) produced nickel
complex 6.
7
a8a
CHCl3
CH2Cl2
592 sh 561 (4.28) ,448 (5.39),
344 (4.48)
8
CHCl3
593 sh 561 (4.32) ,449 (5.36),
346 (4.46)
a
Data of [8].
chloroform–DMF mixture at room temperature
(~12 h). The reaction time was shortened to 4 min
when the reaction was carried out under reflux. The
electronic spectrum of 8 in chloroform contained ab-
sorption bands at λmax 593, 561, and 449 nm, whereas
no bands typical of initial complex 5 (λmax 562, 528,
and 415 nm) were observed (Fig. 2).
The absorption maxima in the electronic spectra of
the isolated compounds in comparison with published
data for nickel octabromoporphyrin 8 [8] are given in
table. It is seen that increase of the number of bromine
atoms in the pyrrole rings of nickel tetraphenylpor-
phyrins is accompanied by red shift of the absorption
maxima relative to unsubstituted complex 5.
By reaction of 5 with 16 equiv of NBS in boiling
chloroform (24 min) we obtained (2,3,12,13-tetra-
bromo-5,10,15,20-tetraphenylporphyrinato)nickel(II)
(7). Complex 7 was also formed in the reaction of 5
with 6 equiv of NBS in chloroform–DMF at room
temperature (2.5 h). The electronic absorption spectra
1
6
A
of 6 and 7 are shown in Fig. 1. In the H NMR spec-
trum of 7, protons in the pyrrole ring resonated as
a singlet at δ 8.54 ppm, and signals from the phenyl
substituents were located at δ 7.86–7.62 ppm.
2.7
7
As reported in [7], tetraphenylporphyrin 1 reacted
with 6 equiv of NBS in boiling chloroform, yielding
2,3,12,13-tetrabromo-5,10,15,20-tetraphenylporphyrin
(3). By heating a mixture of 3 and nickel(II) acetate
(1:10) in boiling DMF for 30 s we obtained nickel(II)
porphyrin 7. In the reaction of 5 with 20 equiv of NBS
in boiling chloroform (30 min), a mixture of β-bromo-
substituted nickel(II) porphyrins containing 4 to
5 bromine atoms was formed.
1.8
0.9
0.0
400
500
600
700
λ, nm
(2,3,7,8,12,13,17,18-Octabromo-5,10,15,20-tetra-
phenylporphyrinato)nickel(II) (8) was synthesized by
reaction of 5 with NBS at a ratio of 1:20 in a 10:1
Fig. 1. Electronic absorption spectra of bromo-substituted
nickel(II) tetraphenylporphyrins 6 and 7 in chloroform.
RUSSIAN JOURNAL OF ORGANIC CHEMISTRY Vol. 53 No. 7 2017

CHIZHOVA et al.
5,10,15,20-Tetraphenylporphyrin (Porphychem),
1096
A
N-bromosuccinimide (Acros Organics), and aluminum
oxide (Merck) were commercial products; the solvents
(chloroform, dimethylformamide, hexane, and aceto-
nitrile) were of chemically pure grade.
5
2.0
1.6
1.2
0.8
0.4
0.0
8
(5,10,15,20-Tetraphenylporphyrinato)cadmium(II)
was synthesized according to Adler [12], following the
procedure described in [13] with the difference that
cadmium(II) acetate was used instead of chloride.
(5,10,15,20-Tetraphenylporphyrinato)nickel(II) was
synthesized by transmetalation of labile porphyrin
complexes [14]. 2-Bromo-5,10,15,20-tetraphenylpor-
phyrin and 2,3,12,13-tetrabromo-5,10,15,20-tetra-
phenylporphyrin were prepared according to [6, 7].
The spectral parameters of brominated porphyrins 2
and 3 were given in [10].
400
500
600
λ, nm
Fig. 2. Electronic absorption spectra of nickel(II) porphyrins
5 and 8 in chloroform.
(5,10,15,20-Tetraphenylporphyrinato)nickel(II)
(5). A solution of 0.05 g (0.0689 mmol) of (5,10,15,20-
tetraphenylporphyrinato)cadmium(II) and 0.033 g
(0.207 mmol) of NiCl2·2H2O in 40 mL of DMF was
heated to the boiling point over a period of 2 min and
was maintained boiling for 30 s. The mixture was
cooled and poured into water, solid sodium chloride
was added, and the precipitate was filtered off, washed
with water, dried, and purified by alumina chromatog-
raphy with chloroform as eluent. Yield 0.04 g
(0.0596 mmol, 87%). IR spectrum, ν, cm–1: 2926 s,
2855 m (C–Harom); 1599 m, 1489 s (C=Carom); 1441 m
(C=N), 1365 m, 1352 s (C–N); 1168 w, 1145 s, 1077 m
(δ C–Harom); 1007 s (C–C), 862 m, 794 m, 775 w
(γC–H, pyrrole); 742 m, 696 m (γC–Harom), 488
The IR spectra of brominated nickel complexes 6–8
differed from the spectrum of initial nickel tetra-
phenylporphyrin 5 by the position of some absorption
bands, appearance of new bands, or enhanced intensity
1
of particular bands. The H NMR spectrum of octa-
bromo derivative 8 lacked signal assignable to pyrrole
protons, and signals of the phenyl protons were located
in a stronger field relative to those of unsubstituted
complex 5 and in a weaker field relative to those of
tetrabromo derivative 7.
In summary, the reaction of (5,10,15,20-tetra-
phenylporphyrinato)nickel(II) (5) with N-bromo-
succinimide in boiling chloroform gives mono-, tetra-,
and pentabromo-substituted nickel porphyrins. The
bromination of 5 with NBS in chloroform–DMF yields
mono-, tetra-, and octabromoporphyrin complexes.
Nickel(II) complexes 6 and 7 with mono- and tetra-
bromotetraphenylporphyrins can also be synthesized
by reaction of the corresponding brominated porphy-
rins with nickel(II) acetate in boiling DMF.
1
(Ni–N). H NMR spectrum, δ, ppm: 7.65–7.70 m
(12H, m-H, p-H), 8.02 d (8H, o-H, J = 7.70 Hz), 8.74 s
(8H, β-H). Mass spectrum, m/z (Irel, %): 671 (82) [M]+,
616 (17.2), 580 (19.5), 441 (46.4). C44H28N4Ni. Cal-
culated: M 672.
(2-Bromo-5,10,15,20-tetraphenylporphyrinato)-
nickel(II) (6). a. N-Bromosuccinimide, 0.0133 g
(0.0746 mmol), was added with stirring to a solution of
0.02 g (0.0298 mmol) of complex 5 in 10 mL of
chloroform. The mixture was heated to the boiling
point and was refluxed for 6 min. It was then cooled
and treated with water, the organic layer was separated,
washed with water, dried over Na2SO4, and evaporat-
ed, and the residue was purified by alumina chroma-
tography using first chloroform–hexane (1:2) and then
chloroform as eluents, followed by reprecipitation
from ethanol. Yield 0.016 g (0.0213 mmol, 72%).
EXPERIMENTAL
The electronic absorption spectra were measured on
a Cary-100 spectrophotometer. The IR spectra were
recorded in KBr on a Bruker Vertex 80v spectrometer
1
with Fourier transform. The H NMR spectra were
recorded on a Bruker AV III-500 instrument using
CDCl3 as solvent and tetramethylsilane as internal
standard. The mass spectra were obtained on
a Shimadzu Biotech Axima Confidence MALDI TOF
mass spectrometer with 2,5-dihydroxybenzoic acid as
matrix.
b. N-Bromosuccinimide, 0.00795 g (0.0447 mmol),
was added to a solution of 0.02 g (0.0298 mmol) of
RUSSIAN JOURNAL OF ORGANIC CHEMISTRY Vol. 53 No. 7 2017

SYNTHESIS AND SPECTRAL PROPERTIES OF β-BROMO-SUBSTITUTED
1097
complex 5 in a mixture of 10 mL of chloroform and
1 mL of DMF, and the mixture was stirred for 40 min
at room temperature (21–22°C) and treated as de-
scribed above in a. Yield 0.017 g (0.0227 mmol, 76%).
and purified by alumina chromatography using chloro-
form as eluent. Yield 0.018 g (0.0182 mmol, 84%). IR
spectrum, ν, cm–1: 2955 m, 2926 s, 2855 m (C–Harom);
1597 w, 1588 w, 1489 s (C=Carom); 1466 m, 1457 m
(C=N); 1367 s, 1351 s (C–N); 1193 m, 1169 m, 1145 s
(δC–Harom); 1071 w, 1024 w (C–C); 910 w, 861 s,
775 m (γC–H, pyrrole); 749 m, 689 m (γC–Harom).
1H NMR spectrum, δ, ppm: 7.62–7.69 m (12H, m-H,
p-H), 7.86 d (8H, o-H, J = 7.70 Hz), 8.54 s (8H, β-H).
Mass spectrum, m/z (Irel, %): 986 (94.2) [M]+, 666
(23.5), 547 (49.6), 413 (69.4), 274 (61.8).
C44H24Br4N4Ni. Calculated: M 987.
c. A mixture of 0.02 g (0.0288 mmol) of porphyrin
2 and 0.05 g (0.288 mmol) of nickel(II) acetate was
dissolved in 10 mL of DMF. The mixture was heated
to the boiling point, refluxed for 4 min, cooled, and
poured into water, and solid sodium chloride was
added. The precipitate was filtered off, washed with
water, dried, and purified by alumina chromatography
using chloroform as eluent. Yield 0.018 g
(0.0240 mmol, 77%). IR spectrum, ν, cm–1: 2926 s,
2855 m (C–Harom); 1711 s, 1599 w, 1488 s (C=Carom);
1457 m, 1441 w, 1424 w (C=N); 1350 s, 1311 s (C–N);
1192 s, 1169 s, 1146 s, 1072 w (δC–Harom); 1007 m
(C–C), 911 w, 861 s, 796 m (γC–H, pyrrole); 750 m,
(2,3,7,8,12,13,17,18-Octabromo-5,10,15,20-tetra-
phenylporphyrinato)nickel(II) (8). N-Bromosuccin-
imide, 0.106 g (0.596 mmol), was added to a solution
of 0.02 g (0.0298 mmol) of complex 5 in a mixture of
10 mL of chloroform and 1 mL of DMF. The mixture
was refluxed for 4 min and evaporated to a minimum
volume, 10 mL of DMF, water, and solid sodium
chloride were added, and the precipitate was filtered
off, washed with water and acetonitrile, dried, and
purified by alumina chromatography using chloroform
as eluent, followed by reprecipitation from ethanol.
Yield 0.027 g (0.0207 mmol, 70%). IR spectrum, ν,
cm–1: 2956 m, 2926 s, 2855 m (C–Harom); 1726 m,
1588 w, 1488 s (C=Carom); 1466 m (C=N); 1366 m,
1351 m (C–N); 1275 w, 1192 m, 1168 m, 1145 s
(δC–Harom); 1071 w, 1042 w, 1026 m (C–C); 926 w,
909 w, 861 s (γC–H, pyrrole); 775 m, 734 m, 690 m
1
689 m, 656 m (γC–Harom); 545 w (Ni–N). H NMR
spectrum, δ, ppm: 7.62–7.70 m (12H, m-H, p-H),
7.81–7.85 m (2H), 7.93–7.98 m (6H, o-H), 8.66–
8.69 m (2H), 8.72–8.77 m (2H), 8.78 s (1H), 8.79–
8.83 m (2H, β-H). Mass spectrum, m/z (Irel, %): 749
(67.8) [M]+, 670 (89.8), 549 (21.7), 368 (69.4).
C44H27BrN4Ni. Calculated: M 750.
(2,3,12,13-Tetrabromo-5,10,15,20-tetraphenyl-
porphyrinato)nickel(II) (7). a. N-Bromosuccinimide
was added in four 0.021-g (0.119-mmol) portions with
stirring to a solution of 0.02 g (0.0298 mmol) of com-
plex 5 in 10 mL of chloroform. The mixture was
heated to the boiling point and was refluxed for 6 min.
It was then cooled and treated with water, the organic
layer was separated, washed with water, dried over
Na2SO4, and evaporated, and the residue was purified
by alumina chromatography using first chloroform–
hexane (1:2) and then chloroform as eluents, followed
by reprecipitation from ethanol. Yield 0.02 g
(0.0203 mmol, 69%).
1
(γC–Harom). H NMR spectrum, δ, ppm: 7.68–7.72 m
(12H, m-H, p-H), 7.92 d (8H, o-H, J = 7.70 Hz). Mass
spectrum, m/z (Irel, %): 1302 (88.4) [M]+, 822 (30.8),
432 (37.5), 363 (100), 313 (49.7), 214 (91.3).
C44H20Br8N4Ni. Calculated: M 1303.
This study was performed under financial support
by the Russian Science Foundation (project no. 14-23-
00204-P) using the equipment of the “Upper Volga
Joint Regional Center for Physicochemical Studies.”
b. N-Bromosuccinimide, 0.0318 g (0.179 mmol),
was added with stirring to a solution of 0.02 g
(0.0298 mmol) of complex 5 in a mixture of 10 mL of
chloroform and 1 mL of DMF. The mixture was stirred
for 2.5 h at room temperature and treated as described
above in a. Yield 0.021 g (0.0213 mmol, 72%).
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