Synthesis and properties of ms- and β-substituted Pt(II) and Pt(IV) tetraphenylporphyrinates

Article abstract of DOI:10.1134/S107036321311025X

The interaction of 5,10,15,20-tetraphenylporphyrin, 5,10,15,20-tetra-(4- chlorophenyl)porphyrin, 2-bromo-5,10,15,20-tetraphenylporphyrin, and 2,3,12,13-tetrabromo-5,10,15,20-tetraphenylporphyrin with platinum(II) chloride in boiling phenol has been studie

Full text of DOI:10.1134/S107036321311025X

ISSN 1070-3632, Russian Journal of General Chemistry, 2013, Vol. 83, No. 11, pp. 2108–2111. © Pleiades Publishing, Ltd., 2013.
Original Russian Text © N.V. Chizhova, O.M. Kulikova, N.Zh. Mamardashvili, 2013, published in Zhurnal Obshchei Khimii, 2013, Vol. 83, No. 11,
pp. 1917–1920.
Synthesis and Properties of ms- and β-Substituted Pt(II)
and Pt(IV) Tetraphenylporphyrinates
N. V. Chizhova, O. M. Kulikova, and N. Zh. Mamardashvili
Krestov Institute of Chemistry of Solutions, Russian Academy of Sciences,
ul. Akademicheskaya 1, Ivanovo, 153045 Russia
e-mail: nvc@isc-ras.ru
Received November 19, 2012
Abstract—The interaction of 5,10,15,20-tetraphenylporphyrin, 5,10,15,20-tetra-(4-chlorophenyl)porphyrin,
2-bromo-5,10,15,20-tetraphenylporphyrin, and 2,3,12,13-tetrabromo-5,10,15,20-tetraphenylporphyrin with
platinum(II) chloride in boiling phenol has been studied. The corresponding platinum(II) porphyrinates have
been synthesized; their subsequent treatment with bromine in chloroform resulted in platinum(IV)
porphyrinates. The Pt(II) and Pt(IV)(Br)2 porphyrinates have been identified by elemental analysis, electron
absorption, IR, and 1H NMR spectroscopy.
DOI: 10.1134/S107036321311025X
R3
R1
Porphyrin complexes of platinum are widely used
for development of new functional materials. Several
methods to prepare the Pt(II) complex with 5,10,15,20-
tetraphenylporphin have been described in the litera-
ture [1–3]. According to [1], the interaction of
R
M
R
R3
R2
R
N
N
N
N
R
5,10,15,20-tetraphenylporphin
I with K2PtCl4 in
boiling benzene affords Pt(II) 5,10,15,20-tetra-
phenylporphyrinate II with 20% yield. The yield of II
can be increased to 80% by performing the reaction
with PtCl2 in benzonitrile at reflux [2]. We have
recently obtained the complex II with a yield of 76%
via the reaction of I with H2PtCl6 in boiling phenol
during 2 h [3].
R2
R3
R2
R3
М = Н2, R = C6H5, R1 = R2 = R3 = H (I); М = Pt(II), R =
C6H5, R1 = R2 = R3 = H (II); М = Н2, R = C6H4-4-Cl, R1 =
R2 = R3 = H (III); M = H2, R = C6H5, R1 = Br, R2 = R3 = H
(IV); М = Н2, R = C6H5, R1 = R2 = Br, R3 = H (V); M =
Pt(II), R = C6H4-4-Cl, R1 = R2 = R3 = H (VI); M = Pt(II),
R = C6H5, R1 = Br, R2 = R3 = H (VII); M = Pt(II), R =
C6H5, R1 = R2 = Br, R3 = H (VIII); М = Pt(IV)(Br)2, R =
C6H5, R1 = R2 = R3 = H (IX); M = Pt(IV)(Br)2, R = C6H4-
4-Cl, R1 = R2 = R3 = H (X); M = Pt(IV)(Br)2, R = C6H5,
R1 = Br, R2 = R3 = H (XI); M = Pt(IV)(Br)2, R = C6H5,
R1 = R2 = Br, R3 = H (XII); M = Zn(II), R = C6H5, R1 =
R2 = R3 = H (XIII).
In this paper we performed spectrophotometry
studies of the complex formation of 5,10,15,20-
tetraphenylporphin I, 5,10,15,20-tetra-(4-chlorophenyl)-
porphyrin III, 2-bromo-5,10,15,20-tetraphenylpor-
phyrin IV, and 2,3,12,13-tetrabromo-5,10,15,20-tetra-
phenylporphyrin V with PtCl2 in boiling phenol.
1
The noticeable difference in the electronic and H
NMR spectra of the starting porphyrins and the formed
platinum(II) and platinum(IV) porphyrinates (see table
and figure) allowed application of the spectroscopy
methods to study the complex formation of I and III–
V with platinum and identification of porphyrinates II
and VI–XII.
The results revealed that the reaction of I with PtCl2
(1 : 2 molar ratio) in boiling phenol occurred within
24 min to form platinum(II) tetraphenylporphyrinate.
The electronic absorption spectrum of the reaction
mixture in DMF contained the bands with λmax
=
2108

SYNTHESIS AND PROPERTIES OF ms- AND β-SUBSTITUTED Pt(II)
2109
The features of electronic absorption spectra of I–XIII in
chloroform [λ, nm (log ε)]
509 nm and 539 nm, whereas the bands of I (λmax
=
513, 547, 590, and 647 nm) disappeared. The hypso-
chromic shift of the Soret band in the absorption
spectrum of II as compared to I was of 15 nm in DMF.
Comp.
no.
Bands
III, IV
Band I
Band II
Soret band
When chlorine atoms were introduced at para-
positions of the tetraphenylporphyrin benzene rings
(+C effect), the rate of complex formation between III
and PtCl2 in phenol increased by about 12 times as
compared to the case of I + PtCl2. The complex
formation rate was about 4 times higher in the case of
β-tetrabromoporphyrin V as compared with porphyrin
β-monobromo derivative IV. According to the litera-
ture data, the electron density increase at the tertiary
nitrogen macrocycle atoms enhanced the coordination
of the solvated cation [MX2(Solv)n–2] to porphyrin in
the transition state [4].
647 (3.89)
591 (3.96)
549 (4.08), 417 (5.61)
514 (4.40)
I
540 (4.10)
645 (3.76)
510(4.40)
590 (3.83)
402 (5.48)
II
550 (4.05), 417 (5.60)
515 (4.36)
III
649 (3.79)
594 (3.81)
552 (3.78), 421 (5.58)
518 (4.33)
IV
683 (4.06)
539 (4.13)
543 (4.06)
561 (4.12)
569 (4.06)
568 (4.08)
572 (4.04)
614 (3.82)
509 (4.46)
512 (4.38)
523 (4.28)
533 (4.29)
532 (4.37)
535 (4.29)
545 (4.24)
558 (4.36)
535 (4.31)
437 (5.46)
401 (5.52)
404 (5.46)
413 (5.31)
424 (5.52)
423 (5.58)
426 (5.48)
439 (5.29)
420 (5.19)
V
VI
VII
VIII
IX
The oxidation of Pt(II) tetraphenylporphyrinate to
the respective Pt(IV) complex with Br2 occurred in
chloroform at 0°C within about 2 h [5]. We observed
the oxidation of Pt(II) porphyrinates VI–VIII with
bromine in CHCl3 at room temperature within 5–
20 min (the macrocycle was not brominated under
those conditions).
X
XI
XII
XIIIа
597 (3.99)
The structures of the prepared complexes were
confirmed by elemental analysis, electronic absorption,
1H NMR, and IR spectroscopy. The hypsochromic
shift of the electronic absorption bands of Pt(II)
tetraphenylporphyrinate with respect to the similar Zn
complex XVI was due to the strong dπ–eg(π*) π-dative
interaction between Pt ion and porphyrin macrocycle.
The Pt(II)→Pt(IV) oxidation of porphyrinates led to
the bathochromic shift of the electron absorption bands
a Data from [5] and [6].
EXPERIMENTAL
The porphyrin ligands I and III were prepared
according to [6, 7]. Compounds IV and V were
obtained via the method adopted from [8, 9] and
further optimized. Phenol, DMF, and CHCl3 of
chemically pure grade, as well as platinum(II) chloride
(Acros) were used as received. The reaction progress
was monitored by spectrophotometry and TLC. In
particular, certain amount of reaction mixture was
sampled at regular time intervals, dissolved in DMF,
1
(Figure and Table). In the H NMR spectrum of Pt(II)
tetraphenylporphyrinate in CDCl3, the signals of β-
pyrrole and ortho-phenyl protons were shifted upfield
by 0.13 and 0.07 ppm, respectively, as compared to the
spectrum of the ligand I. The Pt(II)→Pt(IV) oxidation
of tetraphenylporphyrinate led to shift of β-pyrrole
protons signal downfield by 0.29 ppm as compared to
the complex II. The downfield shift of ortho-, meta-,
and para-proton signals was of 0.10, 0.08, and 0.07 ppm,
respectively. The β-bromine substitution in pyrrole
ring (compounds VII and VIII) altered the IR bands
position and intensity, moreover, the new IR bands
appeared as compared with unsubstituted complex II.
Upon Pt(II)→Pt(IV) oxidation, the stretching and
bending IR bands shifted to lower frequencies; the
metal-sensitive band at ~1025 cm–1, shifted by
~9 cm–1 to higher frequencies, being an exception.
λ, nm
Absorption spectra of (1) VIII and (2) XII in DMF.
RUSSIAN JOURNAL OF GENERAL CHEMISTRY Vol. 83 No. 11 2013

2110
CHIZHOVA et al.
and the electronic absorption spectrum was recorded
with Cary-100 spectrometer at room temperature. TLC
analysis was performed on Silufol plates, with hexane-
78%), Rf = 0.83. IR spectrum, ν, cm–1: 2923 s, 2853 m
1734 m 1596 m 1461 s, 1267 m, 1110 w, 1048 s, 1020
1
s, 794 w, 750 m, 697 m, 526 w, 466 w. H NMR
1
chloroform 1 : 2 as an eluent. H NMR spectra were
spectrum, δ, ppm: 8.52 s (4H), 8.3 d (8H, J 8.2 Hz),
7.78 t (8H, J 8.2 Hz), 7.73 m (4H). Found, %: C 46.89,
H 2.15, N 4.87. C44H24Br4N4Pt. Calculated, %: C
47.04, H 2.22, N 4.99.
recorded with Bruker AV III-500 instrument in CDCl3.
IR spectra were recorded with Avatar 360-FT-IR-ESP
spectrometer (KBr tablets). Element analysis was
performed with Flash EA 1112 analyzer.
Pt(IV)(Br)2 5,10,15,20-tetraphenylporphyrinate
(IX). 25 droplets of bromine solution (12 droplets of
Br2 in 5 mL of CHCl3) were added to the stirred
solution of 0.02 g (0.025 mmol) of Pt(II) tetra-
phenylporphyrinate in 20 mL of CHCl3. The mixture
was incubated at room temperature for 5 min. The
solvent was evaporated, and the residue was washed
with cold ethanol and water, and dried. Obtained 0.019 g
(0.0196 mmol) of IX (80%), Rf = 0.78. IR spectrum, ν,
cm–1: 2923 m, 2853 w, 2362 m, 1605 m, 1449 w, 1365
Pt(II) 5,10,15,20-tetraphenylporphyrinate (II). A
mixture of 0.05 g (0.0813 mmol) of tetraphenylpor-
phyrin I, 0.043 g (0.1626 mmol) PtCl2, and 6 g of
phenol was heated to boiling. The melt was refluxed
during 24 min. After the reaction was completed,
20 mL of DMF was added, and the mixture was
poured into water. The precipitate was filtered off,
washed with hot water, and dried. The residue was
purified by chromatography on Merck aluminum oxide
(eluent: chloroform). Obtained 0.05 g (0.0619 mmol,
1
w, 1323 w, 1078 m, 1025 s, 796 m, 753 s, 702 s. H
76%) of II, Rf = 0.82. Mass spectrum: m/z 807.2 (Irel
=
NMR spectrum, (δ, ppm): 9.06 s (8H), 8.28 d (8H,
J 8.0 Hz), 7.85 t (8H, J 8.0 Hz), 7.82 t (4H, J 8.0 Hz).
Found, %: C 54.28, H 2.80, N 5.59. C44H28Br2N4Pt.
Calculated, %: C 54.62, H 2.92; N 5.79.
76%) [M+]. H NMR spectrum, δ, ppm: 8.77 s (8H),
8.18 d (8H, J 7.9 Hz), 7.77 t (8H, J 7.9 Hz), 7.75 t (4H,
J 7.8 Hz). IR spectrum, ν, cm–1: 2923 s, 2858 m, 2361
w, 1913 w, 1620 s, 1487 m, 1453 m, 1310 s, 1090 s,
1016 s, 897 w, 804 s, 702 m, 509 m. Found, %: C
65.38, H 3.47, N 6.92. C44H28N4Pt. Calculated, %: C
65.41, H 3.50; N 6.94.
1
Pt(IV) porphyrinates X–XII were prepared
similarly from the respective complexes VI–VIII.
Pt(IV)(Br)2 5,10,15,20-Tetra-(4-chlorophenyl) por-
phyrinate (X). Yield 0.022 g (0.0199 mmol, 78%),
Rf = 0.80. IR spectrum, ν, cm–1: 2923 m, 2853 w, 1641
w, 1542 m, 1487 m, 1395 w, 1318 w, 1181 w, 1091 s,
Pt(II) porphyrinates VI–VIII were prepared
similarly from the respective porphyrin ligands III–V.
1
Pt(II) 5,10,15,20-tetra-(4-chlorophenyl)porphy-
rinate (VI). Yield 0.049 g (0.0518 mmol, 78%), Rf =
0.85. IR spectrum VI, ν, cm–1: 2923 s, 2852 m, 1913
w, 1633 s, 1487 s, 1453 m 1395 m 1359 m 1316 m,
1090 s, 1016 s, 880 w, 804 s,710 m, 508 m, 475 w. 1H
NMR spectrum, δ, ppm: 8.77 s (8H), 8.9 d (8H, J
8.0 Hz), 7.74 d (8H, J 8.0 Hz). Found, %: C 55.85, H
2.50, N 5.87. C44H24Cl4N4Pt. Calculated, %: C 55.89,
H 2.56, N 5.92.
1020 s, 892 w, 802 s, 708 w, 507 m. H NMR
spectrum, (δ, ppm): 9.06 s (8H), 8.21 d (8H, J 7.8 Hz),
7.80 d (8H, J 7.8 Hz). Found, %: C 47.50; H 2.13; N
4.93. C44H24Br2Cl4N4Pt. Calculated, %: C 47.81, H
2.19, N 5.07.
Pt(IV)(Br)2 2-bromo-5,10,15,20-tetraphenylpor-
phyrinate (XI). Yield 0.02 g (0.0191 mmol, 77%),
Rf = 0.80. IR spectrum, ν, cm–1: 2923 w, 2847 w, 1598
m, 1442 m, 1370 m, 1290 w, 1170 w, 1072 s, 1025 s,
837 w, 790 m, 752 s, 702 s, 662 w. 1H NMR spectrum,
(δ, ppm): 9.22–9.20 m (2H), 9.06 s (1H), 9.04–8.99 m
(2H), 8.94–8.88 m (2H), 8.29–8.23 m (6H), 8.12–8.08
m (2H), 7.85–7.74 m (12H). Found, %: C 50.28, H
2.48, N 5.21. C44H27Br3N4Pt. Calculated, %: C 50.50,
H 2.60; N 5.35.
Pt(II) 2-bromo-5,10,15,20-tetraphenylporphyri-
nate (VII). Yield 0.049 g (0.0552 mmol, 77%), Rf =
0.83. IR spectrum, ν, cm–1: 2922 m 2852 w, 1809 w,
1634 m 1601 m 1444 m 1355 m 1291 w, 1177 w, 1077
m, 1020 s, 833 m, 792 m, 752 s, 705 s, 666 w, 537 w.
1H NMR spectrum, δ, ppm: 8.96–8.94 m (2H), 8.76 s.
(1H), 8.75–8.70 m (2H), 8.68–8.63 m (2H), 8.18 m
(6H), 8.04 m (2H), 7.78–7.70 m (12H). Found, %: C
59.55, H 3.02, N 6.28. C44H27BrN4Pt. Calculated, %: C
59.60, H 3.07; N 6.32
Pt(IV)(Br)2 2,3,12,13-Tetrabromo-5,10,15,20-tetra-
phenylporphyrinate (XII). Yield 0.025 g (0.0195
mmol, 78%), Rf = 0.78. IR spectrum, ν, cm–1: 2922 s,
2852 m, 1726 m, 1641 m, 1443 s, 1266 w, 1157 w,
1052 s, 1023 s, 792 w, 751 m, 699 m, 533 w, 469 w.
1H NMR spectrum (δ, ppm): 8.85 s (4H), 8.06 d (8H,
Pt(II) 2,3,12,13-tetrabromo-5,10,15,20-tetraphenyl-
porphyrinate (VIII). Yield 0.047 g (0.0418 mmol,
RUSSIAN JOURNAL OF GENERAL CHEMISTRY Vol. 83 No. 11 2013

SYNTHESIS AND PROPERTIES OF ms- AND β-SUBSTITUTED Pt(II)
2111
Naturforsch, B., Anorg. Chem., Org. Chem. B, 1980,
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J 7.6 Hz), 7.81 t (8H, J 7.6 Hz), 7.76 t (4H, J 7.6 Hz).
Found, %: C 41.01, H 1.77, N 4.19. C44H24Br6N4Pt.
Calculated, %: C 41.18, H 1.89; N 4.37.
3. Chizhova, N.V. and Mamardashvili, N.Zh., Russ. J.
Inorg. Chem., 2007, vol. 52, no. 2, p. 250.
ACKNOWLEDGMENTS
4. Berezin,
B.D.,
Koordinatsionnye
soedineniya
This work was financially supported by the
Programs of the Branch of Chemistry and Material
Sciences, Russian Academy of Sciences: no. 1,
“Theoretical and Experimental Study of Chemical
Bonding Nature and Mechanisms of Important
Chemical Reactions and Processes” and no. 6,
“Chemistry and Physico-Chemistry of Supramolecular
Systems and Atomic Clusters” as well as by the
Seventh Framework Program of the European
Community for Research, Technological Development
and Demonstration Activities, IRSES-GA-2009-
247260.
porfirinov i ftalotsianina (Coordination Compounds
of Porphyrins and Phthalocyanine), Moscow: Nauka,
1978.
5. Mink, L.M., Voce, J.W., Ingersoll, J.E., Nguyen, V.T.,
Boggess, R.K. Washburn, H, and Grove, D.I.,
Polyhedron, 2000, vol. 19, p. 1057.
6. Mamardashvili, N.Zh. and Koifman, O.I., Abstract of
Papers, Int. Conf. on Phyical Foundations of Nuvel
Technology of XXI Century, 2005, p. 275.
7. Mamardashvili, N.Zh. and Dehaen, W., Abstracts of
Papaers, Vth Sigma–Aldrich Organic Synthesis
Conference, Cress–Spa (Belgium), 2001, p. 43.
8. Gao, Guang-Yao, Ruppe Joshua, V., Brett Allen, D.,
Chen, Ying, and Zhang Peter, X., J. Org. Chem., 2007,
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