Synthesis of ms- and β-substituted ruthenium(II) porphyrinates

Article abstract of DOI:10.1134/S0036023610090147

The reactions of 5,10,15,20-tetraphenylporphine, 2,3,7,8,12,13,17,18- octaethylporphine, and tetra(4-methoxyphenyl)porphine with Ru ₃(CO)₁₂ in boiling phenol were studied by spectrophotometry. The following compounds were synthesized and identified: Ru²⁺(CO)(H₂O) 5,10,15,20-tetraphenylporphyrinate, Ru ²⁺(CO)(H₂O) 2,3,7,8,12,13,17,18-octaethylporphyrinate, Ru²⁺(CO)(Py) 2,3,7,8,12,13,17,18-octaethylporphyrinate, and Ru ²⁺(CO)(H₂O) tetra(4-methoxyphenyl)porphyrinate. The strong electronic effect of the substituents on the reactivity of the tetrapyrrole cycle during the formation of the corresponding porphyrinates was established.

Full text of DOI:10.1134/S0036023610090147

ISSN 0036ꢀ0236, Russian Journal of Inorganic Chemistry, 2010, Vol. 55, No. 9, pp. 1421–1424. © Pleiades Publishing, Ltd., 2010.
Original Russian Text © N.V. Chizhova, R.S. Kumeev, N.Zh. Mamardashvili, 2010, published in Zhurnal Neorganicheskoi Khimii, 2010, Vol. 55, No. 9, pp. 1506–1509.
COORDINATION COMPOUNDS
Synthesis of msꢀ and βꢀSubstituted Ruthenium(II) Porphyrinates
N. V. Chizhova, R. S. Kumeev, and N. Zh. Mamardashvili
Institute of Solution Chemistry, Russian Academy of Sciences, ul. Akademicheskaya 1, Ivanovo, 153045 Russia
eꢀmail: nvc@iscꢀras.ru
Received December 29, 2008
Abstract—The reactions of 5,10,15,20ꢀtetraphenylporphine, 2,3,7,8,12,13,17,18ꢀoctaethylporphine, and
tetra(4ꢀmethoxyphenyl)porphine with Ru3(CO)12 in boiling phenol were studied by spectrophotometry. The
following compounds were synthesized and identified: Ru2+(CO)(H2O) 5,10,15,20ꢀtetraphenylporphyriꢀ
nate, Ru2+(CO)(H2O) 2,3,7,8,12,13,17,18ꢀoctaethylporphyrinate, Ru2+(CO)(Py) 2,3,7,8,12,13,17,18ꢀ
octaethylporphyrinate, and Ru2+(CO)(H2O) tetra(4ꢀmethoxyphenyl)porphyrinate. The strong electronic
effect of the substituents on the reactivity of the tetrapyrrole cycle during the formation of the corresponding
porphyrinates was established.
DOI: 10.1134/S0036023610090147
Ru2+(CO)(CH3OH)
Porphyrins and related tetrapyrrole macrocycles in [6] synthesized
tetraphenylporꢀ
phyrinate and Ru2+(CO)(CH3OH) octaethylporphyriꢀ
the composition of metal complexes are known to
manifest photochromic and catalytic properties. Porꢀ
phyrin complexes with ruthenium are of special interest
for the design of controlled functional materials [1, 2].
There are described syntheses of Ru2+(CO)(Py) tetꢀ
raphenylporphyrinate and Ru2+(CO)(Py) octaethylꢀ
porphyrinate by the reactions of 5,10,15,20ꢀtetrapheꢀ
nate from ligands
2ꢀ(2ꢀmethoxyethoxy)ethanol in a carbon monoxide
atmosphere. The reaction of compound with
I and II with RuCl3 · H2O in boiling
I
K2RuO4 (1 : 30 mol/mol) in boiling phenol yielded
Ru4+ (diphenoxo)tetraphenylporphyrinate [7], which
underwent no substitution at the extra ligand during
purification on alumina. However, no reaction time
was specified [7], and Ru2+ tetra(4ꢀmethoxypheꢀ
nyl)porphyrinate was not described.
nylporphine (I) and 2,3,7,8,12,13,17,18ꢀoctaethꢀ
ylporphine (II) with Ru2(CО)9 and Ru3(CO)12 in pyriꢀ
dine [3, 4]. Benzene, toluene, and acetic and propiꢀ
onic acids were also used as solvents. In all cases,
prolong heating (22 to 60 h) is required. The use of
2ꢀ(2ꢀmethoxyethoxy)ethanol and decalin as solvents
shortens the reaction time to 4–5 h [4]. It was shown
that Ru2+(CO)(CH3OН) mesoꢀtetra(benzoꢀ15ꢀ
crownꢀ5)porphyrinate was formed from the correꢀ
sponding porphyrin ligand and Ru3(CO)12 in boiling
For the purpose of creating porphyrinꢀcontaining
photochromic systems capable of giving response to
an external action, we developed efficient methods for
the synthesis of ꢀ
and msꢀsubstituted Ru2+ porphyriꢀ
β
nates and studied the influence of the chemical modiꢀ
fication of the molecule on the reactivity of the tetꢀ
1,2,4ꢀtrichlorobenzene for 5 min [5]. Collman et al. rapyrrole cycle toward Ru3(CO)12 in boiling phenol.
R
N
N
N
N
N
N
R
M
M
R
N
N
R
M = H2, R = C6H5 (
M = H2, R = C6H4–4OCH3 (III),
I
),
M = H2 (II),
M = Ru2+(CO)(H2O) (
M = Ru2+(CO)(Ry) (VI).
V
),
M = Ru2+(CO)(H2O), R = C6H5 (IV),
M = Ru2+(CO)(H2O), R = C6H5 –4OCH3 (VII),
M = Zn2+, R = C6H5 (VIII).
1421

1422
CHIZHOVA et al.
(8H), 8.05 d (8H), 8.21 t (8H), 7.70 t (4H), 0.15 s
(2H).
Analogous syntheses were carried out to obtain
Ru2+(CO)(H2O) 2,3,7,8,12,13,17,18ꢀoctaethylporꢀ
phyrinate (
) and Ru2+(CO)(H2O) tetra(4ꢀmethoxyꢀ
A
2
1
0.8
0.6
V
phenyl)porphyrinate (VI).
Ru2+(CO)(H2O) 2,3,7,8,12,13,17,18ꢀOctaethylporꢀ
phyrinate (V) was synthesized from porphyrin II (0.05 g,
0.093 mmol) and Ru3(CO)12 (0.04 g, 0.06 mmol). The
reaction time was 3 min. The yield of compound
V
after column chromatography on silica gel (eluent
CHCl3) was 0.046 g (0.068 mmol, 72%), Rf = 0.79. IR
(cmꢀ1): 2960 s, 2926 s, 2856 m, 1924 s, 1727 w, 1681 w,
1631 w, 1539 w, 1454 m, 1385 m, 1356 m, 1309 w, 1266 m,
1231 m, 1182 w, 1149 s, 1103 m, 1059 m, 1026 m, 985 m,
949 w, 841 w, 7523 m, 736 m, 722 m, 468 w, 408 w.
0.4
0.2
0
1H NMR (
, ppm): 9.95 s (4H), 4.05 q (16H), 1.95 t
δ
500
600
700
, nm
(24H), 0.08 s (2H).
λ
Ru2+(CO)(Py) 2,3,7,8,12,18ꢀOctaethylporphyriꢀ
nate (VI). Complex V (0.02 g) was dissolved in pyridine
Electronic absorption spectra in chloroform of (
pound and ( ) compound IV
1) comꢀ
(7 mL) and refluxed for 5 min. The reaction mixture
was cooled and chromatographed on silica gel using a
СHCl3–Py (10 : 1) system as an eluent. The yield of
I
2
.
EXPERIMENTAL
Porphyrin ligands III were synthesized using a
known method [8]. The solvents were purified accordꢀ
ing to a described procedure [9]. The course of comꢀ
plex formation of the metal cation with the porphyrin
ligand was monitored by spectrophotometry and thin
compound VI was 0.015 g (0.02 mmol, 70%), Rf =
1
0.75. H NMR (
1.88 t (24H), 5.85 m (2H)
НPy), 2.25 br. s (4H) ( ꢀНPy).
δ, ppm): 9.80 s (4H), 3.95 q (16H),
I–
(γ
ꢀНpy), 4.90 m (4H) ( ꢀ
β
α
Ru2+(CO)(H2O) Tetra(4ꢀmethoxyphenyl)porphyriꢀ
nate (VII) was synthesized from porphyrin III (0.05 g,
0.068 mmol) and Ru3(CO)12 (0.029 g, 0.045 mmol).
The reaction time was 8 min. The yield of compound
VI after column chromatography on alumina (eluent
CHCl3) was 0.046 g (0.053 mmol, 76%), Rf = 0.73. IR
(cmꢀ1): 2927 w, 2852 w, 2058 w, 2040 w, 1938 s, 1606 m,
1574 w, 1528 m, 1511 s, 1464 s, 1434 s, 1410 w, 1350 s,
1304 w, 1287 w, 1246 s, 1175 s, 1075 s, 1007 s, 809 m,
layer chromatography (TLC) on Silufol (G/UV254
)
plates using a chloroform–ethanol (20 : 1) system as
an eluent. The spectrophotometric study was as folꢀ
lows: samples of equal volumes were taken from the
reaction mixture at certain time intervals, diluted with
the same amount of dimethylformamide, and transꢀ
ferred to an optical cell. Electronic absorption spectra
(figure) were recorded on a Caryꢀ100 spectrophotomꢀ
eter at 298 K. IR spectra were measured on an Avatar
360 FTꢀIR ESP spectrometer as KBr pellets. 1H NMR
spectra were obtained on a Bruker ACꢀ200 instrument
796 m, 717 w, 673 w, 610 w, 467 s, 408 w. 1H NMR (
,
δ
ppm): 8.7 d (8H), 8.1 m (16H), 4.1 s (12H), 0.05 s
(2H).
in CDCl3. TLC was carried out on Silufol (G/UV254
)
RESULTS AND DISCUSSION
plates. Elemental analysis was performed with a Flash
EA 1112 analyzer. The elemental analysis data correꢀ
spond completely to the presented structures of the
compounds synthesized.
It is known [7, 10] that metal ions in oxidation
states lower than the maximum values are formed in a
reductive medium (phenol). The complex formation
rate with ruthenium carbonyl in phenol increases by
Ru2+(CO)(H2O) 5,10,15,20ꢀTetraphenylporphyriꢀ about eight times on going from compound
I
to its
nate (IV). A mixture of porphyrin
I (0.05 g, 0.081 mmol) tetra(4ꢀmethoxy)ꢀsubstituted derivative III. A similar
and Ru3(CO)12 (0.035 g, 0.054 mmol) was refluxed in example for the highꢀperformance (5 min) synthesis of
phenol (5 g) for 1 h. The melt was cooled, dissolved in Ru2+(CO)(CH3OH) mesoꢀtetra(benzoꢀ15ꢀcrownꢀ
dimethylformamide (20 mL), and poured into water. 5)porphyrinate has already been described [5]. ꢀSubꢀ
β
The precipitate formed was filtered off and washed stituted octaethylporphine coordinates to Ru3(CO)12
with hot water. The residue was doubly chromatoꢀ 20 times more rapidly than msꢀsubstituted tetrapheꢀ
graphed on alumina with chloroform elution. The nylporphine. This indicates that the coordination
yield of compound IV after column chromatography interaction between the metal cation and the nitrogen
was 0.045 g (0.056 mmol, 73%), Rf = 0.81. IR (cm–1): atoms of porphyrin makes the determining contribuꢀ
2929 w, 1958 s, 1650 w, 1596 m, 1521 w, 1430 w, 1351 m, tion to the energy of the transition state during comꢀ
1306 w, 1165 w, 1070 m, 1009 s, 795 m, 753 s, 703 m, plex formation. The electronꢀdonating
nꢀmethoxy
670 w, 520 w, 445 w, 405 w. 1H NMR (
δ
, ppm): 8.65 d groups of the phenyl fragments of porphyrin III and
RUSSIAN JOURNAL OF INORGANIC CHEMISTRY Vol. 55 No. 9 2010

SYNTHESIS OF msꢀ AND
β
ꢀSUBSTITUTED
1423
Electronic absorption spectra of the porphyrin ligands and ruthenium and zinc porphyrinates
Bands
III, IV, V
λ, nm (logε)
Soret band
λ, nm (logε)
Band I
Band II
Compound
Solvent
C5H5N
Source
λ, nm (logε) λ, nm (logε)
I
646 (3.71)
591 (3.71)
549 (3.96)
515 (4.27)
420 (5.73)
[12]
[6]
I
I
ꢀRu2+(CO)(CH3OH)
ꢀRu2+(CO)(H2O) (IV)
C6H6
CHCl3
532
529 (4.30)
412
411 (5.31)
562 sh
[12]
II
C6H6
623 (3.79)
596 (3.18)
568 (3.83)
530 (4.02)
497 (4.15)
399 (5.21)
IIꢀRu2+(CO)(Py)
C
H2Cl2
545 (4.39)
549 (4.38)
548 (4.34)
550 (4.37)
521 (4.58)
518 (4.20)
517 (4.06)
516 (4.11)
518 (4.16)
495 (4.17)
396 (5.37)
393 (5.16)
393 (5.24)
396 (5.37)
395 (5.01)
[3]
[6]
IIꢀRu2+(CO)(CH3OH)
IIꢀRu2+(CO)(H2O) (V)
IIꢀRu2+(CO)(Py) (VI)
IIꢀRu2+(Py)2
C6H6
CHCl3
6H6
C
[11]
C6H6
450 (4.20)
III
C6H6
651 (3.81)
567 (3.94)
598 (3.82)
532 (4.34)
554 (4.01)
517 (4.13)
422 (5.33)
415 (5.34)
VII
CHCl3
[8]
VIII
CHCl3
597 (3.99)
558 (4.36)
420 (5.19)
the
coordination interaction of the metal cation with porꢀ respectively [6]. These bands are not observed in the
phyrin by increasing the electron density on the terꢀ spectra of porphyrin ligands
β
ꢀethyl substituents (compound II) enhance the and II
ꢀ
Ru2+(СО)(СН3ОН) at 1930 and 1928 cm–1,
I
–
III
.
It was shown for Ru2+(CO)(H2O) octaethylporphyꢀ
rinate that pyridine easily substitutes for a water moleꢀ
cule. More severe conditions are required to substitute
pyridine for the second extra ligand (CO) [11].
tiary nitrogen atoms of the macrocycle.
The methods we developed for the synthesis of
ruthenium porphyrinates in boiling phenol substanꢀ
tially simplify the synthesis compared to the stateꢀofꢀ
theꢀart methods [3, 4, 6]. In particular, the time of forꢀ
mation of Ru2+ tetraphenylporphyrinate and Ru2+
octaethylporphyrinate in phenol is one to two orders
of magnitude shorter than is the syntheses of the corꢀ
responding compounds in pyridine [3, 4] and 2ꢀ(2ꢀ
methoxyethoxy)ethanol [6].
In the 1H NMR spectrum of the synthesized
Ru2+(CO)(Py) octaethylporphyrinate (VI), the signals of
Py protons appear at 5.85–2.25 ppm. The signals of proꢀ
tons of coordinated water lie in a high field (~0.08 ppm).
ACKNOWLEDGMENTS
The electronic absorption spectra of the syntheꢀ
sized ruthenium porphyrinates IV–VII agree well with
This work was supported by the Russian Foundaꢀ
the literature data (table). The hypsochromic shift of tion for Basic Research, project no. 08ꢀ03ꢀ90000 Bel.
the bands in the spectra of ruthenium porphyrinates
IV
taining the metal ion with the closed electronic shell
(e.g., Zn2+) is due to the strong
ꢀdative interaction of
the g π*) type between the metal ion and the porꢀ
–VII compared to those of the porphyrinates conꢀ
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