Water-soluble manganese(III) corroles and corresponding (nitrido)manganese(V) complexes

Article abstract of DOI:10.1142/S1088424610002434

Corroles that carry either two or three ortho-pyridyl groups at the meso-carbon atoms form stable manganese(III) complexes, from which corresponding water-soluble derivatives are obtained via N-alkylation. These syntheses and the spectroscopic features ar

Full text of DOI:10.1142/S1088424610002434

Journal of Porphyrins and Phthalocyanines
J. Porphyrins Phthalocyanines 2010; 14: 615–620
DOI: 10.1142/S1088424610002434
Published at http://www.worldscinet.com/jpp/
Water-soluble manganese(III) corroles and corresponding
(nitrido)manganese(V) complexes
Irena Saltsmana, Israel Goldberg*b and Zeev Gross*a
a Schulich Faculty of Chemistry, Technion-Israel Institute of Technology, Haifa 32000, Israel
b School of Chemistry, Sackler Faculty of Exact Sciences, Tel Aviv University, Tel Aviv 69978, Israel
Received 28 March 2010
Accepted 31 May 2010
ABSTRACT: Corroles that carry either two or three ortho-pyridyl groups at the meso-carbon atoms form
stable manganese(III) complexes, from which corresponding water-soluble derivatives are obtained via
N-alkylation. These syntheses and the spectroscopic features are disclosed, together with the molecular
structure of the manganese(III) corrole that carries three ortho-pyridylium groups.All the manganese(III)
corroles may be transformed to stable (nitrido)manganese(V) complexes, whose NMR spectra provide
invaluable structural information regarding the identity and number of atropoisomers.
KEYWORDS: corroles, synthesis, manganese, NMR, X-ray crystallography.
used for two important medicine-oriented aspects: DNA
INTRODUCTION
intercalation, and the decomposition of reactive oxy-
Manganese(III) corroles have lately been shown to
gen and nitrogen species in cellular models of various
display rich redox chemistry and to be effective oxida-
diseases [8]. We now present the synthesis and spectro-
tion catalysts [1, 2]. In addition, they serve as powerful
scopic characterization of manganese(III) and (nitrido)
catalytic antioxidants in models of various diseases [3].
Comparison with analogous porphyrins revealed that the
chemistry of the corrole complexes is distinctively differ-
ent and that they display unique chemistry in many cases
manganese(V) corroles with ortho-pyridyl groups at
the meso-carbon atoms, as well as the water-soluble
N-alkylated analogs, including the molecular structure of
the derivative with three ortho-pyridylium groups.
[4]. One aspect where corroles outperform porphyrins is
in the stabilization the [(nitrido)manganese(V)]2+ moiety
[2, 5], which is of importance regarding the development
of catalytic systems for nitrogen atom transfer reac-
tions and the fixation/activation of molecular nitrogen
EXPERIMENTAL
General
[6]. While the dianionic salen (sal) and porphyrin (por)
ligands are long known to form quite stable [(por)Mn(N)]
and [(sal)Mn(N)] complexes [7], their nitrogen atoms can
still be transferred to manganese(III) complexes chelated
by the trianionic corrolato ligands (cor) to form [(cor)
Mn(N)]- complexes [2]. Electrochemical examinations
further served to confirm the exceptional stability of the
latter. The most recently introduced para-pyridylium-
substituted corrole manganese(III) complexes were already
NMR spectra were recorded at room temperature on
a Bruker Avance 300 spectrometer (AV300) equipped
1
with a QNP H/19F/13C-2H 5 mm probe head (operating
at 300 MHz for 1H and 282 MHz for 19F) or on a Bruker
Avance 500 spectrometer (AV500) equipped with a bbo
probe head (operating at 500 MHz for 1H and 125 MHz
for 13C). Chemical shifts are reported in ppm relative to
solvent signals (δH = 1.94 for acetonitrile). Coupling con-
stants (J) are reported in Hz. A HP 8452A diode array
spectrophotometer was used to record the electronic spec-
tra. Mass spectroscopy was performed by either ESI on
a Waters Micromass LCT Premier instrument with nitro-
gen gas or by Waters MALDI-TOF instrument (direct
SPP full member in good standing
*Correspondence to: Zeev Gross, email: chr10zg@tx.technion.
ac.il, fax: +972 4-8295703 and/or Israel Goldberg, email:
goldberg@chemsg7.tau.ac.il, fax: +972 3-6409293
Copyright © 2010 World Scientific Publishing Company

616
I. SaltSman et al.
probe). All chemicals were used as received unless oth-
erwise noted. Chromatography was performed on silica
(Kieselgel 60, 230–400 mesh).
ortho-F), -156.18–156.48 (1F, m, para-F), -164.35–-
164.93 (2F, m, meta-F).
Preparation of the Mn(III) complex of 5,10,15-tris
(N-methyl-o-pyridylium)corrole (2d) and the Mn(III)
complex of 10-(pentafluorophenyl)-5, 15-bis(N-methyl-
o-pyridylium)corrole (1d). 1b and 2b were dissolved
in the minimum volume of DMF and excess of methyl
iodide (100 equiv.) was added to the solutions. Reac-
tion mixtures were stirred at room temperature over-
night. A small amount of methanol and threefold excess
of diethyl ether were added to the reaction mixtures.
Each precipitated product was collected and washed
with additional portion of diethyl ether. The residues
were dissolved in acetonitrile (grade HPLC) and care-
fully separated by chromatographic column (silica
gel, KCl(H2O, sat.):H2O:acetonitrile, 1:1:8), resulted
75% of 2d and 77% of 1d yields, as dark-green sol-
ids. 2d. Rf (silica, KNO3(H2O, sat.):H2O:acetonitrile,
1:1:8) = 0.24. MS (MALDI-TOF) LD+ (acetonitrile):
m/z 596 [M - (2 × CH3)]+. MS ESI+ (acetonitrile:H2O,
50:50): m/z 208 [M]3+/3. UV-vis (methanol): λmax, nm
(log ε) 416 (9.2), 478 (20.1), 610 (4.2). 1d. Rf (silica,
KNO3(H2O, sat.):H2O:acetonitrile, 1:1:8) = 0.78. UV-
vis (acetonitrile): λmax, nm (log ε) 402 (3.4), 476 (6.7),
630 (1.2). 19F NMR (282 MHz; CD3CN): δF, ppm
-119.29 (2F, br s, ortho-F), -153.63–-154.31 (1F, m,
para-F), -156.78–-157.91 (2F, m, meta-F). MS ESI+
Synthetic methods
Compounds (1a) and (2a) were prepared according to
the previously published procedure (Scheme 1) [9].
Preparation of the Mn(III) complex of 5,10,15-tris
(o-pyridyl)corrole (2b), and the Mn(III) complex of 10-
(pentafluorophenyl)-5, 15-bis(o-pyridyl)corrole (1b).
Based on our previously published procedure [1b], sam-
ples of 2a (50 mg, 86 µmol) or 1a (50 mg, 75 µmol) and
manganese(II) acetate tetrahydrate (221 mg, 900 µmol)
were dissolved in DMF (10 mL) and heated to reflux
for 20 min. Evaporation of the solvent, followed puri-
fication by column chromatography on silica gel
(5% MeOH in ethyl acetate for 2b; ethyl acetate/
hexanes (9:1) for 1b), resulted in the isolation of 2b
(49 mg, 89%) and of 1b (37 mg, 69%). 2b. Rf (silica,
ethyl acetate) = 0.47. MS (MALDI-TOF) LD+ (aceto-
nitrile): m/z 583 [M - H]+. UV-vis (acetonitrile): λmax
,
nm (log ε) 408 (9.4), 476 (5.3), 592 (2.6), 642 (2.8). 1b.
Rf (silica, ethyl acetate) = 0.75. MS (MALDI-TOF) LD+
(acetonitrile): m/z 670 [M]+. UV-vis (methanol): λmax
,
nm (log ε) 400 (9.1), 418 (10.3), 458 (6.6), 624 (2.8).
19F NMR (282 MHz; CD3CN): δF, ppm -140.82 (2F, br s,
Ar
Ar
Ar
N
N
N
N
NH
N
N
N
N
Mn(OAc)24H2O
DMF, reflux
bleach
N
N
N
N
N
N
Mn
Mn
NH3/H2O
N
NH HN
N
1a; 2a
1c; 2c
1b; 2b
Ar
NH
N
+N
N+
CH3I, DMF
NH NH
1a'; 2a'
Ar
Ar
N
N
N
N
N
N
+N
+N
N+
N+
bleach/NH3/H2O
MeOH; rt; 15 min
Mn
N
Mn
N
N
1e; 2e
1d; 2d
CH3
+N
F
F
F
F
N
1a-1e: Ar =
2a; 2b, 2c: Ar =
2d; 2e: Ar =
F
Scheme 1. Synthetic routes for the manganese(III) and (nitrido)manganese(V) corroles
Copyright © 2010 World Scientific Publishing Company
J. Porphyrins Phthalocyanines 2010; 14: 616–620

Water-SOluble manganeSe(III) COrrOleS anD COrreSPOnDIng (nItrIDO)manganeSe(V) COmPlexeS
617
(acetonitrile:H2O, 50:50): m/z 350 [M]2+/2, 370.5 [M +
CH3CN]2+/2.
[M]-. UV-vis (acetonitrile): λmax, nm (log ε) 432 (41.5),
548 (4.2), 584 (6.9). 2e. Rf (silica, KCl(H2O, sat.):H2O:
acetonitrile, 1:1:8) = 0.31. MS ESI+ (acetonitrile:H2O,
50:50): m/z 640 [M]2+. UV-vis (methanol): λmax, nm
(log ε) 432 (78.6), 552 (17.8), 588 (23.7).
Preparation of the (nitrido)Mn(V) complexes of
5,10,15-tris(o-pyridyl)corrole (2c); of 10-(pentafluoro-
phenyl)-5,15-bis(N-methyl-o-pyridylium)corrole (1e); of
10-(pentafluorophenyl)-5, 15-bis(o-pyridyl)corrole (1c);
and of 5,10,15-tris(N-methyl-o-pyridylium)corrole (2e).
Based on the previously published procedure [2b] sam-
ples 10 mg (17 µmol) of 1b; 2b; 1d or 2d (14 µmol) were
added to a 25 mL flask and dissolved in 10 mL of metha-
nol. 15 equiv. (7 µL, 17.6 µmol) of NH4OH and 6 equiv.
(3.7 mL, 70.7 µmol) of NaOCl were added to the solu-
tion. Immediately, the solution color changed from green
to purple-green. The reaction was monitored by UV-vis.
The solution was dried by sodium sulfate, filtered and
evaporated to dryness, affording 2c (9.5 mg, 93%), 1c
(9.3 mg, 91%), 1e (9.2 mg, 90%) and 2e (7.6 mg, 85%).
Crystallography
The diffraction measurements were carried out on a
Nonius KappaCCD diffractometer, using graphite mono-
chromated MoKα radiation (λ = 0.7107 Å). Crystal
data: (C37H35MnN8O2)3+·3I-, orthorhombic, space group
Pbcn, MW = 1059.37, a = 10.0388(2), b = 18.7942(5),
c = 20.1470(7) Å, V = 3801.2(2) Å3, T =110(2) K, Z = 4,
Dcalc = 1.851 g.cm-3, µ(MoKα) = 2.83 mm-1, 4531 unique
reflections, R1 = 0.068 for 3677 reflections with Io >
2σ(Io), wR2 = 0.221 for all unique data.
1
2c. Rf (silica, ethyl acetate/methanol, 1:1) = 0.68. H
NMR (500 MHz, CD3CN): δH, ppm 9.14 (2H, d, 3J(H,H) =
4.03 Hz, pyrrole-H), 9.09 (2H, d, 3J(H,H) = 5.50 Hz, pyr-
role-H), 9.04 (1H, br s, pyridine-H), 8.96 (2H, d, 3J(H,H) =
RESULTS AND DISCUSSION
The corrole ligands 1a and 2a were prepared via the
condensation of 5-(2-pyridyl)dipyrromethane with either
pentafluorophenylbenzaldehyde or 4-pyridinecarboxal-
dehyde, followed by subsequent oxidation by DDQ, as
described by Saltsman and co-workers [9]. This was fol-
lowed by insertion of manganese to afford complexes 1b
and 2b, which were N-methylated by iodomethane, lead-
ing to the water-soluble complexes 1d and 2d (Scheme 1).
This reaction scenario is preferable to the N-alkylation/
metal insertion route (indicated by the broken arrows
in Scheme 1), since we observed that the inner nitro-
gen atoms in the free-base corroles also react with
3
4.77 Hz, pyrrole-H), 8.79 (2H, d, J(H,H) = 4.03 Hz,
pyrrole-H), 8.61 (2H, d, 3J(H,H) = 4.40 Hz, pyrrole-H),
8.44 (2H, d, 3J(H,H) = 7.89 Hz, pyridine-H), 8.17 (2H, t,
3
3J(H,H) = 7.52 Hz, pyridine-H), 8.13 (1H, t, J(H,H) =
7.15 Hz, pyridine-H), 7.70-7.65 (4H, m, pyridine-H).
MS (MALDI-TOF) LD- (acetonitrile): m/z 595 [M]-. UV-
vis (methanol): λmax, nm (log ε) 434 (65.6), 546 (4.8),
588 (12.4). 1e. Rf (silica, ethyl acetate:methanol, 1:1) =
0.80. 1H NMR (500 MHz, CD3CN): δH, ppm 9.37 (1H, d,
3
3J(H,H) = 6.05 Hz, pyridine-H), 9.33 (1H, d, J(H,H) =
3
4.77 Hz, pyrrole-H), 9.20 (1H, d, J(H,H) = 6.24 Hz,
1
pyridine-H), 9.10–9.07 (1H, m, pyridine-H), 9.03 (1H,
d, 3J(H,H) = 7.70 Hz, pyridine-H), 8.89 (1H, t, 3J(H,H) =
7.70 Hz, pyridine-H), 8.82–8.78 (3H, m, pyrrole-H),
iodomethane (easily observable by new H NMR reso-
nances at <0 ppm due to N-CH3 moieties). Treatment of
complexes 1d and 2d with bleach/ammonia led to the
(nitrido)manganese(V) corroles 1e and 2e, respectively.
The analogous complexes 1c and 2c, with non-alkylated
pyridine substituents, were also prepared by the same
procedure, from 1b and 2b, respectively.
The manganese(III) complexes are paramagnetic and
the constitution of these compounds can hence not be
confirmed by 1H NMR spectroscopy. On the other hand,
changes in the electronic spectra are very distinctive
when it comes to the transformation of manganese(III) to
(nitrido)manganese(V) corroles. This is shown in Fig. 1,
for the transformation of 1b to 1c. While the electronic
spectra of the manganese(III) corroles is characteristi-
cally rich throughout the visible range (bands I → VI
in Boucher's nomenclature) [10], the products display
a sharp Soret band and a prominent absorption centered
about 580 nm that is distinctive of (nitrido)manganese(V)
porphyrinoids.
3
8.71 (1H, d, J(H,H) = 4.58 Hz, pyrrole-H), 8.69 (2H,
d, 3J(H,H) = 4.03 Hz, pyrrole-H), 8.67 (1H, t, 3J(H,H) =
4.95 Hz, pyrrole-H), 8.62 (1H, t, 3J(H,H) = 7.70 Hz,
pyridine-H), 8.46–8.40 (2H, m, pyridine-H), 4.38 (s)
and 4.37 (3H, s, CH3), 3.79 (s) and 3.77 (3H, s, CH3).
19F NMR (282 MHz, CD3CN): δF, ppm -140.55–-141.37
3
(2F, m, ortho-F), -157.74 (1F, t, J(F,F) = 20.9 Hz,
para-F), -165.25–-165.32 (2F, m, meta-F). MS ESI+
(acetonitrile:H2O, 50:50): m/z 357 [M]+/2. UV-vis (meth-
anol): λmax, nm (log ε) 430 (3.3), 582 (1.1). 1c. Rf (silica,
1
ethyl acetate) = 0.85. H NMR (500 MHz, CD3CN): δH,
3
ppm 9.16 (2H, d, J(H,H) = 3.67 Hz, pyrrole-H), 9.09
3
(2H, br s, pyridine-H), 8.99 (2H, d, J(H,H) = 4.40 Hz,
pyrrole-H), 8.82 (2H, d, 3J(H,H) = 3.67 Hz, pyrrole-H),
8.59 (2H, d, 3J(H,H) = 4.40 Hz, pyrrole-H), 8.44 (2H, d,
3
3J(H,H) = 7.70 Hz, pyridine-H), 8.18 (2H, t, J(H,H) =
7.34 Hz, pyridine-H), 7.74–7.68 (2H, m, pyridine-H).
19F NMR (282 MHz, CD3CN): δF, ppm -140.45 (1F, dd,
3J(F,F) = 25.6 Hz, 4J(F,F) = 7.9 Hz, ortho-F), -141.09 (1F,
dd, 3J(F,F) = 25.4 Hz, 4J(F,F) = 7.9 Hz, ortho-F), -158.87
(1F, t, 3J(F,F) = 19.7 Hz, para-F), -165.90–-166.45 (2F, m,
meta-F). MS (MALDI-TOF) LD- (acetonitrile): m/z 684
The most valuable tool regarding unambiguous identi-
fication of a (nitrido)manganese(V) moiety in 1c and 2c
is NMR spectroscopy, which is characterized by high-
resolution resonances indicative of diamagnetic com-
plexes. The diamagnetism by itself is fully (and only)
Copyright © 2010 World Scientific Publishing Company
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618
I. SaltSman et al.
Fig. 3. ORTEP view of the molecular structure of complex
2d·(H2O)2, characterized by a C2 symmetry. The empty ellip-
soids indicate the two disordered orientations of the methyl-
pyridinium group on C10 around the two-fold axis
Fig. 1. Spectral changes upon treatment of manganese(III)
corrole 1b (λmax = 418 nm; ~10-5 M) in MeOH with ammonia
(3.6 × 10-4 M)/bleach (1.4 × 10-4 M) in H2O at 25 °C, indicat-
ing its transformation to (nitrido)manganese(V) complex 1c
(λmax = 432 nm)
room temperature. Nevertheless, the non-equivalency of
the above and below corrole plane due to the presence of
the (nitrido)manganese(V) moiety in complex 1c is evi-
dent in its 19F NMR spectrum (Fig. 2(b)), since the dif-
ferences in chemical shifts (in Hz) are larger. Particularly
indicative for that purpose are the two sets of double dou-
blets (rather than one set) of ortho-F resonances at -140.4
and -141.1 ppm that are obtained for the meso-C6F5 ring.
N-alkylation of the pyridine groups may safely be pre-
dicted to stop the abovementioned dynamic atropoiso-
merization progress, which we have previously verified
by HPLC separation of the free-base αα and αβ isomers
of 1a′ and the ααα, ααβ, and αβα– isomers of 2a′. This
is further illustrated in Fig. 3, which displays the molecu-
lar structure of the manganese(III) corrole 2d·(H2O)2
(with two additional weakly coordinated axial water
ligands). The corrole molecule is located in the crystal
on a C2 axis, which passes through the C1-C19 bond, the
metal ion and the center of the methylpyridylium group at
C10. Correspondingly, the latter exhibits a two-fold ori-
entational disorder, while the methyl groups of the aryls
located on C5 and C15 (which also reveal partial disorder
due to loose crystal packing) point in opposite directions.
The corrole macrocycle is essentially planar. The man-
ganese ion is six-coordinate with a distorted octahedral
environment characterized by Mn-N(pyrrole) equatorial
distances of 1.894(5) and 1.912(5) Å and Mn-O(water)
axial coordination bonds of 2.328(6) Å. The iodide coun-
ter ions are located in intermolecular voids between the
corrole units.
consistent with a Mn5+ ion whose low-spin d2 is enforced
by a strong π-donating (and triply bound) N3- ligand. The
1
additional information that is obtainable from the H
NMR spectra is shown in Fig. 2(a), for complex 1c. The
four doublets (between 9.16 and 8.59 ppm) with small J
coupling constants (3.67 and 4.40 Hz) are safely assigned
to the four kinds of β-pyrrole protons [11], while the four
other resonances are fully consistent with the hydrogen
atoms on the meso-pyridine substituents. Complex 1c
should be a mixture of three different atropoisomers with
respect to the relative orientations of the N-atoms of the
pyridine rings (α or β) and the (nitrido)manganese(V)
moiety (A or B): αAα, αBα and αAβ (≡ αBβ), where α
vs. β and A vs. B are used as abbreviations for “above vs.
below the corrole plane”. This phenomenon is, however,
not reflected in the 1H spectrum, suggesting that rotation
of the pyridine rings is fast on the 1H NMR time scale at
Similar to the earlier discussion, the (nitrido)
manganese(V) complexes of the N-alkylated corroles
could be fully analyzed by NMR spectroscopy. What is
more, it also allows for the appreciation of the relative
amounts of the different atropoisomers. This is shown in
Fig. 4, which compares the 1H NMR spectra of the reso-
nances due to the methyl groups in the ortho-pyridylium-
alkylated free-base corrole 1a′ and in its corresponding
(nitrido)manganese(V) complex 1e. The two singlets at
about 4.15 ppm in Fig. 4(a) may be straightforwardly
assigned as reflecting the one kind only of methylpyridy-
lium groups in each of the atropoisomers of 1a′ (αα and
Fig. 2. 1H (a) and 19F (b) NMR spectra of (nitrido)manganese(V)
complex 1c
Copyright © 2010 World Scientific Publishing Company
J. Porphyrins Phthalocyanines 2010; 14: 618–620

Water-SOluble manganeSe(III) COrrOleS anD COrreSPOnDIng (nItrIDO)manganeSe(V) COmPlexeS
619
corrolato manganese(III) revealed one particular
atropoisomer, which displays a planar macrocycle due
to the coordination of two axial water molecules to the
metal. The corresponding (nitrido)manganese(V) deriva-
tives are very stable low-spin d2 complexes, whose dia-
magnetism allows for a detailed NMR-based structural
analysis. The 19F NMR spectra are particularly illuminat-
ing in terms of identifying that they are five-coordinated
due to the strong trans-effect of the [Mn≡N]2+ moiety.
Acknowledgements
This research was supported by the Israel Science
Foundation, Grants 890015 (ZG) and 502/08 (IG). The
funding of I.S. by the Center for Absorption in Science,
Ministry of Immigration, is also acknowledged (KAMEA
Foundation).
Supporting information
Crystallographic data for compound 2d·(H2O)2 have
been deposited at the Cambridge Crystallographic Data
Center (CCDC) under deposition number 780238.
Copies can be obtained on request, free of charge, via
www.ccdc.cam.ac.uk/conts/retrieving.html or from the
Cambridge Crystallographic Data Centre, 12 Union
Road, Cambridge CB2 1EZ, UK (fax: +44 1223-336-033
or email: deposit@ccdc.cam.ac.uk).
Fig. 4. Partial 1H NMR spectra of a) 1a′ and b) 1e, emphasizing
the two and four different resonances assigned to methylpyri-
dinium singlets, respectively
αβ). They are identical due to a σh symmetry operation
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moiety in the corresponding (nitrido)manganese(V) cor-
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different complexes with Cs symmetry: one wherein the
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SUMMARY AND CONCLUSION
We have devised synthetic access to manganese(III)
corroles with either two or three ortho-pyridyl meso-
substituents, which upon N-alkylation are converted into
water-soluble derivatives. These complexes have most
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