Electronic and steric effects of the peripheral substitution in deca- and undecaaryl metallocorroles

Article abstract of DOI:10.1002/ejic.201301314

The first example of a copper decaarylcorrole, 6, was isolated during the Suzuki cross-coupling synthesis of the corresponding undecaaryl derivative 2c. Compounds 6 and 2c were demetalated to produce the free bases 7 and 8, which were used to prepare the cobalt deca- and undecaarylcorroles 9 and 10. The effects of meso versus β substituents in peraryl copper corroles is highlighted by an electrochemical study of nine saddled copper undecaarylcorroles. The crystal structures of 1c, 6, 9, and 10 illustrate the impact of the deca- and undecaaryl substitutions on the macrocycle conformation in metallocorroles. The effects of meso versus β substituents in peraryl copper corroles is highlighted by an electrochemical study of nine undecaaryl copper corroles. The impact of peraryl substitution on corrole conformation is illustrated by the crystal structures of undecaaryl copper and cobalt corroles. The ring distortion is also studied in the first examples of copper and cobalt decaaryl corroles.

Full text of DOI:10.1002/ejic.201301314

FULL PAPER
DOI:10.1002/ejic.201301314
Electronic and Steric Effects of the Peripheral Substitution
in Deca- and Undecaaryl Metallocorroles
Di Gao,[a] Gabriel Canard,*[a,b] Michel Giorgi,[c] Pierre Vanloot,[d]
and Teodor Silviu Balaban[a]
COVER PICTURE
Keywords: Porphyrinoids / Macrocycles / Copper / Cobalt / Corroles
The first example of a copper decaarylcorrole, 6, was isolated
during the Suzuki cross-coupling synthesis of the corre-
sponding undecaaryl derivative 2c. Compounds 6 and 2c
were demetalated to produce the free bases 7 and 8, which
were used to prepare the cobalt deca- and undecaarylcor-
roles 9 and 10. The effects of meso versus β substituents in
peraryl copper corroles is highlighted by an electrochemical
study of nine saddled copper undecaarylcorroles. The crystal
structures of 1c, 6, 9, and 10 illustrate the impact of the deca-
and undecaaryl substitutions on the macrocycle conforma-
tion in metallocorroles.
been described and have been applied, for example, in the
field of chiral recognition[10] or for the preparation of sup-
ramolecular assemblies.[11] A metal–porphyrin orbital inter-
action[12] or the introduction of straps on the macrocycle[5a]
can induce nonplanar porphyrin deformation. However, in
most cases, this distortion is caused by steric hindrance be-
tween peripheral substituents,[13] for example, as in dodeca-
arylporphyrin derivatives.
Introduction
The nonplanar distortion of the porphyrin macrocycle is
now known to play a significant role in the biological ac-
tivity of natural tetrapyrrole–protein complexes.[1] For ex-
ample, the stabilization of a nonplanar tetrapyrrole confor-
mation is involved in the ferrochelatase-catalyzed ferrous
ion insertion into protoporphyrin IX to form protoheme.[2]
There are multiple consequences of the out-of-plane defor-
mation of the porphyrin skeleton. It has a strong impact
on the electronic absorption and emission of the distorted
compounds.[3] Consequently, it also controls photoinduced
electron transfers in porphyrin–chromophore dyads.[4] In
metalloporphyrins, the macrocycle deformation can also af-
fect strongly the coordination sphere of the metal ion and,
therefore, its electronic configuration,[5] magnetic proper-
ties,[6] or ability to bind axial ligands.[7] The electrochemical
properties of porphyrins and their metal complexes are also
sensitive to the macrocycle conformation,[8] which can be
either saddled, ruffled, waved, or domed.[1b,9] As the inter-
relationship between macrocycle conformation and
physicochemical properties in porphyrins has been estab-
lished, numerous examples of distorted porphyrins have
During the last decade, corroles, which are cousins of
porphyrins contracted by one carbon atom and still aro-
matic tetrapyrrolic macrocycles, have received increased at-
tention as their synthesis[14] and functionalization[15] are
now well developed. These compounds are also particularly
attractive because they stabilize metal ions in high oxidation
states such as FeIV,[16] AuIII [17] PV,[18] or recently ThIV.[19]
,
Consequently, simple to sophisticated synthetic corroles
were prepared and applied in the fields of catalysis,[20] sen-
sors,[21] and medicine.[22] In all these research areas, the dis-
tortion of the corrole moiety would increase their potential
to bind or recognize substrates selectively.
Copper corroles are saddled.[23] This distortion has been
attributed to an energetically favorable Cu(dx2–y2)–cor-
role(π) orbital interaction, which leads to the description of
these complexes as a CuIII corrole in equilibrium with a
CuII corrole π-cation radical with two strongly antiferro-
magnetically coupled unpaired electrons.[24] The nonplanar
conformation of these metallocorroles is also strongly sensi-
tive to peripheral substituents.[25] We[26] and others[27] have
recently disclosed the synthesis of copper undecaarylcor-
roles by a Suzuki cross-coupling procedure. The impact of
the peraryl substitution on the saddling potential of the
copper complexes was studied as well as its consequences
on their UV/Vis absorption. The influence of β-aryl substi-
tution on the electrochemical properties of copper corroles
[a] Aix Marseille Université, Centrale Marseille, CNRS, iSm2
UMR 7313,
13397 Marseille, France
[b] Aix Marseille Université, CNRS, CINaM UMR 7325,
13288 Marseille, France
E-mail: gabriel.canard@univ-amu.fr
http://www.cinam.univ-mrs.fr
[c] Aix Marseille Université, Fédération des Sciences Chimiques de
Marseille – Spectropole FR 1739,
13397 Marseille, France
[d] Aix Marseille Université, LISA EA 4672,
13397 Marseille, France
Supporting information for this article is available on the
WWW under http://dx.doi.org/10.1002/ejic.201301314.
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1a–1c, 2a–2c, and 3a–3c is reported here (Scheme 1) and
Results and Discussion
compared with those of 4a–4c reported elsewhere.[27a] The
effects of numerous bulky aryl groups on the macrocycle
conformation are also delineated by the first examples of
copper and cobalt decaarylcorroles. Their structures were
solved by single-crystal X-ray diffraction and are described
here together with those of undecaaryl metallocorroles in-
corporating copper and cobalt.
Synthesis
When a Suzuki cross-coupling procedure is applied to
copper β-octabromo-meso-triarylcorrole derivatives, the
corresponding copper undecaarylcorroles are obtained with
yields that depend on the nature of the starting corrole and
the arylboronic acid. We have already described the use of
this palladium-catalyzed procedure to prepare nine different
copper perarylcorroles 1a–1c, 2a–2c, and 3a–3c with yields
of 10–70% (Scheme 1). The competing dehalogenation re-
action is one of the causes of low isolated yields. For exam-
ple, during the synthesis of the copper complex 2c, a te-
dious chromatographic purification afforded the corre-
sponding decaaryl derivative 6 with a yield of 9%
(Scheme 2). Mass spectrometry and 1H NMR analysis con-
firmed the decaaryl substitution, and the dehalogenation of
the last bromine atom is most probably favored by moist-
ure. The UV/Vis spectrum of 6 has a Soret band located at
Scheme 1. Copper undecaarylcorroles (χ is the dihedral angle that
characterizes the distortion of the macrocycle).
Scheme 2. (i) Pd2(dba)3, K2CO3, toluene. (ii) FeCl2, H2SO4. (iii) Co(OAc)2·4H2O, PPh3, EtOH.
Table 1. Sums of the meso and β Hammett constants, half-wave potentials (V vs. SCE),[a] saddling dihedral angles (χ), and Soret band
maxima[b] of copper undecaarylcorroles.
Compound Σσmeso
Σσβ
Ring oxidation
CuIII/CuII
Ring reduction
X [°]
λmax [nm]
3rd
2nd
1st
1a
–0.81
–0.81
–0.81
1.35
1.35
1.35
3.66
3.66
3.66
0
–2.16
–1.36
0.496
–2.16
–1.36
0.496
–2.16
–1.36
0.496
–1.36
0
1.36
1.38
1.49
–
–
–
–
–
–
1.14
1.17
1.25
1.18
1.22
1.32
1.37
1.42
1.51
1.23
1.25
1.36
0.55
0.55
0.72
0.72
0.73
0.86
1.01
1.03
1.16
0.65
0.7
–0.58
–0.58
–0.40
–0.34
–0.33
–0.22
0.02
0.04
0.20
–0.50
–0.45
–0.17
–
–
–
–
–
–
–
–
463
464
461
451
446
439
413
419
421
445
441
442
1b
60.1
49.6
41.9
57.3
1c
2a
2b
2c
3a
31.8
24.7
33.3
3b
3c
–1.69
4a[c]
4b[c]
4c[c]
–
–
–
–
–
–
0
0
4.32
0.89
66.0
[a] Measured in CH2Cl2 containing 0.1 m [(nBu4N)ClO4]. [b] Recorded in CH2Cl2. [c] From ref.[27a]
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437 nm, which is blueshifted by 2 nm compared to that of tron-withdrawing ones. This effect has been clearly assessed
the corresponding decaaryl complex 2c (Table 1). This small in copper meso-triarylcorroles for which the E1/2 values are
blueshift illustrates the small effect of the removal of only linearly related to the sum of the Hammett meso-substitu-
one β-aryl group on the saddling conformation of the cop- ent constants (Σσmeso).[24a,30c,30e,31] The redox potentials
per complexes. Other analytical data were required to ident- also vary with the nature of the β substituents, but their
ify the unsubstituted position. A single crystal of 6 was effect has not yet been addressed.
grown, and its analysis by X-ray diffraction afforded the
structure of 6, which ascertains unambiguously that the β-
hydrogen atom is placed on the carbon atom C-13 borne
by the pyrrole ring C (Figure 4). This result confirms the
lower reactivity of the corrole B and C rings commonly
observed during the functionalization of corroles.[15]
The stabilities of corrole free bases increase as the elec-
tron deficiency of the peripheral substituent increases.[28]
The metallocorroles 2c and 6 bear sufficient electron-with-
The cyclic voltammetry (CV) of 1a–1c, 2a–2c, and 3a–3c
were examined at room temperature in CH2Cl2 containing
0.1 m [(nBu4N)ClO4] and compared with those of 4a–c re-
corded under identical experimental conditions (Figure 1).
For the convenience of the readers used to corrole electro-
chemistry, the CVs are presented according to previously
published results. Each copper corrole has two reversible
ring-centered oxidations and one reversible metal-centered
reduction. A second reduction is seen for 3c, for which all
the peripheral substituents are electron-withdrawing
groups. On the other hand, the cyclic voltammograms of
1a–1c, which bear efficient meso electron-donating groups,
display a third oxidation at high potential. At room tem-
perature, the electrooxidation of copper corroles is some-
times associated with a dimer formation that is favored by
electron-donating substituents.[30b,32] The steric hindrance
of the peraryl substitution is probably high enough to pre-
vent the dimerization of the corrole cations. Berg et al. ob-
served a second reduction peak for 4a–4c with an E1/2 value
of –0.90 V versus the saturated calomel electrode (SCE) that
is independent of the peripheral substituents.[27a] The same
phenomenon occurred during our study when more than
one reductive scan was conducted on all copper corroles.
The appearance of this second reduction process is illus-
trated by Figure 2, which shows eight consecutive reductive
scans on a solution of 2a. As for 4a–4c, the half-wave po-
tential of this reduction is located at –0.90 V versus the SCE
and is independent of the substitution. Moreover, the mag-
nitude of this reduction increases with the number of scans.
As copper corroles are readily demetalated under reductive
experimental conditions,[29,33] this reduction peak is proba-
bly caused by the increasing presence of free CuII ions at
the electrode–solution interface.
drawing groups, and their demetalations with concentrated
[29]
H2SO4 and FeCl2
gave the corresponding free bases 7
and 8 in 50 and 87% yield, respectively (Scheme 2). These
metal-free derivatives afforded the pentacoordinate cobalt
corroles 9 and 10 by reaction with cobalt(II) acetate and
with triphenylphosphine as an axial ligand. Owing to its
dissymmetric substitution, the metallocorrole 9 is inherently
chiral. Unfortunately, all attempts to separate the two
enantiomers of 9 by chiral HPLC failed. This result was
attributed to the loss of the axial phosphine ligand on the
chiral supports.
Electrochemical Analysis of Copper Undecaarylcorroles
Numerous analyses of the electrochemical properties of
copper corroles have been reported.[24a,30] These studies
show that the number of detected oxidations and reductions
depends strongly on the solvent, the temperature, and the
electron deficiency of the substituents.[31] In most cases, the
oxidations are ring-centered, whereas the first reduction is
metal-centered. When electron-withdrawing groups are
borne by the macrocycle or when the solvent is carefully
chosen, up to two supplementary corrole-centered re-
ductions can occur. Both the oxidation and the reduction
The half-wave potentials of 1a–1c, 2a–2c, and 3a–3c are
half-wave potentials are shifted tremendously when the pe- summarized in Table 1, which also includes literature data
ripheral electron-donating substituents are changed to elec- for 4a–4c. A comparative examination of the E1/2 values of
Figure 1. Cyclic voltammograms of 1a–1c, 2a–2c, and 3a–3c in CH2Cl2 {0.1 m [(nBu4N)ClO4]} recorded at room temperature.
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For the first ring oxidation (E1/2ox1), the value of 35 mV
is almost identical to the one reported for meso-triaryl cop-
per corroles, which reaches 32 mV.[24a] This result shows
that this ring-centered oxidation is not affected by the sad-
dled conformation of the macrocycle and is governed by
the electron-donating efficiency of the substitution. On the
contrary, in peraryl derivatives, the meso-substituent effect
on the metal-centered reduction (47 mV) is twice that ob-
served in the meso-triaryl series (23 mV). This increasing
effect is probably a consequence of the enhancement of the
saddling distortion of the copper complexes and, therefore,
the copper(d)–corrole(π-HOMO) orbital overlapping by the
β-aryl substitution.
Figure 2. Multiple reduction scans of 2a in CH2Cl2 {0.1 m [(nBu4N)-
ClO4]} recorded at room temperature.
the CuIII/CuII reduction and of the first two macrocycle-
centered oxidations affords new insights into effects of meso
versus β substituents. The meso substituents exert a strong
influence on the half-wave potentials of the first oxidation
and the first reduction. For example, when the three meso-
p-methoxyphenyl groups of 1a are changed into three
pentafluorophenyl groups in 3a, the E1/2 value of the CuIII
/
For comparison, the β-substituent effects are given by:
CuII reduction changes from –0.58 to 0.02 V. On the other
hand, the effect of the β substituents is much smaller. When
the eight β electron-donating groups of 1a are replaced by
electron-withdrawing groups in 1c, the variation of the E1/2
value of the metal-centered reduction is only 0.17 V. The
same trends are observed for the second ring-centered oxi-
dation but are less pronounced as, above all, the higher en-
ergy of this redox transfer is due to the oxidation of an
already oxidized π system.
The stronger electronic influence of the meso substituents
versus the β substituents is in accordance with the ampli-
tudes of the highest occupied molecular orbitals (HOMOs)
and the lowest unoccupied molecular orbital (LUMOs) of
copper corroles, which are much larger at the meso posi-
tions. Consequently, different weights should be given to
the meso and β substituents in the search for correlations
between the different E1/2 values and the Hammett substitu-
ent constants of 1a–1c, 2a–2c, 3a–3c, and 4a–4c. Therefore,
the sum of the Hammett meso group constants (Σσmeso) was
separated from the corresponding β component (Σσβ;
Table 1). A multiple linear regression (MLR) was used to
fit the three half-wave potentials E1/2red1, E1/2ox1, and
E1/2ox2 as linear combinations of Σσmeso and Σσβ (Support-
ing information). The results show that these three redox
potentials exhibit very good correlations with the Hammett
variables Σσmeso and Σσβ in Equations (1–3).
These results confirm the higher efficiency of the meso-
aryl groups at tuning the electronic character of the copper
corroles. Their electronic effect is more than five times
larger than the β-aryl one.
Crystal Structures of Copper Corroles 1c and 6
In copper undecaarylcorroles, the stronger electronic in-
fluence of the meso versus the β substituents is also seen
through the saddling distortion of the macrocycle and is
usually illustrated by the values of the saddling dihedral
angle χ between the two adjacent B and C pyrrole units
(Scheme 1, Table 1). The highest χ values are reached for
complexes bearing meso electron-donating groups, whereas
the β substituents are either electron-donating or electron-
withdrawing groups (Table 1). The β substitution by aryl
groups exercises a steric effect close to that of bromine
atoms and intensifies the saddling distortion of the corroles.
Single crystals of 1c and 6 suitable for X-ray diffraction
were grown by slow diffusion of n-heptane into concen-
trated dichloromethane solutions (Figures 3, 4, and S1).
The crystal structures of 1c and 6 show features similar to
those previously reported for 1b, 2a–2b, and 3a–3c.[26] The
average Cu–N distances are 1.91 Å in 1c and 1.90 Å in 6,
and the copper atom lies exactly in the mean plane of the
four nitrogen atoms in both structures. In 1c, each meso-
(1)
(2)
(3)
As there are three meso-aryl groups, the substituent ef- aryl group interacts with the two adjacent β-aryl substitu-
fects for each meso-aryl group are given by:
ents through π–π stacking interactions, which also occur
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between the two β-aryl groups adjacent to the direct pyr- groups such as bromine atoms[14e] or alkyl chains[35] at the
role–pyrrole bond. The macrocycle in 1c is strongly saddled β positions of meso-triaryl cobalt(III) corroles does not pro-
and has a χ value of 49.6° (Figure 3). This value reflects the duce any distortion of the macrocycle, which remains sub-
strong electron-donating properties of the meso-p-meth- stantially planar. The planarity of the 23-atom core in co-
oxyphenyl groups.
balt corroles is also maintained when bulky alkyl chains are
located at the meso positions.[36] To check if the deca- or
the undecaaryl substitution induces unusual distortions of
cobalt(III) corroles, single crystals suitable for X-ray dif-
fraction of the pentacoordinate cobalt(III) corroles 9 and
10 were grown.
The structures of 9 and 10 show four sets of π–π stacking
interactions between peripheral aryl groups, analogous to
those observed in the copper series (Figures 5 and S2). As
for 6, the structure of 9 unambiguously proves that the last
β-hydrogen atom is borne by C-13. As for all cobalt(III)
corroles, the structure of 9 and 10 show a cobalt(III) ion in
an approximately square-pyramidal environment. The coor-
dination of the metallic center is not affected by the missing
aryl substituent, as the average Co–N (1.885 Å) and the
Co–P (2.205 Å) distances in 9 are nearly the same as those
in 10 (1.891 Å and 2.204 Å). The displacement of the cobalt
atom from the mean plane of the four nitrogen atoms by
0.272 Å in 9 is also very close to that of 10 (0.276 Å). Sim-
ilar or equal distances were measured in the structures of
simpler triphenylphosphino cobalt corroles.[37] Conse-
quently, the steric peripheral congestion has no detectable
Figure 3. Views of the X-ray structures of saddled copper corroles
1c and 6 along the Cu–C10 axis (aryl groups and solvent molecules
are omitted for clarity).
Figure 4. View of the X-ray structure of copper corrole 6 (solvent
molecules are omitted for clarity).
The structure of 6 confirmed unambiguously the replace-
ment of one β-aryl group by one hydrogen atom at the 13-
position (Figure 4). This is the first example of a decaaryl-
substituted metallocorrole. The decaaryl substitution does
not produce any unusual effect on the saddling distortion
of 6 and it has a χ value of 29.1° (Figure 3). Unfortunately,
we cannot precisely compare this value with that of 2c, for
which all attempts to obtain strongly diffracting crystals
failed. Nevertheless, the saddling dihedral angle of 6 is sim-
ilar to those of 2a and 2b, which bear the same meso-aryl
groups (Table 1).
Crystal Structures of Cobalt Corroles 9 and 10
Corrole was discovered by Johnson and Kay in 1965
while they were preparing synthetic models of corrins, the
chromophore of vitamin B12 that chelates a cobalt ion.[34]
Consequently, cobalt(III) corroles were among the first re-
ported metallocorroles and have been extensively studied.
Among all the available X-ray structures of cobalt(III) cor-
roles, few examples concern fully substituted complexes.
Figure 5. Views of the X-ray structure of cobalt corroles 9 and 10
Two of these structures show that the introduction of bulky (hydrogen atoms and solvent molecules are omitted for clarity).
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umn chromatography was performed with silica gel 60 (230–
400 mesh).
1H nuclear magnetic resonance (NMR) spectra were recorded with
effect on the cobalt coordination. Moreover, an analysis of
the macrocycle conformation of 9 and 10 confirms the abil-
ity of cobalt corroles to retain an almost planar conforma-
tion when they are fully substituted (Figure 6). In both Bruker Avance 300 or Bruker Avance 400 Ultrashield NMR spec-
trometers. Chemical shifts are given in ppm relative to the residual
peaks of chloroform (δ = 7.26 ppm), [D8]THF (δ = 1.73 and
3.58 ppm), or [D5]pyridine (δ = 7.22, 7.58, and 8.74 ppm).
structure, the 23-atom core of the corrole moiety is fairly
planar and has a mean plane deviation of 0.103 Å in 9 and
0.086 Å in 10 with largest deviations of 0.303 and 0.231 Å,
respectively. In metallocorroles, when the ligand is innocent, UV/Vis spectra were measured with a Shimadzu UV-2401 (PC) in-
strument.
that is, when no metal(d)–corrole(π) orbital interaction oc-
curs, the corrole macrocycle remains planar even if bulky
groups are placed at all the peripheral positions.
High-resolution mass spectrometry (HRMS-ESI) was performed
with a QStar Elite (Applied Biosystems SCIEX) spectrometer or a
SYNAPT G2 HDMS (Waters) spectrometer. These two instru-
ments are equipped with an electrospray ionization source and were
used in the positive-ion mode with a capillary voltage set at
+5500 V. MALDI-TOF mass spectra were obtained with a Voyager
instrument from Applied Biosystems with anhydrous glycerol, 2Ј-
(4-hydroxyphenylazo)benzoic acid (HABA), or 1,8,9-anthracen-
triol (dithranol) matrices.
Cyclic voltammetric (CV) data were acquired by using a BAS 100
Potentiostat (Bioanalytical Systems) and the BAS100W software
(version 2.3). A three-electrode system with a Pt working electrode
(diameter 1.6 mm), a Pt counterelectrode, and a Ag/AgCl (with 3 m
NaCl filling solution) reference electrode was used. (nBu)4ClO4
(0.1 m in CH2Cl2) served as an inert electrolyte. Cyclic voltammog-
rams were recorded at a scan rate of 100 mVs–1. Ferrocene was
used as internal standard.[38] The oxidation and reduction poten-
tials were modeled by using a multiple linear regression. The mod-
els were built by a cross validation method during the calibration
Figure 6. Views of the structures of cobalt corroles 9 and 10 along
the Co–C10 axis (aryl groups and solvent molecules are omitted
for clarity).
Conclusions
The conformation of the porphyrin skeleton is extremely developments. The chemometric procedures were performed by the
UNSCRAMBLER software version 9.2 from CAMO (Computer
Aided Modelling, Oslo, Norway).
sensitive to numerous parameters such as metal-orbital in-
teractions or steric hindrance between peripheral substitu-
ents. The control of the nonplanar porphyrin distortion is
The intensity data of the X-ray-quality crystals were collected with
crucial as this deformation tunes all the physicochemical a Bruker–Nonius KappaCCD diffractometer with Mo-Kα radiation
(λ = 0.71073 Å). Data collection was performed with COL-
LECT,[39] and cell refinement and data reduction were preformed
with DENZO/SCALEPACK.[40] The structures were solved with
SIR92,[41] and SHELXL-97[42] was used for full-matrix least-
squares refinement. Compound 6 cocrystallized with a CH2Cl2 sol-
vent molecule in the asymmetric unit that was disordered over two
sites, the occupancies of which were fixed to 0.7 and 0.3. Com-
pound 1c cocrystallized with half a disordered water molecule posi-
tioned on two sites, the occupancies of which were fixed to 0.3
and 0.2. Moreover, one methoxy substituent was disordered and its
properties of distorted porphyrin derivatives. The first ex-
amples of cobalt(III) deca- and undecaarylcorroles show
here that the introduction of multiple peripheral bulky aryl
groups is not sufficient to induce a corrole out-of-plane de-
formation. Nevertheless, the peripheral steric congestion
can be used to tune the corrole skeleton distortion pro-
duced when the aromatic macrocycle plays a noninnocent
role in metallocorroles. In these cases, the β versus meso
substituent effects rely on the amplitudes of the HOMO
and LUMO at the β and meso positions. For example, in oxygen atom was refined on two sites with occupancies fixed to 0.5.
For 9 and 10, the PLATON/SQUEEZE correction[43] was applied
copper undecaarylcorroles, the β-aryl groups enhance the
because the highly disordered solvent molecules could not be iden-
saddling distortion, which is mostly guided by the electron-
tified on the Fourier difference map. The SORTAV multiscan ab-
donating properties of the meso substituents. The electronic
sorption correction[44] was applied to the data for 9. When neces-
properties of the meso groups control predominantly the
sary, FLAT, DELU, and SIMU restraints were incorporated in the
electrochemical properties and the redshifted UV/Vis ab-
refinements for 1c and 10. The hydrogen atoms were all introduced
sorption, which vary slightly with the nature of the β-aryl
substituents (Table 1). The introduction of extremely bulky
at geometrical positions, and their Uiso parameters were fixed to
1.2Ueq(parent atom) for the aromatic atoms, the carbon atoms of
groups or the fabrication of straps seem to be the only way
to induce corrole distortion if no metal–corrole(π) orbital
interaction occurs.
the cyclohexane, or the CH2Cl2, whereas the hydrogen atoms of the
methyl groups were fixed to 1.5Ueq(parent atom).
CCDC-924362 (for 1c), -924361 (for 6), -924363 (for 9), and
-924364 (for 10) contain the supplementary crystallographic data
for this paper. These data can be obtained free of charge from The
Cambridge Crystallographic Data Centre via www.ccdc.cam.ac.uk/
data_request/cif.
Experimental Section
General Remarks: All reagents were used as received. Toluene was
distilled from sodium and benzophenone. Dichloromethane, hex-
ane, and n-heptane were distilled from calcium hydride. Flash col-
Copper corroles 1a–1c, 2a–2c, 3a–3c, and 5 and corrole 8 were
prepared and purified according to literature procedures.[26] Single
Eur. J. Inorg. Chem. 2014, 279–287
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crystals of 1c were grown by slow diffusion of n-heptane into a
concentrated solution of 1c in dichloromethane.
6.68 (m, 6 H, ArH), 6.45 (m, 6 H, ArH), 3.93 (s, 3 H, CO2CH3),
3.86 (t, 6 H, CO2CH3) ppm. UV/Vis (CH2Cl2): λmax (ε ϫ10–3) =
453 (109.0), 610 (27.1), 693 (22.9) mn. HRMS (ESI): calcd. for
β-Octa(p-fluorophenyl)-meso-tris(p-methoxycarbonylphenyl)corrole
CuIII Complex (2c) and β-Hepta(p-fluorophenyl)-meso-tris(p-meth-
oxycarbonylphenyl)corrole CuIII Complex (6): CuIII β-octabromo-
meso-tris(p-methoxycarbonylphenyl)corrole (5; 22 μmol, 30 mg),
Pd2(dba)3 (0.05 equiv., 1.1 μmol, 1 mg; dba = dibenzylideneace-
tone), and 4-fluorophenylboronic acid (32 equiv., 689 μmol,
96 mg), K2CO3 (32 equiv., 689 μmol, 95) were added to a round-
bottomed flask. The flask was evacuated and backfilled with argon
three times before toluene (15 mL) was added with a syringe. The
mixture was stirred at 100 °C for 60 h and then cooled to room
temp. The solvent was evaporated under reduced pressure. The
crude product was chromatographed (silica gel, CH2Cl2/hexane 4:1)
to afford 2c (21 mg, 13 μmol, 63%) and 6 (3 mg, 2.1 μmol, 9%) as
brown solids. 2c: Rf = 0.23 (CH2Cl2). 1H NMR (400 MHz, CDCl3,
C85H54N4O6F7 [M + H]+ 1359.3853; found 1359.3928.
+
β-Hepta(p-fluorophenyl)-meso-tris(p-methoxycarbonylphenyl)corrole
CoIII Complex (9): Co(OAc)2·4H2O (0.01 mmol, 3.3 mg) and PPh3
(0.01 mmol, 3.3 mg) were added to a solution of corrole 7 (3 μmol,
5 mg) in EtOH (5 mL) in one portion at room temperature. The
solvent was heated to reflux. TLC examinations (silica, CH2Cl2/
EtOAc 50:1) revealed that the starting material was fully consumed
at room temperature within 3 h. The solvent was evaporated, and
the mixture was chromatographed on silica gel (CH2Cl2). After
evaporation of the solvent, recrystallization from CH2Cl2/heptane
afforded 9 as a red solid (2.7 mg, 1.6 μmol, 53 %). Rf = 0.39
1
3
(CH2Cl2). H NMR (400 MHz, CDCl3, 25 °C): δ = 8.02 (d, JH,H
3
= 7.8 Hz, 2 H, ArH), 7.91 (d, JH,H = 8.0 Hz, 2 H, ArH), 7.87 (s,
1 H, β-H), 7.57 (d, JH,H = 6.4 Hz, 2 H, ArH), 7.40 (d, JH,H
3
3
3
3
=
25 °C): δ = 7.22 (d, JH,H = 8.3 Hz, 4 H, ArH), 7.17 (d, JH,H
=
3
3
7.4 Hz, 2 H, ArH), 7.34 (d, JH,H = 8.8 Hz, 2 H, ArH), 7.23 (d,
8.4 Hz, 2 H, ArH), 7.08 (d, JH,H = 8.3 Hz, 2 H, ArH), 6.95 (d,
3JH,H = 8.4 Hz, 2 H, ArH), 7.14 (d, JH,H = 8.1 Hz, 2 H, ArH),
3
3JH,H = 8.3 Hz, 4 H, ArH), 6.78 (d, JH,H = 8.6 Hz, 2 H, ArH),
3
3
4
3
3
6.94 (td, JH,H = 7.3 Hz, JH,H = 1.3 Hz, 3 H, H PPh3), 6.92 (td,
6.76 (d, JH,H = 8.6 Hz, 2 H, ArH), 6.56 (d, JH,H = 8.6 Hz, 2 H,
3JH,H = 8.1 Hz, JH,H = 2.4 Hz, 6 H, H PPh3), 6.89 (d, JH,H
=
4
3
ArH), 6.55 (d, 3JH,H = 8.7 Hz, 4 H, ArH), 6.51 (d, JH,H = 8.7 Hz,
3
3
3
8.4 Hz, 2 H, ArH), 6.78 (m, 8 H, ArH), 6.62 (m, 16 H, ArH), 5.12
(m, 6 H, H PPh3), 3.98 (s, 3 H, CO2CH3), 3.93 (s, 3 H, CO2CH3),
3.90 (s, 3 H, CO2CH3) ppm. 19F NMR (400 MHz, CDCl3, 25 °C):
δ = –116.97 (m, 1 F), –117.09 (m, 2 F), –117.38 (m, 2 F), –117.72
(m, 1 F), –117.79 (m, 1 F) ppm. UV/Vis (CH2Cl2): λmax (ε ϫ10–3)
= 416 (157.4), 572 (40.6) nm. MS (MALDI-TOF): m/z = 1414.4
[M – PPh3]+, 1437.4 [M – PPh3 + Na]+. Single crystals of 9 were
grown by slow diffusion of n-heptane into a concentrated solution
of 9 in dichloromethane.
2 H, ArH), 6.43 (d, JH,H = 8.6 Hz, 3 H, ArH), 6.42 (d, JH,H
=
3
8.2 Hz, 4 H, ArH), 6.41 (d, JH,H = 8.3 Hz, 2 H, ArH), 6.39 (d,
3JH,H = 8.7 Hz, 2 H, ArH), 6.35 (d, JH,H = 8.7 Hz, 2 H, ArH),
3
3
3
6.31 (d, JH,H = 8.7 Hz, 4 H, ArH), 6.27 (d, JH,H = 8.6 Hz, 3 H,
ArH), 3.87 (s, 6 H, CO2CH3), 3.83 (s, 3 H, CO2CH3) ppm. 19F
NMR (400 MHz, CDCl3, 25 °C): δ = –115.17 (m, 2 F), –116.17 (m,
2 F), –116.23 (m, 2 F), –116.65 (m, 2 F) ppm. UV/Vis (CH2Cl2):
λmax (ε ϫ 10–3) = 439 (118.9), 557 (19.4), 639 (11.8) nm. MS
(MALDI-TOF): m/z = 1512.2 [M]+, 1535.2 [M + Na]+. 6: Rf =
0.24 (CH2Cl2). 1H NMR (400 MHz, CDCl3, 25 °C): δ = 7.71 (d,
β-Octa(p-fluorophenyl)-meso-tris(p-methoxycarbonylphenyl)corrole
CoIII Complex (10): Co(OAc)2·4H2O (0.04 mmol, 10.3 mg) and
PPh3 (0.04 mmol, 10.5 mg) were added to a solution of corrole 8
(0.01 mmol, 15 mg) in EtOH (10 mL) in one portion at room tem-
perature. The solvent was heated to reflux. TLC examinations (sil-
ica, CH2Cl2/EtOAc 50:1) revealed that the starting material was
fully consumed at room temperature within 3 h. The solvent was
evaporated, and the mixture was chromatographed on silica gel
(CH2Cl2). After evaporation of the solvent, recrystallization from
CH2Cl2/heptane afforded 10 as a red solid (10.5 mg, 5.9 μmol,
59 %). Rf = 0.38 (CH2Cl2). 1H NMR (400 MHz, [D5]pyridine,
25 °C): δ = 7.68 (s, 8 H, ArH), 7.56 (s, 2 H, H PPh3), 7.46 (m, 13
3
3JH,H = 8.2 Hz, 2 H, ArH), 7.39 (d, JH,H = 8.2 Hz, 2 H, ArH),
3
3
7.22 (d, JH,H = 8.2 Hz, 2 H, ArH), 7.15 (t, JH,H = 8.4 Hz, 4 H,
3
ArH), 7.05 (s, 1 H, β-H), 6.92 (d, JH,H = 8.2 Hz, 2 H, ArH), 6.77
4
4
(m, 4 H, ArH), 6.68 (dd, JH,H = 5.5 Hz, JH,H = 8.4 Hz, 2 H,
ArH), 6.39 (m, 22 H, ArH), 3.93 (s, 3 H, CO2CH3), 3.88 (s, 3 H,
CO2CH3), 3.83 (s, 3 H, CO2CH3) ppm. 19F NMR (400 MHz,
CDCl3, 25 °C): δ = –115.21 (m, 2 F), –115.77 (m, 1 F), –116.29 (m,
2 F), –116.73 (m, 2 F) ppm. UV/Vis (CH2Cl2): λmax (ε ϫ10–3) =
437 (128.8), 555 (21.8), 633 (12.1) nm. MS (MALDI-TOF): m/z =
1418.2 [M]+. Single crystals of 6 were grown by slow diffusion of
n-heptane into a concentrated solution of 6 in dichloromethane.
3
H, H PPh3), 7.37 (m, 8 H, ArH), 7.18 (d, JH,H = 8.5 Hz, 2 H,
β-Hepta(p-fluorophenyl)-meso-tris(p-methoxycarbonylphenyl)corrole
(7): Copper corrole 6 (3 μmol) and anhydrous FeCl2 (5 equiv.,
15 μmol, 1.90 mg) were introduced into a 50 mL round-bottomed
flask under argon. Concentrated H2SO4 (96%, 2 mL) was added
dropwise, and the reaction mixture was stirred for 1 h. The progress
of the reaction was monitored by the disappearance of the copper
corrole as followed by UV/Vis spectroscopy and TLC. After the
complete consumption of the starting corrole, the reaction was
quenched with distilled water and extracted with CHCl3. The or-
ganic layer was washed once with water, twice with a saturated
aqueous solution of NaHCO3, and dried with anhydrous Na2SO4.
After filtration and evaporation, the green residue was chromato-
graphed on silica gel (CH2Cl2/EtOAc 100:1Ǟ100:3). After evapora-
tion and recrystallization from CH2Cl2/heptane, 7 was obtained as
a dark green solid (2.1 mg, 1.5 μmol, 50%). Rf = 0.26 (CH2Cl2/
3
3
ArH), 7.17 (d, JH,H = 8.4 Hz, 2 H, ArH), 7.08 (d, JH,H = 8.5 Hz,
3
3
2 H, Ar H), 7.07 (d, JH,H = 8.5 Hz, 2 H, ArH), 6.97 (d, JH,H
=
3
8.6 Hz, 2 H, ArH), 6.96 (d, JH,H = 8.5 Hz, 2 H, ArH), 6.76 (td,
3JH,H = 6.3 Hz, JH,H = 3.8 Hz, 8 H, ArH), 6.66 (m, 8 H, ArH),
4
3.90 (s, 6 H, CO2CH3), 3.86 (s, 3 H, CO2CH3) ppm. 19F NMR
(400 MHz, [D5]pyridine, 25 °C): δ = –116.18 (m, 4 F), –116.34 (m,
2 F), –116.42 (m, 2 F) ppm. UV/Vis (CH2Cl2): λmax(ε ϫ10–3) = 416
(83.1), 572 (21.4) nm. MS (MALDI-TOF): m/z = 1508.4 [M –
PPh3]+, 1531.4 [M – PPh3 + Na]+. Single crystals of 10 were grown
by slow diffusion of cyclohexane into a concentrated solution of
10 in chloroform.
Supporting Information (see footnote on the first page of this arti-
cle): Supplementary figures; details of the MLR realized on the
electrochemical data; structural analysis and refinement of corroles
1
1c, 6, 9, and 10; H NMR spectra of all new compounds.
1
EtOAc, 10:1). H NMR (400 MHz, [D8]THF, 25 °C): δ = 8.17 (s,
3
3
1 H, β-H), 7.88 (q, JH,H = 8.4 Hz, 2 H, ArH), 7.76 (d, JH,H
=
3
7.8 Hz, 2 H, ArH), 7.63 (d, JH,H = 8.3 Hz, 2 H, ArH), 7.54 (d,
Acknowledgments
3JH,H = 8.3 Hz, 2 H, ArH), 7.46 (d, JH,H = 8.3 Hz, 2 H, ArH),
3
3
3
7.26 (q, JH,H = 8.3 Hz, 2 H, ArH), 7.18 (d, JH,H = 8.3 Hz, 2 H, D. G. gratefully acknowledges the China Scholarship Council for
ArH), 7.10 (m, 4 H, ArH), 7.01 (m, 4 H, ArH), 6.86 (m, 6 H, ArH), financial support.
Eur. J. Inorg. Chem. 2014, 279–287
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Received: October 8, 2013
Published Online: November 19, 2013
Eur. J. Inorg. Chem. 2014, 279–287
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