Demetalation of copper undecaarylcorroles: Molecular structures of a free-base undecaarylisocorrole and a gold undecaarylcorrole

Article abstract of DOI:10.1016/j.jinorgbio.2016.06.026

Copper undecaarylcorroles were found to undergo acid-induced demetalation with unusual ease under both reductive and nonreductive conditions. The resulting free-base undecaarylcorroles were found to be rather reactive, readily photooxygenating to yield 5/10-hydroxyisocorroles and open-chain tetrapyrroles. The use of nonreductive conditions led to 50-75% yields of undecaarylisocorroles, a new class of sterically hindered ligands, of which one proved amenable to single-crystal X-ray structural analysis. In one case, interaction of an undecaarylisocorrole with gold(III) acetate resulted in aromatization of the macrocycle and a gold undecaarylcorrole. The Au complex exhibited Au-N distances of 1.941(3)–1.965(3) ?, and no significant nonbonded interactions involving the gold. The significant solubility of this complex in organic solvents, compared with the relative insolubility of gold β-octabromo-meso-triarylcorroles, appears to be related to the lack of aurophilic and metallophilic interactions.

Full text of DOI:10.1016/j.jinorgbio.2016.06.026

JIB-10028; No of Pages 8
Journal of Inorganic Biochemistry xxx (2016) xxx–xxx
Contents lists available at ScienceDirect
Journal of Inorganic Biochemistry
journal homepage: www.elsevier.com/locate/jinorgbio
Demetalation of copper undecaarylcorroles: Molecular structures of a free-base
undecaarylisocorrole and a gold undecaarylcorrole
a
a
a
a
b
Jan Capar , Job Zonneveld , Steffen Berg , Johan Isaksson , Kevin J. Gagnon ,
a,
a,
Kolle E. Thomas ⁎, Abhik Ghosh ⁎
Department of Chemistry and Center for Theoretical and Computational Chemistry, University of Tromsø, N-9037 Tromsø, Norway
a
b
Advanced Light Source, Lawrence Berkeley National Laboratory, Berkeley, CA 94720-8229, USA
a r t i c l e i n f o
a b s t r a c t
Article history:
Copper undecaarylcorroles were found to undergo acid-induced demetalation with unusual ease under both re-
ductive and nonreductive conditions. The resulting free-base undecaarylcorroles were found to be rather reac-
tive, readily photooxygenating to yield 5/10-hydroxyisocorroles and open-chain tetrapyrroles. The use of
nonreductive conditions led to 50-75% yields of undecaarylisocorroles, a new class of sterically hindered ligands,
of which one proved amenable to single-crystal X-ray structural analysis. In one case, interaction of an
undecaarylisocorrole with gold(III) acetate resulted in aromatization of the macrocycle and a gold
undecaarylcorrole. The Au complex exhibited Au-N distances of 1.941(3)–1.965(3) Å, and no significant non-
bonded interactions involving the gold. The significant solubility of this complex in organic solvents, compared
with the relative insolubility of gold β-octabromo-meso-triarylcorroles, appears to be related to the lack of
aurophilic and metallophilic interactions.
Received 11 March 2016
Received in revised form 22 May 2016
Accepted 23 June 2016
Available online xxxx
Keywords:
Isocorrole
Corrole
Gold
Reductive demetalation
©
2016 Elsevier Inc. All rights reserved.
1
. Introduction
reported that thiacorroles, which are structurally similar to isocorroles,
give rise to intermediate-spin iron(III) complexes [23]. A second re-
markable feature of isocorroles is their strong absorption in the near-
infrared [18], which is of great relevance to photodynamic therapy
[24]. Reported herein are optimized syntheses for a family of sterically
hindered undecaarylisocorrole ligands, including the first, single-
crystal X-ray structure of a free-base undecaarylisocorrole.
Furthermore, we have attempted to determine whether
undecaarylisocorrole ligands can be rearomatized on metal complexation,
yielding novel undecaarylcorrole complexes. This is an important ques-
tion because, as of today, only copper and cobalt undecaarylcorroles
have been reported [15-17]. New metalloundecaarylcorroles are of con-
siderable interest as shape-selective catalysts and other functional mate-
rials. As shown in Fig. 2, we found that at least one free-base
undecaarylisocorrole could be smoothly converted to the corresponding
gold undecaarylcorrole. The same gold complex could also be obtained
from a gold β-octabromo-meso-triarylcorrole via a tedious, week-long
Suzuki coupling procedure. Remetalation and aromatization of isocorroles
to corroles, when feasible, thus promises to be a useful transformation.
Metallocorroles [1–4], particularly copper corroles, are typically
much more readily functionalized and elaborated in a controlled manner
than free-base corroles. Subsequent demetalation then has the potential
to yield novel, substituted free-base corrole ligands. Unfortunately, the
demetalation of metallocorroles is generally more difficult than that of
common metalloporphyrins, requiring both strong acid and an excess
of a reductant such as a Fe(II) or Sn(II) salt [5–10]. A notable success of
this ‘reductive demetalation’ approach has been the synthesis of free-
base β-octabromocorroles [11] and their subsequent use as ligands [12,
1
3,14]. Here we report that copper undecaarylcorroles [15–17]
demetalate with unusual ease, in a matter of minutes, on exposure to
acid, under both reductive and nonreductive conditions.
In what initially appeared to be
a
setback, free-base
undecaarylcorroles were found to be rather reactive, readily reacting
with ambient oxygen to generate 5-hydroxy- and 10-hydroxy-
undecaarylisocorroles as well as open-chain dioxo compounds. As
shown in Fig. 1, isocorroles are fascinating ligands in their own right:
they are porphyrin-like by virtue of their diprotic or dianionic character
and corrole-like in affording a spatially constricted cavity for metal coor-
dination [18–22]. They are thus promising platforms for unusual transi-
tion metal spin states. In a pertinent study, Bröring and coworkers have
2. Results and discussion
2.1. Demetalation of copper undecaarylcorroles and isocorrole formation
Four different copper undecaarylcorroles were demetallated in this
⁎
Corresponding authors.
E-mail addresses: thomas.kolle@uit.no (K.E. Thomas), abhik.ghosh@uit.no (A. Ghosh).
study, copper β-octakis(p-X-phenyl)-meso-tris(p-methylphenyl)corrole,
http://dx.doi.org/10.1016/j.jinorgbio.2016.06.026
162-0134/© 2016 Elsevier Inc. All rights reserved.
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Please cite this article as: J. Capar, et al., Demetalation of copper undecaarylcorroles: Molecular structures of a free-base undecaarylisocorrole and
a gold undecaarylcorrole, J. Inorg. Biochem. (2016), http://dx.doi.org/10.1016/j.jinorgbio.2016.06.026

2
J. Capar et al. / Journal of Inorganic Biochemistry xxx (2016) xxx–xxx
quantities for full characterization. Fig. 4 presents the UV–vis absorption
spectra of these two isomeric compounds; note the intense Soret-like
features, despite the lack of aromaticity, and strong absorption in the
red and near-infrared. Examples of preferential formation of one or
the other regioisomer is well-documented in the literature [25–27].
Thus, a convenient isocorrole synthesis, involving DDQ oxidation of
meso-triarylcorroles in methanol, was found to lead preferentially to
5
-OMe isocorroles [22]. On the other hand, nonreductive demetalation
of Cu[Br ] (i.e., copper β-octabromo-meso-triphenylcorrole) with
/CHCl led to preferential formation of the 10-OH isocorrole,
(10-OH)] [6]. A combination of electronic and steric factors is
8
H
3
H
H
2
SO
[Br
4
3
2
8 3
H
presumably responsible for the preponderance of one isomer over the
other.
Literature reports suggest that the oxygen in 5/10-OH isocorroles
2
arises from O rather than water, although the latter has not been strict-
ly ruled out [26,27]. To determine the source of oxygen in the
isocorroles obtained in this study, we carried out isotope labeling exper-
Fig. 1. Steric and electronic relationships between porphyrin, corrole, and isocorrole
ligands. Whereas porphyrin and isocorroles share the same proticity (both coordinate as
dianionic ligands), isocorroles and corroles share similar, constricted coordination cavities.
18
18
iments with H
[(CF Me ], upon stirring in anhydrous dichloromethane and H
under argon, showed no evidence of
electrospray ionization (ESI) mass spectrometry (MS). In contrast, bub-
bling 16
into a solution of pure H [(CF Me ] in anhydrous dichloro-
methane revealed the incorporation of both one and two oxygen atoms
2
O and
2
O . The freshly purified, vacuum-dried corrole
18
H
3
)
3 8
3
2
O
18
O
incorporation with
where X = H, F, CF
meso-triphenylcorrole (Fig. 3). For brevity, we will refer to these com-
plexes as Cu[X Me ]. We will also refer to the corresponding free-base
corroles as H [X Me ] and the isocorroles as H [X Me (5-OH)]. Reduc-
tive demetalation of Cu[X Me ] with concentrated sulfuric acid and
10 equiv. of anhydrous FeCl led to ~70% yields of the free-base corroles,
[X Me ], in a matter of minutes, but in the presence of air and
3
, and copper β-octakis(p-trifluoromethylphenyl)-
O
2
3
)
3 8
3
8
3
1
8
3
8
3
2
8
3
via ESI-MS. Flushing the ESI mass spectrometer with
in the incorporation of both one and two
O
2
also resulted
18
8
3
O atoms into
~
2
3 3 8 3
H [(CF ) Me ], confirming the strong affinity of free-base
H
3
8
3
undecaarylcorroles for dioxygen. One plausible pathway for the oxida-
tive decomposition of free-base corroles, based on both literature prece-
dence [20,21,28,29] and our own experiments, is depicted in Fig. 5.
A single-crystal X-ray structure could be obtained for the free-base
light, free-base undecaarylcorroles quickly decomposed to open-
chain dioxotetrapyrroles and small quantitites of the isocorroles,
H [X Me (5/10-OH)]. Eliminating reductive conditions (i.e., FeCl )
2 8 3 2
proved to be an effective way of improving the yield of isocorroles,
the key targets of this study, as did the presence of an organic solvent
such as dichloromethane. The final optimized conditions, involving
demetalation in dichloromethane and concentrated sulfuric acid,
led to 50–75% yields of highly stable, free-base isocorroles, with neg-
ligible quantities of corroles and open-chain tetrapyrroles.
undecaarylisocorrole H
the considerable steric crowding, the macrocyclic skeleton of
[(CF Me (5-OH)] was found to be essentially planar, as for other
free-base isocorroles, but in sharp contrast to free-base corroles,
which are generally strongly buckled as a result of steric repulsion
among the three inner hydrogens [30,31]. The two central hydrogens
2 3 8 3
[(CF ) Me (5-OH)] (Fig. 6, Table 1). Despite
H
2
3
)
8
3
Each demetalation led to both 5- and 10-OH isocorroles, with the
former dominating. Although not separable by column chromatogra-
phy, the two regioisomers could be separated by preparative thin-
2 3 8 3
of H [(CF ) Me (5-OH)] could be unambiguously located from the dif-
ference map. The skeletal bond distances, which are broadly similar to
those observed for other 5-isocorrole structures [21,25], are consistent
with strong localization of single and double bonds, with no significant
indication of homoaromaticity.
layer chromatography. Except for one case, H
2 3 8 3
[(CF ) Me (10-OH)],
however, the pure 10-regioisomer was not obtained in large enough
3 8 3
Fig. 2. Two alternative synthetic routes to the gold undecaarylcorrole Au[(CF ) H ].
Please cite this article as: J. Capar, et al., Demetalation of copper undecaarylcorroles: Molecular structures of a free-base undecaarylisocorrole and
a gold undecaarylcorrole, J. Inorg. Biochem. (2016), http://dx.doi.org/10.1016/j.jinorgbio.2016.06.026

J. Capar et al. / Journal of Inorganic Biochemistry xxx (2016) xxx–xxx
3
Fig. 3. Corrole and isocorrole derivatives investigated in this study.
2
.2. Synthesis and molecular structure of a gold undecaarylcorrole
triarylcorroles are only slightly saddled [35], a recent X-ray structure
Fig. 7 has provided an example of a strongly saddled silver β-
octabromocorrole [36]. The substantial variations in corrole geometry
in the silver case have been attributed to variations in noninnocent
character among the different ligands. By contrast, corrole ligands in
gold corroles are thought to be innocent.
Given the oxidative instability of free-base undecaarylcorroles, we
were intrigued by the question whether metal insertion into a free-
base undecaarylisocorrole might proceed with concomitant aromatiza-
tion, thereby providing a pathway to novel metalloundecaarylcorroles.
Although a full exploration of this question, involving different
isocorroles and metal ions, has not yet been carried out, we were grati-
fied to discover that interaction of free-base H
gold(III) acetate in pyridine leads to the new, fully aromatized
undecaarylcorrole complex Au[(CF ] in yields of ~40% [32,33]. We
3
[(CF
3
)
8
H
3
(5-OH)] and
3. Conclusion
) H
3 8 3
In summary, copper undecaarylcorroles were found to demetallate
with unusual ease under standard reductive demetalation conditions.
The free-base undecaarylcorroles, however, proved to be light- and
oxygen-sensitive, readily oxidizing to open-chain dioxotetrapyrroles
and 5/10-OH isocorroles. Nonreductive conditions could be devised
that led to good yields 50–75% of 5/10-OH undecaarylisocorroles, a
new class of sterically hindered and relatively stable macrocyclic li-
gands. Interaction of one such ligand with gold(III) acetate resulted in
rearomatization of the macrocycle and a gold undecaarylcorrole,
which proved amenable to single-crystal X-ray diffraction analysis. Un-
like the rather insoluble gold β-octabromo-meso-triarylcorroles, the
gold undecaarylcorrole was found to be moderately soluble in organic
solvents. The relatively high solubility appears to be related to the lack
are currently examining the generality of this process and will report
on our findings in due course.
Unlike many gold β-octabromocorrole complexes, which tend to be
quite insoluble, presumably because of intermolecular metallophilic
Au…Br interactions [32], Au[(CF ) H ] was found to be moderately sol-
3 8 3
uble. X-ray quality crystals were obtained and single-crystal structure
determination revealed a planar Au corrole, Au-N distances of
1
.941(3)–1.965(3) Å, and no significant nonbonded interactions involv-
ing the gold (Fig. 7) [34]. The planarity of the gold corrole may be
contrasted with the strong nonplanarity of copper corroles, which is be-
lieved to be due to ligand noninnocence. Silver corroles exhibit more
variable behavior in this regard. Thus, whereas simple silver meso-
2 3 8 3 2 3 8 3
Fig. 4. UV–vis spectra of H [(CF ) H (5-OH)] and H [(CF ) H (10-OH)].
Please cite this article as: J. Capar, et al., Demetalation of copper undecaarylcorroles: Molecular structures of a free-base undecaarylisocorrole and
a gold undecaarylcorrole, J. Inorg. Biochem. (2016), http://dx.doi.org/10.1016/j.jinorgbio.2016.06.026

4
J. Capar et al. / Journal of Inorganic Biochemistry xxx (2016) xxx–xxx
Fig. 5. Proposed pathway for photooxygenation of a free-base undecaarylcorrole. Analogous mechanisms can be drawn for O
2
attack at the 2- and 10-positions.
of intermolecular aurophilic and metallophilic interactions involving
the gold atom.
equiv). After degassing with argon, dry toluene (10 mL) was added.
After purging with argon for 10 min, the suspension was stirred at
100–105 °C under argon for 1–2 days. Progress of the reaction was mon-
4
. Experimental section
itored by mass spectrometry. When product formation appeared to have
stabilized, the reaction mixture was cooled to room temperature, diluted
4
.1. Materials
with 10 mL of CH
then with distilled water. The CH
Na SO , filtered, and evaporated. The brown residue obtained was
chromatographed on a silica gel column with hexane/CH Cl as eluent.
The product eluted as a dark brown band, which was collected and evap-
orated to dryness. The residue was purified by preparative thin-layer
chromatography (PLC), as detailed below for each corrole.
2
Cl
2
, and washed with saturated aqueous NaHCO
3
and
2
Cl phase was dried with anhydrous
2
All reagents and solvents were used as purchased unless stated oth-
2
4
erwise. Anhydrous toluene (Sigma-aldrich) was stored over pre-
activated 3 Å molecular sieves. Silica gel 150 (35–70 μm particle size,
Davisil) was used for flash chromatography and silica gel 60 plates
2
2
(
20 × 20 cm; 0.5 mm thick, Merck) were used for preparative thin-
layer chromatography (PLC). Copper β-octabromo-meso-tris(4-
methylphenyl)corrole, Cu[Br Me ] and copper β-octabromo-meso-
triphenylcorrole, Cu[Br ], served as the starting materials for copper
8
3
4.4. Synthesis of copper 2,3,7,8,12,13,17,18-octakis(4-fluorophenyl)-meso-
H
8 3
tris(p-methylphenyl)corrole, Cu[F Me ]
8
3
undecaarylcorroles and were synthesized as previously described [37].
Copper β-octakis(p-trifluoromethylphenyl)-meso-triphenylcorrole],
The reaction employed 0.025 mol (32 mg) of Cu[Br TMePC] and was
8
Cu[(CF
3
)
8
H
3
], was also synthesized according to a literature method
complete after ~2 days (45 h). Both the column chromatography and
[15].
subsequent PLC were carried out with 3:1 hexane/CH Cl as eluent.
2
2
The pure product Cu[F
8
Me
3
] (26.6 mg, 76%) eluted as the most intense
−
4
−1
−1
4
.2. Instrumentation
brown band. UV–vis (CH
2
Cl
2
): λmax, nm (ε × 10 , M cm ): 448
, 400 MHz, δ in ppm): δ 6.87 (d,
Ph), 6.80–6.74 (m, 4H, 2.18-o, 4-FPh; 4H,
Ph), 6.57–6.51 (m, 4H, 3,17-o, 4-FPh; 4H, 2,18-m, 4-FPh),
6.47–6.26 (m, 4H, 8,12-o, 4-FPh; 4H, 7,13-o, 4-FPh; 4H, 3,17-m, 4-FPh;
4H, 5,15-m, 4-CH Ph; 4H, 7,13-m, 4-FPh; 4H, 8,12-m, 4-FPh; 2H, 10-
m, 4-CH Ph), 2.02 (s, 6H, 5,15-p, 4-CH Ph), 1.91 (s, 3H, 10-p, 4-
): δ −116.31 to −116.39 (m, 2F), −118.08 to
(
3.56), 644 (0.32). 1H NMR (CDCl
3
Ultraviolet-visible (UV–vis) spectra were recorded with CH
solvent on an HP 8453 spectrophotometer. H NMR spectra were ob-
tained at 298 K on either a Mercury Plus Varian spectrometer
2
Cl
2
as
J = 8.0 Hz, 2H, 10-o, 4-CH
5.15-o, 4-CH
3
1
3
(
400 MHz) in CDCl
to 5.30 ppm), and in C
spectrometer (600 MHz) equipped with a cryogenically cooled inverse
triple-resonance probe in 1,1,2,2-tetrachloroethane-d (CDCl -CDCl
3
(referenced to 7.26 ppm), in CD
2
Cl
2
(referenced
3
D
6 6
(referenced to 7.20 ppm) or a Varian Inova
3
3
CH
3 3
Ph). 1 F NMR (CDCl
9
−118.21 (m, 4F), −118.62 to −118.70 (m, 2F). MS (HR-ESI, major
2
2
2
,
1
9
+
referenced to 5.91 ppm). F NMR spectra (376 MHz) were recorded
isotopomer): [M] = 1380.3440 (expt), 1380.3438 (calcd).
at 298–333 K on a Mercury Plus Varian spectrometer and referenced
to 2,2,2-trifluoroethanol-d
3
(δ = −77.8 ppm). [Note: Overlapping
4.5. Synthesis of copper 2,3,7,8,12,13,17,18-octakis(4-trifluoromethylphenyl)
peaks are indicated below as o and conformationally broadened peaks
as b.] Electrospray ionization mass spectra were recorded on an LTQ
Orbitrap XL spectrometer.
-5,10,15-tris(4-methylphenyl)corrole, Cu[(CF ) Me ]
3
8
3
The reaction employed 0.020 mol (25 mg) of Cu[Br TMePC] and was
8
complete after 24 h. Both the column chromatography and subsequent
4
.3. General procedure for the synthesis of copper undecaarylcorroles
PLC were carried out with 3:1 hexane/CH
uct Cu[(CF Me ] (18.4 mg, 52%) eluted as the most intense brown
band. UV–vis (CH
642 (0.44), 841 (0.59). H NMR (CDCl
J = 4.0 Hz, 4H, 2,18-o, 4-CF Ph), 6.97 (d, J = 4.0 Hz, 4H, 2,18-m, 4-
CF Ph), 6.94 (d, J = 4.0 Hz, 4H, 3,17-o, 4-CF Ph), 6.89 (d, J = 4.0 Hz,
4H, 7,13-o, 4-CF Ph), 6.85 (d, J = 4.0 Hz, 4H, 8,12-o, 4-CF Ph), 6.81 (d,
2 2
Cl as eluent. The pure prod-
3
)
8
3
−
4
−1
−1
The syntheses were carried essentially according to the procedure re-
2 2
Cl ): λmax, nm (ε × 10 , M cm ): 454 (4.34),
1
ported by Ghosh and coworkers [15]. Into a 50-mL three-necked round-
bottomed flask equipped with a magnetic stirring bar and a reflux con-
denser were introduced Cu[Br
equiv), potassium carbonate (40 equiv), and Pd
3
, 600 MHz, δ in ppm): δ 7.09 (d,
3
8
Me
3
], the arylboronic acid of choice (40
(dba) ·CHCl (0.1
3
3
2
3
3
3
3
2 3 8 3
Fig. 6. X-ray structure of free-base undecaarylisocorrole H [(CF ) Me (5-OH)]: (a) top view with skeletal bond distances (Å) and (b, c) side views.
Please cite this article as: J. Capar, et al., Demetalation of copper undecaarylcorroles: Molecular structures of a free-base undecaarylisocorrole and
a gold undecaarylcorrole, J. Inorg. Biochem. (2016), http://dx.doi.org/10.1016/j.jinorgbio.2016.06.026

J. Capar et al. / Journal of Inorganic Biochemistry xxx (2016) xxx–xxx
5
Please cite this article as: J. Capar, et al., Demetalation of copper undecaarylcorroles: Molecular structures of a free-base undecaarylisocorrole and
a gold undecaarylcorrole, J. Inorg. Biochem. (2016), http://dx.doi.org/10.1016/j.jinorgbio.2016.06.026

6
J. Capar et al. / Journal of Inorganic Biochemistry xxx (2016) xxx–xxx
Table 1
Crystallographic data for H
4.6. Synthesis of copper 2,3,7,8,12,13,17,18-octaphenyl-5,10,15-tris(4-
methylphenyl)corrole, Cu[H Me
2 3 8 3 3 8 3
[(CF ) Me (5-OH)] and Au[([(CF ) H ].
8
3
]
Sample
H
2
[(CF Me (5-OH)]
3
)
8
3
Au[(CF
3
) H
8 3
]
The reaction employed 0.021 mol (27 mg) of Cu[Br
complete after 48 h. Column chromatography was carried out with hex-
ane/CH Cl as eluent, while 3:1 n-hexane/CH Cl was used for the PLC.
The pure product Cu[H ] (12.1 mg, 46%) eluted as the most intense
brown band. UV–vis (CH
8
TMePC] and was
Chemical formula
Formula mass
Crystal system
Space group
λ (Å)
a (Å)
b (Å)
c (Å)
C
96
H
56
F
24
N
4
C
95
H
51
F
24
N
4
Cl
4
Au
1737.44
Triclinic
P1
2043.16
Triclinic
P-1
2
2
2
2
8
Me
3
0.7749
0.7749
−4
−1
−1
2
Cl
2
): λmax, nm (ε × 10 , M cm ): 448
12.783(3)
18.085(4)
18.600(4)
102.363(3)
108.203(3)
96.468(3)
2
3914.7(15)
100(2)
1.474
15.4998(6)
16.8410(6)
16.9639(6)
106.229(2)
91.961(2)
106.901(2)
2
4035.8(3)
100(2)
1.681
1
(
6.17), 544 (0.77), 645 (0.49). H NMR (CD
6.86 (d, J = 8.4 Hz, 2H, 10-o, 4-CH Ph), 6.85–6.82 (m, 4H, 2,18-o, Ph;
2H, 2.18-p, Ph), 6.80–6.76 (m, 4H, 2,18-m, Ph), 6.74 (d, J = 7.8 Hz, 4H,
2 2
Cl , 600 MHz, δ in ppm): δ
3
α (deg.)
β (deg.)
γ (deg.)
Z
5
,15-o, 4-CH
3
Ph), 6.72–6.68 (m, 2H, 3,17-p, Ph), 6.65–6.63 (m, 4H,
3
,17-o, Ph; 4H, 3,17-m, Ph), 6.62–6.58 (m, 2H, 7,13-p, Ph; 4H, 7.13-m,
3
Ph), 6.58–6.57 (m, 2H, 8,12-p, Ph), 6.57–6.54 (m, 4H, 8,12-m, Ph; 4H,
8,12-o, Ph), 6.54–6.52 (m, 4H, 7,13-o, Ph), 6.19 (d, J = 7.2 Hz, 4H,
V (Å )
Temperature (K)
3
Density (g/cm )
5
,15-m, 4-CH
3
Ph), 6.16 (d, J = 7.8 Hz, 2H, 10-m, 4-CH
3
Ph), 1.90 (s,
Measured reflections
Unique reflections
Parameters
40,303
15,237
1169
78,866
29,236
1256
6
H, 5,15-p, 4-CH
3
Ph), 1.80 (s, 3H, 10-p, 4-CH Ph). MS (HR-ESI, major
3
+
isotopomer): [M] = 1237.4223 (expt), 1237.4220 (calcd).
Restraints
66
646
R
int
0.0670
2.587–28.553
0.0683, 0.2226
1.024
0.410/−0.349
0.0524
2.165–36.007
0.0459, 0.1140
1.030
2.151/−1.956
4.7. Undecaarylisocorrole H [F Me (5-OH)]
2
8
3
θ range (deg.)
, wR all data
S (GooF) all data
Max/min res. Dens. (e/Å )
R
1
2
Into a 50 mL round-bottomed flask was placed 25 mg (0.018 mmol)
of Cu[F Me ] and dissolved in 3 mL of CH Cl . Subsequently, 3 mL of
concentrated H SO (95–97%, Merck) was added. The mixture was
3
8
3
2
2
2
4
then stirred and sonicated at room temperature. Progress of the reaction
was monitored by ESI mass spectrometry. After 2 h, the reaction mix-
J = 8.0 Hz, 2H, 10-o, 4-CH
3
Ph), 6.75 (d, J = 4.0 Hz, 4H, 3,17-m, 4-CF
.69 (d, J = 8.0 Hz, 4H, 5,15-o, 4-CH
,8,12,13-m, 4-CF Ph), 6.25 (d, J = 4.0 Hz, 4H, 5,15-m, 4-CH
Ph), 1.93 (s, 6H, 5,15-p, 4-CH
Ph). F NMR (CDCl ): δ −63.07 (s, 6F), −63.17 (s,
F), −63.29 (s, 6F), −63.46 (s, 6F). MS (HR-ESI, major isotopomer):
3
Ph),
6
7
3
Ph), 6.62 (d, J = 8.0 Hz, 8H,
Ph), 6.19
Ph), 1.82
ture was carefully poured into 300 mL of distilled H
ed with CHCl . The organic phase was washed once with distilled water
and twice with saturated aqueous NaHCO . Upon washing with
NaHCO3, the color of the organic phase changed from brown to green.
The organic phase was then dried with anhydrous Na SO , filtered,
and the filtrate rotary-evaporated to dryness. The residue obtained
was chromatographed on a silica gel column with CH Cl /1%-MeOH.
The product was further purified by PLC with 2:3 n-hexane/CH Cl
upon completion of the PLC, the pure product H [F Me (5-OH)]
14.4 mg, 60%) was obtained as the most intense green band in the mid-
2
O and then extract-
3
3
3
(
(
d, J = 8.0 Hz, 2H, 10-m, 4-CH
3
3
3
1
9
s, 3H, 10-p, 4-CH
3
3
6
2
4
+
[M] = 1781.3211 (expt), 1781.3261 (calcd).
2
2
2
2
;
2
8
3
(
−
4
−1
−1
dle of the plate. UV–vis (CH
2
Cl
2
): λmax, nm (ε × 10 , M cm ): 433
, 600 MHz, δ in ppm): δ 8.05 (d, J =
Ph), 7.01 (d, J = 8.3 Hz, 2H, 5-m, 4-FPh), 6.81
d, J = 8.1 Hz, 1H, 10-o, 4-CH Ph), 6.80 (d, J = 8.6 Hz, 2H, 3-o, 4-FPh),
.70 (d, J = 8.0 Hz, 1H, 7-o, 4-FPh), 6.69 (t, J = 7.6 Hz, 1H, 7-m, 4-
FPh), 6.60 (d, J = 8.6 Hz, 2H, 2-o, 4-FPh), 6.55 (t, J = 8.5 Hz, 2H, 3-m,
-FPh), 6.44 (overlapping, 1H, 7-o, 4-FPh), 6.42 (o, 12-o, 4-FPh), 6.36
o, 1H, 7-m, 4-FPh), 6.33 (o, 1H, 10-m, 4-CH Ph), 6.29 (o, 1H, 8-m, 4-
FPh), 6.25 (t, J = 8.8 Hz, 2H, 2-m, 4-FPh), 6.20 (o, 1H, 8-o, 4-FPh), 6.11
o, 1H, 8-m, 4-FPh), 6.07 (d, J = 8.4 Hz, 1H, 10-o, 4-CH Ph), 6.02 (t,
J = 8.5 Hz, 0.5H, 12-m, 4-FPh), 5.65 (d, J = 7.8 Hz, 1H, 10-m, 4-
CH Ph), 2.29 (s, 1H, –OH), 2.05 (s, 3H, 5-p, 4-CH Ph), 1.86 (s, 3H, 15-
p, 4-CH Ph), 1.72 (s, 3H, 10-p, 4-CH ): δ −115.96
Ph). 19F NMR (CDCl
to −116.08 (m, 1F), −116.25 to −116.36 (m, 1F), −116.45 to −
16.59 (m, 1F), −117.38 to −117.49 (m, 1F), −117.79 to −117.88
m, 1F), −117.95 to −118.09 (m, 2F), −118.25 to −118.35 (m, 1F).
1
(
3.37), 683 (0.69). H NMR (C
6
D
6
8
(
6
.1 Hz, 2H, 5-o, 4-CH
3
3
4
(
3
(
3
3
3
3
3
3
1
(
+
MS (HR-ESI, major isotopomer): [M + H] = 1337.4415 (expt),
1337.4399 (calcd).
2 3 8 3 2 3 8 3
4.8. Undecaarylisocorroles H [(CF ) Me (5-OH)] and H [(CF ) Me (10-
OH)]
Into a 50 mL round-bottomed flask, 20 mg (0.0112 mmol) of
Cu[(CF Me ] was added and dissolved in 4 mL of CH Cl . Subsequent-
ly, 2 mL of concentrated H SO (95–97%, Merck) was added. The mix-
)
3 8
3
2
2
2
4
ture was stirred and sonicated at room temperature. The progress of
the reaction was monitored by ESI mass spectrometry. After 4 h the re-
action was quenched by pouring the mixture into 300 mL distilled H
and then extracted with CHCl . The brown organic phase was washed
once with distilled water and once with saturated aqueous NaHCO
2
O
Fig. 7. X-ray structure of the gold undecaarylcorrole Au[(CF
b) side view.
3 8 3
) H ]: (a) top view and
3
(
3
.
Please cite this article as: J. Capar, et al., Demetalation of copper undecaarylcorroles: Molecular structures of a free-base undecaarylisocorrole and
a gold undecaarylcorrole, J. Inorg. Biochem. (2016), http://dx.doi.org/10.1016/j.jinorgbio.2016.06.026

J. Capar et al. / Journal of Inorganic Biochemistry xxx (2016) xxx–xxx
7
Upon washing with NaHCO
brown to green. The organic phase was dried with anhydrous Na
filtered and evaporated under vacuum. The residue obtained was
3
the color of organic phase changed from
atoms. Additional crystallographic information has been summarized
in Table 1 and full details can be found in the crystallographic informa-
tion file provided in the Supplementary Information.
2 4
SO ,
chromatographed on a silica gel column with 2:1 n-hexane/CH
The product was further purified by PLC with 2:1 n-hexane/CH
2
Cl
Cl
2
.
.
2
2
The most intense green band in the middle of the plate was pure
[(CF Me (5-OH)] (11 mg, 57%) and the most intense light-green
band below that was H [(CF Me (10-OH)] (3.7 mg, 19%). X-ray qual-
ity crystals of H [(CF Me (5-OH)] were grown by slow diffusion of n-
heptane into the benzene solution. Analytical data for the two isomers
are as follows.
2 8 3
4.12. Undecaarylisocorrole H [H Me (5-OH)]
H
2
)
3 8
3
2
)
3 8
3
Into a 50 mL round-bottomed flask, 12 mg (0.0097 mmol) of
Cu[H Me ] was added and dissolved in 2 mL of CH Cl . Subsequently,
2 mL of concentrated H SO (95–97%, Merck) was added. The mixture
2
3
)
8
3
8
3
2
2
2
4
was stirred and sonicated at room temperature. The progress of the re-
action was monitored by ESI mass spectrometry. After 2 h the reaction
4
.9. Undecaarylisocorrole H
2
[(CF
3
)
8
Me
3
(5-OH)]
was quenched by pouring the mixture into 300 mL distilled H
then extracted with CHCl . The brown organic phase was washed
once with distilled water and once with saturated aqueous NaHCO
Upon washing with NaHCO the color of organic phase changed from
brown to green. The organic phase was dried with anhydrous Na SO
filtered and evaporated under vacuum. The residue obtained was
chromatographed on a silica gel column with CH Cl /5%-MeOH. The
product was further purified by PLC with 1:2 n-hexane/CH Cl . The
olive-green band at the bottom of the plate was pure H [H Me (5-
OH)]. Yield: 5.6 mg, 48%. UV–vis (CH Cl ): λmax, nm (ε × 10
cm ): 439 (0.69), 689 (0.15). 1H NMR (C
, 600 MHz, δ in
ppm): δ 8.22 (d, J = 7.8 Hz, 2H, 5-o, 4-CH Ph), 7.07 (d, J = 7.2 Hz, 2H,
3-o, Ph), 7.04 (d, J = 8.1 Hz, 2H, 5-m, 4-CH Ph), 7.03 (o, 7-o, Ph), 7.0
(b, 1H, 10-o, 4-CH Ph), 6.94 (d, J = 7.2 Hz, 2H, 2-o, Ph), 6.94 (o, 7-p,
2
O and
3
UV–vis (CH
2
Cl
2
): λmax, nm (ε × 10−4, M−1 cm−1): 435 (4.19), 683
, 600 MHz, δ in ppm): δ 7.95 (d, J = 8.0 Hz, 2H,
Ph), 7.22 (d, J = 8.0 Hz, 1H, 7-m, 4-CF Ph), 7.05 (d, J =
.0 Hz, 2H, 3-m, 4-CF Ph), 7.03 (d, J = 8.1 Hz, 2H, 5-m, 4-CH Ph), 6.87
Ph), 6.75 (d, J = 8.4 Hz, 1H, 7-m, 4-
3
.
1
(
0.92). H NMR (C
6
D
6
3
5
8
-o, 4-CH
3
3
2
4
,
3
3
(
d, J = 7.9 Hz, 2H, 3-o, 4-CF
CF Ph), 6.72 (d, J = 8.0 Hz, 1H, 7-o, 4-CF
CH Ph), 6.61 (d, J = 8.6 Hz, 1H, 8-m, 4-CF
CF Ph), 6.61 (o, 1H, 15-m, 4-CH
H, 2-o, 4-CF Ph), 6.57 (o, 1H, 15-m, 4-CH
H, 8-m, 4-CF Ph), 6.44 (d, J = 8.4 Hz, 1H, 7-o, 4-CF
H, 15-o, 4-CH Ph), 6.35 (d, J = 8.6 Hz, 1H, 8-o, 4-CF
5-o, 4-CH Ph), 6.17 (d, J = 7.9 Hz, 1H, 10-m, 4-CH
.2 Hz, 1H, 8-o, 4-CF
d, J = 7.8 Hz, 1H, 10-m, 4-CH
H, –OH), 1.86 (s, 3H, 15-p, 4-CH
NMR (C 6, 60 °C): δ −62.58 (s, 3F), −62.72 (s, 9F), −62.88 (s, 3F), −
2.95 (s, 3F), −63.06 (s, 3F), −63.32 (s, 3F). MS (HR-ESI, major
3
2
2
3
3
Ph), 6.68 (o, 1H, 10-o, 4-
Ph), 6.61 (o, 2H, 12-m, 4-
2
2
3
3
2
8
3
−
4
3
3
Ph), 6.6 (o, 2H, 2-m, 4-CF
Ph), 6.53 (d, J = 8.2 Hz,
Ph), 6.37 (broad,
3
Ph), 6.6 (o,
2
2
,
−
1
−1
2
1
1
1
8
3
3
M
6 6
D
3
3
3
3
3
Ph), 6.26 (b, 1H,
Ph), 6.13 (d, J =
3
3
3
3
3
Ph), 5.93 (d, J = 7.8 Hz, 1H, 10-o, 4-CH
Ph), 2.07 (s, 3H, 5-p, 4-CH Ph), 1.97 (s,
Ph), 1.68 (s, 3H, 10-p, 4-CH
Ph). 19
3
Ph), 5.48
Ph), 6.86 (t, J = 7.5 Hz, 2H, 3-m, Ph), 6.81 (d, J = 7.2 Hz, 1H, 3-p, Ph),
6.77 (o, 7-m, Ph), 6.73 (o, 7-m, Ph), 6.66 (o, 7-o, Ph), 6.56 (t, J =
(
1
3
3
3
3
F
6.8 Hz, 2H, 2-m, Ph), 6.56 (o, 15-o, 4-CH
(12-m, Ph), 6.48 (o, 15-m, 4-CH Ph), 6.43 (o, 8-m, Ph), 6.37 (b, 1H,
10-m, 4-CH Ph), 6.23 (b, 1H, 10-o, 4-CH Ph), 5.56 (b, 1H, 10-m, 4-
CH Ph), 2.52 (s, 1H, –OH), 2.08 (s, 3H, 5-p, 4-CH Ph), 1.82 (s, 3H, 15-
p, 4-CH Ph), 1.68 (s, 3H, 10-p, 4-CH Ph). MS (HR-ESI major
isotopomer): [M + H] = 1193.5179 (expt), 1193.5153 (calcd).
3
Ph), 6.55 (o, 8-m, Ph), 6.51
6
D
3
6
3
3
+
isotopomer): [M + H] = 1738.4250 (expt), 1738.4177 (calcd).
3
3
3
3
+
4
.10. Undecaarylisocorrole H [(CF Me (10-OH)]
2
3
)
8
3
UV–vis (CH
0.26). H NMR (C
2
Cl
2
): λmax, nm (ε × 10−4, M−1 cm−1): 458 (1.86), 658
, 600 MHz, δ in ppm): δ 7.46 (d, J = 8.3 Hz, 2H,
Ph), 6.95 (d, J = 8.1 Hz, 4H, 12-m, 4-CF Ph), 6.80 (d, J =
.2 Hz, 4H, 18-m, 4-CF Ph), 6.77 (d, J = 8.1 Hz, 2H, 10-m, 4-CH Ph),
.72 (d, J = 8.3 Hz, 4H, 18-o, 4-CF Ph), 6.68 (d, J = 8.0 Hz, 4H, 17-m,
-CF Ph), 6.68 (b, 12-o, 4-CF Ph), 6.62 (d, J = 8.0 Hz, 4H, 13-m, 4-
Ph), 6.40 (d, J = 7.9 Hz, 4H, 17-o, 4-CF Ph), 6.30 (d, J = 8.0 Hz, 4H,
3-o, 4-CF Ph), 6.28 (d, J = 7.9 Hz, 4H, 15-o, 4-CH Ph), 5.86 (d, J =
.8 Hz, 4H, 15-m, 4-CH Ph), 2.39 (s, 1H, –OH), 1.98 (s, 3H, 10-p, 4-
Ph), 1.80 (s, 6H, 5.15-p, 4-CH ): δ −63.06 (s,
Ph). 19F NMR (CDCl
F), −63.15 (s, 6F), −63.19 (s, 6F), −63.54 (s, 6F). MS (HR-ESI, major
1
(
6
D
6
2 3 8 3
4.13. Undecaarylisocorrole H [(CF ) H (5-OH)]
1
8
6
4
CF
1
7
0-o, 4-CH
3
3
3
3
To a solution of Cu[(CF
(7.0 mL) was added dropwise 1 mL H
suspension was stirred for 30 min. The mixture was poured into cold,
distilled water and extracted with CH Cl . The green organic phase
was washed once with distilled H O and once with saturated aqueous
NaHCO , dried with anhydrous Na SO , and filtered. After concentration
to a minimum volume, the organic phase was chromatographed on a
silica gel column with 1:1 hexane/CH Cl , whereupon the isocorrole iso-
mers eluted as a green band. PLC with 3:2 hexane/CH Cl yielded the 5-
OH-isocorrole (17 mg, 0.01, 71.6%) as the first intense green band. Free
base H [(CF ] (1.8 mg, 7%) followed as a second, thinner green
3
)
8
H
3
] (25 mg, 0.014 mmol) in CH
2 2
Cl
3
2
SO (95–97%) and the resulting
4
3
3
3
3
2
2
3
3
2
3
3
2
4
CH
6
3
3
3
2
2
+
isotopomer): [M + H] = 1738.4135 (expt), 1738.4177 (calcd).
2
2
4
.11. Single-crystal X-ray diffraction analysis of undecaarylisocorrole
[(CF Me (5-OH)]
3
3 8 3
) H
H
2
)
3 8
3
band, closely followed by a third, bright green band containing the 10-
OH-isocorrole (2.5 mg, 11%). The latter two products were not fully
characterized because of the small quantities obtained so analytical
X-ray data for H
2 3 8 3
[(CF ) Me (5-OH)] were collected on beamline
1
1.3.1 at the Advanced Light Source, Lawrence Berkeley National Labo-
data are only reported for the 5-OH isomer. UV–Vis (CH
2
Cl
nm (ε × 10 , M cm ): 433 (4.30), 681 (0.98). H NMR (C
8.0 (d, 2H, 5-o, Ph), 7.20 (m, 1H, 7-m, 4-CF Ph), 7.15 (t, 2H, 5-m, Ph);
7.05–7.0 (m, 3H, 5-p, Ph and 3-m, 4-CF Ph), 6.82 (d, 2H, 3-o, 4-CF Ph),
6.75 (d, 1H, 10-o, Ph), 6.75–6.56 {m, 7-m (1H, 4-CF Ph), 2-o, m (4H,
4-CF Ph), 8-m (1H, 4-CF Ph), 7-o (1H, 4-CF Ph), 15-m (2H, Ph)}, 6.54
(d, 1H, 8-m, 4-CF Ph), 6.42 (d, 1H, 7-o, 4-CF Ph), 6.40–6.25 {m, 15-p
(1H, Ph), 10-m (1H, Ph), 8-o (2H, 4-CF Ph), 15-o (2H, Ph)}, 6.20 (t,
1H, 10-p, Ph), 6.10 (d, 1H, 8-o, 4-CF Ph), 6.0 (d, 1H, 10-o, Ph), 5.65 (t,
): δ −− 62.88 (s, 3F), −63.02 (s, 3F), −
2
): λmax
,
−
4
−1
−1
1
ratory. Samples were mounted on MiTeGen® kapton loops and placed
in a 100(2) K nitrogen cold stream provided by an Oxford Cryostream
7
D8 diffractometer equipped with a APEX-II CCD detector. Diffraction
data were collected with synchrotron radiation monochromated using
silicon(111) to a wavelength of 0.7749(1)Å. An approximate full-
sphere of data was collected using a ω scans with scan rates of 3 s per
6 6
D ): δ
3
00 Plus low temperature apparatus on the goniometer head of a Bruker
3
3
3
3
3
3
3
3
3
0
.5° with 2θ = −36°. The structures were solved by intrinsic phasing
3
2
19
(
2
SHELXT) and refined by full-matrix least squares on F (SHELXL-
014). All non-hydrogen atoms were refined anisotropically. Hydrogen
6 6
1H, 10-m, Ph). F NMR (C D
63.41 to −63.46 (m, 3F), −63.48 (s, 6F), −63.53 (s, 3F), −63.61 (s,
+
atoms were geometrically calculated and refined as riding atoms. The
hydrogen atoms on the nitrogen and oxygen atoms were found in the
Fourier difference map and allowed to ride on their respective N or O
3F), −63.71 to −63.76 (m, 3F). HRMS (ESI , major isotopomer):
+
[M + H] = 1696.3692 (expt), 1696.3708 (calcd). Elemental analysis.
Found (calcd): C, 65.86 (65.88); H, 3.20 (2.97), N, 3.27 (3.30).
Please cite this article as: J. Capar, et al., Demetalation of copper undecaarylcorroles: Molecular structures of a free-base undecaarylisocorrole and
a gold undecaarylcorrole, J. Inorg. Biochem. (2016), http://dx.doi.org/10.1016/j.jinorgbio.2016.06.026

8
J. Capar et al. / Journal of Inorganic Biochemistry xxx (2016) xxx–xxx
4
.14. Synthesis of gold β-octakis(p-trifluoromethylphenyl)-meso-
Appendix A. Supplementary data
3 8 3
triphenylcorrole, Au[(CF ) H ]
1
UV–vis, H NMR, and high-resolution mass spectra (42 pages); crys-
tallographic information files for [(CF Me (5-OH)] and
Au[(CF ]. Supplementary data associated with this article can be
found in the online version, at [http://dx.doi.org/10.1016/j.jinorgbio.
2016.06.026].
Gold(III) acetate (11 mg, 5 equiv) was added to a green solution of a
mixture of the isomeric isocorroles H [(CF (5/10-OH)] (15 mg,
.009 mmol) in pyridine (5.0 mL). After overnight stirring, the resulting
reddish-brown suspension was evaporated and the residue
chromatographed on a silica gel column with 7:3 hexane/CH Cl , yield-
ing the gold undecaarylcorrole as the first red band (7 mg, 41.5%). Va-
pour diffusion of hexane into a CH Cl solution yielded tiny
rectangular needles of x-ray quality in approximately a month. UV–Vis
H
2
3
)
8
3
2
3
)
8
H
3
3 8 3
) H
0
2
2
References
2
2
[
1] For a review on applications of corroles, see: I. Aviv-Harel, Z. Gross, Chem. Eur. J. 15
2009) 8382–8394.
[2] K.E. Thomas, A.B. Alemayehu, J. Conradie, C.M. Beavers, A. Ghosh, Acc. Chem. Res. 45
2012) 1203–1214.
(
−
4
−1
−1
(
CH
2
Cl
80 (2.0). H NMR (600 MHz, (CDCl
,18-o,4-CF Ph), 7.15 (d, 4H, 5, 15-o, Ph), 7.09 (d, 2H, 10-o, Ph), 7.05
Ph), 7.02 (d, J = 8.1 Hz, 4H, 2,18-m, 4-
Ph), 6.96 (d, J = 7.9 Hz, 4H, 3,17-m, 4-CF Ph), 6.93–6.89 (m, 8H, 7,
, 12,13-m, 4-CF Ph), 6.87 (d, J = 8.0 Hz, 4H, 7,13-o, 4-CF Ph), 6.82 (d,
J = 7.9 Hz, 4H, 8,12-o, 4-CF Ph), 6.74 (t, J = 7.7 Hz, 2H, 5,15-p, Ph),
2
): λmax, nm (ε × 10 , M
cm ): 434 (6.08), 544 (0.58).
1
(
5
2
2 2
)
): δ 7.29 (d, J = 8.2 Hz, 4H,
[
3] J.H. Palmer, Struct. Bond. 142 (2012) 49–89.
3
[
4] H.L. Buckley, J. Arnold, Dalton Trans. 44 (2015) 30–36.
(
d, J = 8.1 Hz, 4H, 3,17-o, 4-CF
3
[5] C. Capar, K.E. Thomas, A. Ghosh, J. Porphyrins Phthalocyanines 12 (2008) 964–967.
[
6] F. Mandoj, S. Nardis, G. Pomarico, R. Paolesse, J. Porphyrins Phthalocyanines 12
CF
3
3
(2008) 19–26.
8
3
3
[
7] H.Y. Liu, L. Chen, F. Yam, H.Y. Zhan, X. Ying, X.L. Wang, H.F. Jiang, C.K. Chang, Chin.
3
Chem. Lett. 19 (2008) 1000–1003.
6
6
1
.65 (t, J = 7.6 Hz, 1H, 10-p, Ph), 6.49 (t, J = 7.7 Hz, 4H, 5,15-m, Ph),
[8] T.H. Ngo, W. Van Rossom, W. Dehaen, W. Maes, Org. Biomol. Chem. 7 (2009) 439–443.
[9] C. Capar, L.-K. Hansen, J. Conradie, A. Ghosh, J. Porphyrins Phthalocyanines 14
.41 (t, J = 7.7 Hz, 2H, 10-m, Ph). 1 F NMR (CDCl
9
3
): δ − 63.31 (s,
(
2010) 509–512.
10] J. Capar, J. Conradie, C.M. Beavers, A. Ghosh, J. Phys. Chem. A 119 (2015) 3452–3457.
[11] J. Capar, S. Berg, K.E. Thomas, C.M. Beavers, K.J. Gagnon, A. Ghosh, J. Inorg. Biochem.
53 (2015) 162–166.
+
2F); −63.42 (s, 6F); −63.49 (s, 6F). HRMS (ESI , major isotopomer):
[
+
[
M] = 1873.3112 (expt), 1873.3110 (calcd). Elemental analysis.
1
Found (calcd): C, 59.90 (59.63); H, 2.77 (2.53), N, 3.11 (2.99).
[
[
[
12] A. Alemayehu, A. Ghosh, J. Porphyrins Phthalocyanines 15 (2011) 106–110.
13] E. Rabinovitch, I. Goldberg, Z. Gross, Chem. Eur. J. 17 (2011) 12294–12301.
14] A.M. Albrett, K.E. Thomas, S. Maslek, A. Młodzianowska, J. Conradie, C.M. Beavers, A.
Ghosh, P.J. Brothers, Inorg. Chem. 53 (2014) 5486–5493.
[15] S. Berg, K.E. Thomas, C.M. Beavers, A. Ghosh, Inorg. Chem. 51 (2012) 9911–9916.
16] D. Gao, G. Canard, M. Giorgi, T.S. Balaban, Eur. J. Inorg. Chem. (2012) 5915–5920.
4
.15. Single-crystal X-ray diffraction analysis of the gold undecaarylcorrole
Au[(CF
3 8 3
) H ]
[
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(
FRINATEK project 231086, AG) and the Advanced Light Source,
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Please cite this article as: J. Capar, et al., Demetalation of copper undecaarylcorroles: Molecular structures of a free-base undecaarylisocorrole and
a gold undecaarylcorrole, J. Inorg. Biochem. (2016), http://dx.doi.org/10.1016/j.jinorgbio.2016.06.026