Clean Ar-Me conversion to Ar-aldehyde with the aid of carefully designed metallocorrole photocatalysts

Article abstract of DOI:10.1039/d0pp00218f

Toluene, p-xylene and mesitylene were cleanly converted to their corresponding monoaldehydes via mild photooxygenation utilizing transition metal and main group β-CF3-substituted corroles. Aldehyde yield increased as more electron-donating CH3 groups are present on the substrate. 4-P was most efficient (TON ～ 1072, mesitylene) via the singlet oxygen vis the superoxide mechanism.

Full text of DOI:10.1039/d0pp00218f

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Kolanu, S. Fite, Q. Chen, W. Lee, D. G. Churchill and Z. Gross, Photochem. Photobiol. Sci., 2020, DOI:
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DOI: 10.1039/D0PP00218F
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Clean Ar–Me conversion to Ar–aldehyde with the aid of carefully
designed metallocorrole photocatalysts
Xuan Zhana, Kolanu Sudhakara, Shachar Fitea, Qiu–Cheng Chena, Woohyun Leeb, David G.
+Received 00th January 20xx,
Accepted 00th January 20xx
Churchilla,b,c,d* and Zeev Grossa*
DOI: 10.1039/x0xx00000x
Toluene, p–xylene and mesitylene were cleanly converted to their particularly appealing due to its strong electronic effect and
corresponding monoaldehydes via mild photooxygenation utilizing limited steric effects.5 The presence of fluorine, being the most
transition metal and main group β–CF3–substituted corroles. electronegative element, easily alters the electronic properties
Aldehyde yield increased as more electron–donating CH3 groups of molecules, e.g. affecting the basicity/acidity of neighboring
are present on the substrate. 4–P was most efficient (TON ~1072, groups, the dipole moment and overall reactivity, stability and
mesitylene) via the singlet oxygen vis the superoxide mechanism.
photophysical properties.6 Therefore, the formal replacement
of H for F, or CH3 for CF3 etc, plays an important part in
contemporary substituent chemistry; in fact, the most
intensively studied corroles have C6F5 groups present in the 5,
10, and 15 positions. The successful preparation of some
metallocorroles appropriate for photosensitization revealed
that the CF3 effects imparted to the redox properties are
intriguing indeed.7a β–CF3–substituted gold corroles for
example have been reported by our group; the CF3 groups
influence the photophysical and redox properties noticeably.7b
Herein, the goal of our present work was to explore
Synthetic methodologies to access functionalized corrole
complexes (e.g., β–substitution) continue to be explored.1
Porphyrinoid and chromophore/fluorophore researchers
expand the potential applications of substituted corroles as
photosensitizers in energy–related catalysis and preparative
organic chemistry. Recently, Dorota Gryko’s group reported
that porphyrins can be used for photocatalytic C–C bond
formation and C–H activation reactions.2 We are seeking yet
unidentified corrole complexes that could surpass present
candidates in the artificial photosynthesis/health sciences
fields. One specific aim is to determine which important C–X
transformations may be achieved under mild and ambient
conditions.3 To reach a more thorough scientific understanding
of corrole theory and applications, new discretely β-
functionalized compound classes are being explored and
studied in the context of photosynthesis, photolysis,
photosensitization etc.
photooxidation
reactions
of
newly–synthesized
β–
trifluoromethylated metallocorroles.7–8
Our previous work reported the photo–bromination of
selected aromatics such as phenol, toluene and benzene using
corroles as the photocatalysts (photosensitizers).7-8 These
studies enlightened us to explore other reactions such as the
oxygenation of aromatic alkanes to the corresponding
aldehydes, important precursors in organic synthesis.9 The
photo–oxygenation of toluene to benzaldehyde was reported
with specific materials serving as the catalyst10 such as V–Sb
oxide, V/Al2O3–TiO2, CdS and tungsten oxide. However, studies
of homogeneous systems are scarce. Fukuzumi et al. made
noteworthy progress on the topic of the photocatalytic
oxygenation of aromatic alkane compounds.11 For example, the
oxygenation of p–xylene to p–tolualdehyde and p–
methylbenzyl alcohol was made possible by using 9–mesityl–
10–methylacridinium ion (Acr+–Mes);11d and the oxygenation
mechanism of this photocatalyst was thoroughly studied in
their work.11d This enlightened us about the possibility of
checking these types of reactions with CF3–functionalized
corroles. The photo–oxidation studies here include the
oxygenations of toluene, p–xylene and mesitylene to their
In 2015, we reported metallocorroles as photocatalysts in
promoting facile bromide–to–bromine conversion under mild
conditions.4 We found that tuning the HOMO and LUMO gap is
a
very important factor in predicting photocatalytic
performance. Corrole trifluoromethyl-substitution is
a. Schulich Faculty of Chemistry, Technion-Israel Institute of Technology, Haifa
32000 (Israel). E-mail: chr10zg@technion.ac.il.
b. Department of Chemistry Korea Advanced Institute of Science and Technology
(KAIST) Daejeon (Republic of Korea) E-mail: david.churchill.korea@gmail.com.
c. Center for Catalytic Hydrocarbon Functionalizations, Institute for Basic Science
(IBS), Daejeon (Republic of Korea).
d. KAIST Institute for Health Science and Technology (KIHST) (Therapeutic
Bioengineering Section), 291 Daehak–ro, Yuseong–gu, Daejeon 34141,(Republic
of Korea).
† Electronic Supplementary Information (ESI) available: Experimental details, Tables
and supporting Figures. See DOI: 10.1039/x0xx00000x
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corresponding aldehydes, i.e., benzaldehyde, p–tolualdehyde, photocatalysts with toluene as a substrate was determined to
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and 3,5–dimethylbenzaldehyde. The catalytic performance be as follows: 4–P (248) >> 4–Ga (70) > 3–DPO(I5:010).>1043–9/ADl0(P4P30)0=2138–F
among the compounds was successfully tuned by formal Al (43) > 4–Au (38) > 3–Au (30) > 3–Ga (27) > 3–Co (5). Still, the
substitution at both (i) the central element chelated by the highest yield of 3.9% underscores the general difficulty of
corrole and (ii) introduction of 3 or 4 –CF3 groups at the β– achieving this photocatalytic conversion. Taking advantage of
pyrrolyl positions.
C6F5
Substrate
N
N
N
N
M
C6F5
X
C6F5
X
toluene
mesitylene
p-xylene
Y
X
3-Ga
: X = CF3, Y = H, M = Ga
4-Ga
: X = Y= CF3, M = Ga
3-Al
3-Au
: X = CF3, Y = H, M = Al
4-Al
4-Au
: X = Y= CF3, M = Al
: X = CF3, Y = H, M = Au
: X = CF3, Y = H, M = P
: X = Y= CF3, M = Au
: X = Y= CF3, M = P
4-P
3-P
3-Co
: X = CF3, Y = H, M = Co
Scheme 1. The chemical structures of the nine metallocorroles used for catalyzing the
photo-aerobic oxidation of the substrates investigated in this study (axial ligands in the
drawings have been omitted for clarity).
The investigated compounds are shown in Scheme 1 and may
be classified into two categories of β–functionalized corroles:
tris–CF3 substituted E(tpfc)(CF3)3 (E = Ga, Al, P, Au, Co) and
tetra–CF3 substituted E(tpfc)(CF3)4 (E = Ga, Al, P, Au). The details
for preparing these CF3–substituted complexes are available by
way of our previous literature reports.7–8 Notice here that,
except for the cobalt complex, the other corrole complexes
exhibit fluorescence (or phosphorescence as in the case of 3-Au
and 4-Au).
Figure 1. General procedure: acetonitrile solution (5 mL) charged with photocatalyst (15
µM, 0.015%), substrate (0.1 M), TFA (78 µL, 0.20 M)) under LED irradiation (λmax = 400
nm, 400±5 nm) for 20 h. (a) Metallocorrole–catalyzed oxygenation of toluene to
benzaldehyde (TON values shown); (b) Metallocorrole–catalyzed oxygenation of p–
xylene into p–tolualdehyde (TON values shown); c) Metallocorrole–catalyzed
oxygenation of mesitylene into 3,5–dimethylbenzaldehyde (TON values shown); the
turnover number (TON = the sum of moles of product divided by the moles of
photocatalyst used). All values of TON were measured three times and the average value
is reported; (d) Absorbance values at 400 nm with the same concentration of 5.0 × 10–6
M and the 1st oxidation potentials for all corrole complexes studied here (glassy carbon
working electrode, a platinum wire counter–electrode, Ag/AgNO3 as the reference
electrode, in acetonitrile with TBAP, scan rate of 100 mV s–1 was applied).
The photooxidations of toluene, p–xylene and mesitylene
were performed in acetonitrile containing trifluoroacetic acid
(TFA), substrate (0.10 M) and photocatalyst (15 µM, 0.015
mol%). Conversion to their corresponding aldehydes was
examined (Table S1, Figure 1) after irradiation for 20 h; product
formation and conversion efficiency was tested for the nine
metallocorroles. While each showed a different photocatalytic
efficiency for these conversions, compound formation was
uniform (Table S1, Figure 1). Rather than a range of products
being generated, as reported by the Fukuzumi group for the
Acr+–Mes system,11 only aldehyde was obtained through our
oxygenation assays, as determined by GC analysis (Figures S1-
S3). NMR spectroscopic evidence also supported the selective
formation of the targeted aldehydes, i.e. benzaldehyde, p–
tolualdehyde, and 3,5–dimethylbenzaldehyde (Figures S4–S6):
each of these products displays one characteristic singlet at ~10
ppm corresponding to the –CHO proton. The product yields
increased as more electron donating CH3 groups were present
on the benzene ring of the substrate; thus, the ease with which
oxygenation is imparted to these substrates is shown to be in
this order: toluene < p–xylene < mesitylene, as confirmed by the
catalytic performance (TON and yield: detailed values are
shown in Table S1). Another possible consideration for this
increase in reactivity is a statistical effect based on the greater
overall number of methyl groups per substituent and which can
collide with the photosensitizer or oxidant. The catalytic
efficiency (TON in parentheses) determined for these
the CH3–directing group, the p–xylene assay was then
conducted. The highest product yield was 8.2%, with 4–P as
photocatalyst; the catalytic efficiencies (TON) were also
determined: 4–P (536) >> 3–Au (286) > 4–Au (266) > 3–P (198)
> 3–Al (117) > 4–Al (99) > 4–Ga (72) > 3–Ga (47) >> 3–Co (9).
This general improvement of catalytic performance inspired us
to perform oxygenation trials for mesitylene: similar orders of
catalytic efficiency (TON) were determined here as well: 4–P
(1072) > 3–Au (606) > 4–Au (549) > 3–P (397) ≈ 4–Ga (388) > 3–
Ga (247) > 3–Al (84) > 4–Al (80) >> 3–Co (6). A much higher yield
of 3,5–trimethylbenzaldehyde (17.2 %) was obtained when 4–P
was used; this photocatalyst outperforms all other complexes
in all aldehyde conversions. Additional optimization involved a
time–dependent formation experiment using 4–P as the
catalyst; the formation of different types of aldehydes was
examined with a time delay of 30 h, leading to higher yields:
4.6% for benzaldehyde, 10.2% for p–tolualdehyde, and 20.2%
for 3,5–dimethylbenzaldehyde (Fig. 2).
The oxygenation reactions were performed with the aid of
different catalysts. The different central element, as well as the
conditions, resulted in changes upon various experiments which
helped establish the chemical mechanism(s) at play based on
the photochemical conditions. Control experiments were
2 | J. Name., 2012, 00, 1-3
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performed (Table S2) and demonstrated that the photocatalytic method, as monitored by UV–vis spectroscopy (e.gV.i4ew–PAr,ticFliegO3ndlin)e.
oxygenation reactions strictly required oxygen, acid conditions, This, in turn, implied the participatiDoOnI: 1o0f.10a39/sDu0pPePr0o0x2i1d8eF
the presence of a photosensitizer as the photocatalyst, and light mechanism. The existence of a superoxide mechanism can be
energy. The optimization of catalyst 4-P loading was suggested by results found from the use of Tiron™; decreases in
investigated and revealed the concentration of 15 µM was the 3,5–dimethylbenzaldehyde generation were observed with
ideal choice. A comparison to other acids like acetic and sulfuric various catalysts: (i) from 17.2 % to 14.7 %, (ii) from 6.2 % to 5.2
acid, TFA showed better performance in our photo-catalytic %, (iii) from 1.3 % to 1.0 % for catalysts 4–P, 4–Ga and 4–Al,
oxidation reactions as show in Table S3. The stability of our respectively. However, a more dramatic decrease in yield was
catalysts was also checked exemplified by the one photo- observed in the case of catalyst 4–Au: from 8.8 % to 3.8 %. The
oxidation reaction of toluene for 24 hours with 4-P as the addition of the H2O2 scavenger–tmtu (0.1 M) also induced a
catalyst; it displayed good stability (Fig S9). Reactive oxygen decrease in yield when 4–Au was used as the catalyst (8.8 % to
species are expected to mediate the mechanism. Our recent 4.3 %). On the other hand, only a slight inhibition was found in
publication
the presence of 4–P/Ga/Al catalyst: (i) from 17.2 % to 16.4 %,
(ii) from 6.2 % to 6.0 % and (iii) from 1.3 % to 1.2 %, respectively.
Another important control involved using H2O2 without catalyst
to oxidize p–xylene performed under irradiation for 2 h to
produce p–tolualdehyde efficiently (around 4% yield); no
reaction occurred under dark conditions (Table S2, entries 26 &
27). Fukuzumi and coworkers reported that both p-
methylbenzyl alcohol and p–tolualdehyde formed when they
conducted the photo-oxygenation of p-xylene by their ionic
catalyst; and the p-methylbenzyl alcohol would convert into p–
tolualdehyde efficiently under the irradiation and aerobic
conditions. Similarily, we observed full conversion into
benzaldehyde when treating benzyl alcohol (52 µL, 0.1 M ) with
TFA (39 µL, 0.1 M) under LED irradiation (λmax = 400 nm, 400 ± 5
nm) for 2 h under air in the absence of catalyst, suggesting
benzyl alcohol may be generated in situ.
Seeking to increase yields in these photocatalysis trials in
the future might include (further) adjusting parameters such as
temperature, solvent and solvent purity, choice of additive,
further corrole photocatalyst derivatization, reaction time,
irradiation energy, nature of oxidant intermediate, as well as
adjusting certain hard-wired aspects regarding the
experimental set-up.
Benzaldehyde
p-tolualdehyde
3,5-dimethylbenzaldehyde
20
15
10
5
0
0
5
10
15
20
25
30
Time / h
Figure 2. Time–dependent formation of aldehydes in the presence of 15 µM 4–P, 0.10 M
substrate (toluene: 54 µL; p–xylene: 62 µL; mesitylene: 68 µL) and 0.20 M TFA (78 µL).
pointed out that the photo–generated singlet oxygen (1O2) and
superoxide (O2 ) radical formed and competed under
–
irradiation in the presence of fluorescent phosphorus
corroles.12 The mesitylene assays were tested with different
scavengers:13 NaN3 for singlet oxygen; disodium 4,5–dihydroxy–
1,3–benzenedisulfonate
(Tiron™)
for
superoxide;
tetramethylthiourea (tmtu) for hydrogen peroxide. These were
used to gain deeper insights into the photochemical
mechanism. The formation of 3,5–dimethylbenzaldehyde was
inhibited when the sample contained 0.1 M NaN3; the yields
decreased (i) from 17.2% to 9.3%, (ii) from 6.2% to 1.2, (iii) from
1.3% to 0.3% and (iv) from 8.8% to 6.1% in the presence of 4–P,
4–Ga, 4–Al and 4–Au, respectively (Table S2). This finding
indicated that singlet oxygen concentration constitutes a
significant part of the chemical oxidant generated during
reaction and used in creating aldehyde based on the presence
of P, Ga and Al-containing catalysts. The effect of quenching
singlet oxygen (NaN3) upon addition of increasing concentration
was demonstrated with 4–P (Fig 3c). The yield of 3,5–
dimethylbenzaldehyde reduced to 4.0 % when [NaN3] was
treated at 1.0 M, indicating the predominance of a singlet
oxygen mechanism. Hydrogen peroxide was detected in all
Figure 3. Yields of 3,5-dimethylbenzaldehyde produced by using either 4-P (a) or
4-Au (b) as catalyst and employing the normal procedure: a 5 mL acetonitrile vial
containing 15 µM (0.015 mol%) cat, 68 µL (0.10 M) mesitylene inside and 78 µL
TFA (0.20 M) under irradiation for 20 h, the yield was checked by GC (nitrobenzene
as the internal standard) (A), and by introducing the following changes: omitting
light (B); omitting acid (C); omitting oxygen (D); omitting catalyst (E); adding NaN3
(0.10 M) before irradiation (F); adding tiron (0.10 M) before irradiation (G); adding
tmtu (0.10 M) before irradiation; (c) influence of the concentration of NaN3 on the
–
oxygenation assays in the presence of all catalysts by the I–/I3
This journal is © The Royal Society of Chemistry 20xx
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–
yield of 3,5–dimethylbenzaldehyde with 4–P as catalyst; (d) The UV-vis I–/I3
method for checking H2O2 (4-P (15 µM) + mesitylene (68 µL, 0.1 M) + TFA (78 µL,
0.2 M) in 5 mL MeCN, irradiation for 12 hours (LED, 400 nm). 20 µL was extracted
from the reaction mixture and added into a 3 mL cuvette charged with
acetonitrile; the UV-vis spectra was checked before and after 10 mg TBAI addition
into this cuvette.)
4
5
A. Mahammed, Z. Gross, Metallocorroles as Photocatalysts
View Article Online
for Driving Endergonic Reactions, Exemplified by Bromide to
DOI: 10.1039/D0PP00218F
Bromine Conversion. Angew. Chem. Int. Ed., 2015, 127,
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In summary, we report
a range of novel multi β-
trifluoromethylated corrole complexes, both d–block and main
group species, as photocatalysts for the oxygenation of toluene,
p–xylene and mesitylene. Only corresponding aldehydes were
discovered as products. The substrate with additional methyl
groups experienced better photocatalytic conversion with the
highest yield (17.2%) observed in the case of mesitylene. The
non–metallic complex, 4–P, experimentally outperforms other
species among these photocatalysts; its 1st oxidation potential
and absorbance at the wavelength of the irradiation source
(LED: λmax = 400 nm, 400 ± 5 nm) are both found to be highest
among the catalysts tested herein; all photocatalytic
oxygenation reactions required oxygen, Brønsted–Lowry acid
conditions, a photosensitizer as the photocatalyst and a
working irradiation source. The photo–oxygenation mechanism
was strongly supported to be a leading singlet oxygen
mechanism with our P/Ga/Al corrole catalysts; the superoxide
mechanism predominated in the presence of Au catalysts. The
outstanding photocatalytic performance of this catalytic
combination will be helpful when seeking novel economical
photocatalysts for broad applications including solar energy as
well as biomedical applications.
6
7
Z. G. acknowledges the support of this research by a grant
from the Israel Science Foundation. D. G. C. acknowledges
Z. G., the Schulich Faculty of Chemistry, Technion-Israel
Institute of Technology, and support from KAIST for facilitating
his sabbatical year.
8
(a) K. Sudhakar, A. Mahammed, N. Fridman, Z. Gross,
Trifluoromethylation for affecting the structural, electronic
and redox properties of cobalt corroles, Dalton Trans., 2019,
48, 4798–4810; (b) X. Zhan, P. Yadav, Y. Diskin–Posner, N.
Fridman, M. Sundararajan, Z. Ullah, Q.-C. Chen, L. J. Shimon,
A. Mahammed, D. G.Churchill, M. Baik, Z. Gross, Positive
shift in corrole redox potentials leveraged by modest β-CF3-
substitution helps achieve efficient photocatalytic C–H bond
functionalization by group 13 complexes, Dalton Trans.,
2019, 48, 12279–12286; (c) X. Zhan, Yael Z, N. Fridman, Q.-C.
Chen, D. G. Churchill, Z, Gross, “
Conflicts of interest
There are no conflicts to declare.
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DOI: 10.1039/D0PP00218F
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Photochemical & Photobiological Sciences
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DOI: 10.1039/D0PP00218F
Graphical abstract
Mild photo-oxygenation of toluene derivatives with β–CF3–substituted corroles helped elucidate
formation rates and mechanisms (singlet oxygen-mediated vs the superoxide-mediated) of
corresponding aldehyde formation.

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Photochemical & Photobiological Sciences
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DOI: 10.1039/D0PP00218F