Dechlorination of DDT catalyzed by visible-light-driven system composed of vitamin B12 derivative and Rhodamine B

Article abstract of DOI:10.1142/S1088424612501398

The visible-light-driven dechlorination of 1,1-bis(4-chlorophenyl)-2,2,2- trichloroethane (DDT) was carried out in the presence of a hydrophobic vitamin B₁₂, heptamethyl cobyrinate perchlorate and Rhodamine B. DDT was successfully dechlorinated to form 1,1-bis(4-chlorophenyl)-2,2-dichloroethane (DDD) as the mono-dechlorinated product upon visible light irradiation with a tungsten lamp (λ > 440 nm). Upon prolonged visible light irradiation to DDT, DDMU (1-chloro-2,2-bis(4-chlorophenyl)ethylene), DDMS (1-chloro-2,2-bis(4-chlorophenyl)ethane) and DCS (trans-4,4′- dichlorostilbene) were obtained as the di- and tri-dechlorinated products. The use of the photostable organic sensitizer enabled prolonged photocatalysis via a noble-metal-free process. The vitamin B₁₂ derivative was replaced by an imine/oxime-type cobalt complex although the cobalt complex system showed a lower catalytic activity than the B₁₂ derivative system. The dechlorination mechanism in the B₁₂-Rhodamin B system was investigated by various methods such as UV-vis absorption and fluorescence quenching. Copyright

Full text of DOI:10.1142/S1088424612501398

Journal of Porphyrins and Phthalocyanines
J. Porphyrins Phthalocyanines 2013; 17: 135–141
DOI: 10.1142/S1088424612501398
Published at http://www.worldscinet.com/jpp/
Dechlorination of DDT catalyzed by visible-light-driven
system composed of vitamin B12 derivative and Rhodamine B
Keishiro Taharaa,b, Kumiko Mikuriyaa, Takahiro Masukoa, Jun-ichi Kikuchib and
Yoshio Hisaeda*a,c◊
a Department of Chemistry and Biochemistry, Graduate School of Engineering, Kyushu University,
Fukuoka 819-0395, Japan
b Graduate School of Materials Science, Nara Institute of Science and Technology, Ikoma 630-0192, Japan
c Center for Molecular Systems (CMS), Kyushu University, Fukuoka 819-0395, Japan
Received 18 October 2012
Accepted 2 November 2012
ABSTRACT: The visible-light-driven dechlorination of 1,1-bis(4-chlorophenyl)-2,2,2-trichloroethane
(DDT) was carried out in the presence of a hydrophobic vitamin B12, heptamethyl cobyrinate
perchlorate and Rhodamine B. DDT was successfully dechlorinated to form 1,1-bis(4-chlorophenyl)-
2,2-dichloroethane (DDD) as the mono-dechlorinated product upon visible light irradiation with a
tungsten lamp (l > 440 nm). Upon prolonged visible light irradiation to DDT, DDMU (1-chloro-2,2-
bis(4-chlorophenyl)ethylene), DDMS (1-chloro-2,2-bis(4-chlorophenyl)ethane) and DCS (trans-4,4′-
dichlorostilbene) were obtained as the di- and tri-dechlorinated products. The use of the photostable
organic sensitizer enabled prolonged photocatalysis via a noble-metal-free process. The vitamin B12
derivative was replaced by an imine/oxime-type cobalt complex although the cobalt complex system
showed a lower catalytic activity than the B12 derivative system. The dechlorination mechanism in the
B12-Rhodamin B system was investigated by various methods such as UV-vis absorption and fluorescence
quenching.
KEYWORDS: vitamin B12, Rhodamine B, organic photosensitizer, DDT, dechlorination, visible-light-
driven catalysis.
To meet the increasing demand for eco-friendly
catalytic processes, photocatalysis with visible light is
INTRODUCTION
Since a vitamin B12 derivative was isolated from
regarded as a promising method [12–14]. In this context,
an anaerobic microbe as a cofactor of a reductive
inorganic sensitizers, such as [Ru(bpy)3]2+ (bpy =
dehalogenase involved [1], vitamin B12 and derivatives
have received much attention from the viewpoint of
2,2′-bipyridine), have been combined with conventional
catalytic systems [15–19]. Moreover, readily available
remediation catalysts. Vitamin B12 and derivatives can
organic dyes have been used to overcome the high
acquire oxidation states Co(III), Co(II) or Co(I) [2–4], and
cost of the ruthenium complex [20–22]. We have been
the latter has been demonstrated to dehalogenate several
dealing with a hydrophobic vitamin B12, heptamethyl
halogenated pollutants utilizing its supernucleophilicity
cobyrinate perchlorate [Cob(II)7C1ester]ClO4 1 [23,
[5–11], in which an eco-friendly catalytic process is also
24], as shown in Chart 1 and succeeded in combining
required.
it with [Ru(bpy)3]2+ to develop visible-light-driven
dehalogenation systems [25–27]. Furthermore, we have
attempted to replace the ruthenium complex by a well-
SPP full member in good standing
known xanthene dye, Rose Bengal [28]. However, the
*Correspondence to: Yoshio Hisaeda, email: yhisatcm@mail.
previous B12 model complex-Rose Bengal system was
not applicable to prolonged photocatalysis due to the low
cstm.kyushu-u.ac.jp, tel: +81 92-802-2826, fax: +81 92-802-
2827
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136
K. TAHARA ET AL.
The GC-MS data were obtained using
a Shimadzu GC-QP5050A equipped
with a J&W Scientific DB-1 column
(length 30 m; ID 0.25 mm, film 0.25
μm). The quenching experiments of
the singlet excited state of Rhodamine
B 2 were performed using a Hitachi
F-4501 spectrofluorometer at 25 °C.
The fluorescence quenching of 2
by triethanolamine (TEOA) was
analyzed using the Stern–Volmer
plot [32].
Chart 1.
Photocatalysis
photostability of the organic dye. To achieve both a good
photostability and a noble-metal-free process, we herein
chose Rhodamine B 2 [29, 30] as a new sensitizer. Our
choice of 2 was based on its excellent photostability and
potential use as an electron mediator (E0(Rho/Rho●-) =
-0.8 V vs. SCE)) [20, 30], although the application of
2 to reductive organic transformations represents almost
unexplored research area. In this study, we demonstrate
that the present B12 model complex-Rhodamine B system
efficiently dechlorinates 1,1-bis(4-chlorophenyl)-2,2,2-
trichloroethane (DDT) and 1,1-bis(4-chlorophenyl)-
2,2-dichloroethane (DDD) via a visible-light-driven
process without noble metal complexes as sensitizers.
An imime/oxime-type cobalt complex was also used to
investigate appreciate reaction conditions for the efficient
dechlorination. Furthermore, we demonstrate that the use
of the photostable organic sensitizer enables prolonged
photocatalysis.
As a typical experiment of the photochemical
reduction of 1, the EtOH solution containing 1 (2.5
× 10-5 M), 2 (2.5 × 10-6 M) and TEOA (2.5 × 10-2 M)
was degassed for 10 min then irradiated with a 200 W
tungsten lamp with a cutoff filter (l > 440 nm). After
irradiation, the photochemical reaction was followed
by UV-vis spectroscopy. Reference experiments in the
absence of either TEOA, 2 or in the dark was performed
in the same manner.
As a typical experiment of the photocatalytic
dechlorination, the EtOH solution containing 1 (5.0 ×
10-4 M), 2 (5.0 × 10-5 M), TEOA (5.0 × 10-1 M) and DDT
(1.0 × 10-2 M) was degassed for 10 min. The solution
was stirred and irradiated with a 200 W tungsten lamp
with a cutoff filter (l > 440 nm) at ambient temperature
for 1 h. After irradiation, water was added to the reaction
solution and the products were extracted with diethylether
1
and hexane. The products were identified by H NMR
comparisons with the corresponding authentic samples
[33–35]. The authentic samples of DCS [7], DDMU
[33] and DDMS [36] were synthesized according to the
previously reported methods. The product yields were
quantified by 1H NMR comparisons with 1,4-dioxane as
the internal standard in the same manner as the previous
reports. The photocatalytic dechlorination was carried
out in EtOH-d6, the deuterium incorporation ratio in the
EXPERIMENTAL
Materials
All chemicals were of reagent grade and used as
received. Ethanol-d6 (C2D5OD) was purchased from
ISOTEC. DDT and DDD were purchased from TCI.
Heptamethyl cobyrinate perchlorate, [Cob(II)7C1ester]
(1) [23] and diaqua(11-hydroxyimino-4,10-dipropyl-
1
dechlorinated product was determined by H NMR and
GC-MS. The photocatalysis of DDD was performed in a
similar manner.
5,9-diazatrideca-4,9-dien-3-one
oximato)cobalt(II)
tetraphenylborate, [Co(II){(C2C3)(DO)(DOH)pn}]
B(C6H5)4 (3) [31] were synthesized by previously
RESULTS AND DISCUSSION
reported methods.
Photochemical reduction of vitamin B12 derivative
General analyses and measurements
We first attempted to activate 1 to the supernucleophilic
Co(I) species by a photocatalytic process. We chose
TEOA as an electron donor for the present B12-Rhodamine
B system. This is because TEOA has been widely used
as a sacrificial reducing agent for photocatalytic systems
[37, 38]. Indeed, it was demonstrated that Rhodamine B
was reductively quenched by tertiary amines [39]. The
UV-vis absorption spectrum of an EtOH solution of 1
The UV-vis absorption spectra were measured
using a Hitachi U-3300 spectrometer at room
1
temperature. The H NMR spectra were recorded by
a Bruker Avance 500 spectrometer installed at the
Center of Advanced Instrumental Analysis of Kyushu
University, and the chemical shifts (in ppm) were
referenced relative to the residual protic solvent peak.
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DECHLORINATION OF DDT CATALYZED BY VISIBLE-LIGHT-DRIVEN SYSTEM
137
containing 2 (0.1 equiv. Vs. 1) and TEOA is shown in
system [28], the color of the bleached solution of Rose
Bengal did not reappear upon exposure to air, indicating
the low photostability of Rose Bengal. In the present B12
model complex-Rhodamine B system, the Co(I) species
of 1 was observed again upon subsequent visible light
irradiation under an N2 atmosphere as shown in Fig. 2
(solid line). Therefore, the present B12 model complex-
Rhodamine B system can be applied to photocatalytic
reactions due to the good photoredox stability of 2.
Fig. 1 (broken line). This is simply the sum of 1 and
2, indicating no interaction between both compounds
in the ground state. Upon visible light irradiation (l >
440 nm), the characteristic strong absorption at 391 nm,
indicative of the Co(I) species of 1, was observed under
an N2 atmosphere as shown in Fig. 1 (solid line). Such
a spectral change was not observed in the absence of
TEOA, 2 or in the dark. This spectral change strongly
suggests that the compound 2 sensitizes the reduction of
1 with TEOA as an electron donor.
Catalytic dehalogenation of DDT and DDD
The photochemical reduction of 1 was accompanied
with the reductive bleaching of 2 as indicated by the
disappearance of the adsorption of 2 at 542 nm in Fig. 1
(solid line). However, when the bleached solution was
exposed to air, the absorption of 2 appeared again
as shown in Fig. 2 (broken line). This is due to the
oxygenation of the photoreduced species of 2. A similar
reversible behavior of 2 was also reported in a Rhodamine
B system containing Pt/TiO2 and oxalic acid [40]. In
contrast, in the previous B12 model complex-Rose Bengal
We then examined the dechlorination of DDT, a
well-known trihalomethane insecticide [41]. DDT was
successfully dechlorinated upon visible light irradiation for
2 h using 1 (5 mol.%), 2 (0.5 mol.%) and TEOA (50 equiv.)
in EtOH to form DDD as the major product as shown in
Entry 1 in Table 1. This dechlorination did not efficiently
proceed in the absence of either TEOA, 2 or in the dark as
shown in Entries 2–4 in Table 1. Accordingly, it is obvious
that compound 2sensitizes the B12-mediated dechlorination
with TEOA as an electron donor upon visible light
irradiation. Combined with the former spectroscopic study,
these results suggest that the generated Co(I) species of 1
is the active form of the dechlorination. When the reaction
was carried out in EtOH-d6, the deuterium incorporation
ratio in DDD was only 7%, which was determined by 1H
NMR and GC-MS. This result indirectly suggests that the
TEOA is likely the major hydrogen atom source of the
catalytic hydrodehalogenation.
We were able to replace 1 by an imime/oxime-
type cobalt complex, [Co(II){(C2C3)(DO)(DOH)pn}]
B(C6H5)4 3 (Chart 2) as shown in Entry 7 in Table 1.
However, the cobalt complex system showed a lower
catalytic activity than the B12 derivative system. The
solution of the cobalt complex was decolorized during
the course of the photochemical reaction, indicating the
low stability of 3. In contrast, the B12 model complex-
Rhodamine B system (Entry 1 in Table 1) maintained over
99% of the amount of 1 after the dechlorination of DDT,
which was determined by UV-vis spectrometric analyses.
Furthermore, the B12 model complex-Rhodamine B
system (Entry 1 in Table 1) showed a comparable activity
even upon the subsequent addition of DDT. These
results confirmed the good stability of 1 and 2 under the
photocatalytic condition (Entry 1 in Table 1). Actually,
the present B12 model complex-Rhodamine B system can
be used for the prolonged photocatalysis of DDT. Upon
prolonged visible light irradiation for 30 h, DCS (trans-
4,4’-dichlorostilbene), DDMU (1-chloro-2,2-bis(4-
chlorophenyl)ethylene) and DDMS (1-chloro-2,2-bis(4-
chlorophenyl)ethane) were obtained as the dechlorinated
products as shown in Entry 6 in Table 1. In this case,
DDD was not produced suggesting that all of the DDD
formed from DDT was converted into DCS, DDMU and/
or DDMS. It should be noted that the present B12 model
complex-Rhodamine B system can dechlorinate DDT to
Fig. 1. UV-vis spectra of EtOH solution containing 1 (2.5 × 10-5
M), 2 (2.5 × 10-6 M) and TEOA (2.5 × 10-2 M) before and after
visible light irradiation (l > 440 nm)
Fig. 2. UV-vis spectra of EtOH solution containing 1 (2.5 ×
10-5 M), 2 (2.5 × 10-6 M) and TEOA (2.5 × 10-2 M) (a) upon
exposure to air after visible light irradiation (broken line) and
(b) upon 2nd visible light irradiation under N2 atmosphere (l >
440 nm) (solid line)
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K. TAHARA ET AL.
Table 1. Catalytic dechlorination of DDT mediated by B12 model complex-Rhodamine B systema
Product yields, %c
Entry
Compound
Conversion, %b
DDD
DCS
DDMU
DDMS
TNd
1
2
3
4
5
6
7
8
1, 2
1, 2e
1, 2f
100
3
93
1
0
0
0
0
0
0
186
2
0
—
23
16
0
—
0
—
0
—
0
0
1
29
19
100
71
100
—
32
364
94
178
2
1, 2g
2, 3h
0
0
0
58
0
13
0
20
0
47
89
1, [Ru(bpy)3]2+ i
0
0
0
aConditions: [1] = 5.0 × 10-4 M, [2] = 5.0 × 10-5 M, [DDT] = 1.0 × 10-2 M, [TEOA] = 5.0 × 10-1 M, solvent: EtOH,
N2 atmosphere with irradiation by a 200 W tungsten lamp (l > 440 nm) for 2 h. bConversion was estimated by the
c
d
recovery of DDT. Products were analyzed by NMR. Total turnover numbers based on the initial concentration
e
f
g
of Rhodamine B. The reaction was carried out in the dark. In the absence of TEOA. Prolonged visible light
irradiation for 30 h. h[3] = 5.0 × 10-4 M. i [[Ru(bpy)3]2+] = 5.0 × 10-5 M.
above-mentioned suggestion that DDT was dechlorinated
to DDD, which was further dechlorinated to the di- and/
or tri-dechlorinated products in Entry 6 in Table 1.
Mechanistic aspects
To gain a mechanistic insight into the photochemical
reduction of 1, quenching experiments of the singlet
excited state of 2 in EtOH were performed. Fluorescence
quenching of 2 was observed upon the addition of
TEOA and analyzed using the Stern–Volmer plot [32]
as shown in Fig. 3. The quenching rate constant (kq)
Chart 2.
was determined to be 4.7 × 108 M-1.s-1. This result is
consistent with a previous report that the singlet excited
state of 2 is reductively quenched by tertiary amines such
as triethylamine [39]. On the other hand, the fluorescent
quenching of 2 was not observed upon the addition of 1.
Based on the present and previous studies [33, 36, 42],
a plausible reaction mechanism for Entry 1 in Table 1
is proposed as shown in Fig. 4. Initially, the singlet
excited state of 2 is reductively quenched by TEOA to
form the one-electron-reduced species of 2 (Rho●-) and
the nitrogen-centered radical cation (TEOA●+). It was
proposed that the deprotonation of TEOA●+ by TEOA
yields a carbon-centered radical and that the hydrogen
atom abstraction at TEOA by TEOA●+ yields another
form the tri-dechlorinated compound (DCS) as the major
product.
The B12 model complex-Rhodamine B system was
further utilized for the dechlorination of the relatively
less reactive DDD. DDD was successfully dechlorinated
upon visible light irradiation for 30 h to form DCS,
DDMU and DDMS as dechlorinated products as shown
in Entry 1 in Table 2. These dechlorinated products
were also obtained from DDD in the previous catalytic
systems mediated by 1 [34, 36]. The product distribution
from DDD in Entry 1 in Table 2 is similar to that from
DDT in Entry 6 in Table 1. These results confirm the
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DECHLORINATION OF DDT CATALYZED BY VISIBLE-LIGHT-DRIVEN SYSTEM
139
Table 2. Catalytic dechlorination of DDD mediated by B12 model complex-Rhodamine B systema
Product yields, %c
Entry
Compound
Conversion, %b
DCS
DDMU
DDMS
TNd
1
2
3
1, 2
1
94
1
56
0
25
0
14
0
190
0
2
2
0
1
0
2
aConditions: [1] = 5.0 × 10-4 M, [2] = 5.0 × 10-5 M, [DDT] = 1.0 × 10-2 M, [TEOA] = 5.0 × 10-1
M, solvent: EtOH, N2 atmosphere with irradiation by a 200 W tungsten lamp (l > 440 nm) for 30
h. bConversion was estimated by the recovery of DDD. cProducts were analyzed by NMR. dTotal
turnover numbers based on the initial concentration of Rhodamine B.
carbon-centered radical [43–45]. These carbon-centered
radicals denote a second electron to form the products
as shown in Fig. 4 [43–45]. The electron transfer from
Rho●- to 1 affords the formation of the Co(I) species
of the B12 derivative because the combination of 1 and
2 is thermodynamically favorable (E0(Co(II)/Co(I)) =
-0.64 V vs. SCE [24], E0(Rho/Rho●-) = -0.8 vs. SCE
[20, 30]). The resulting supernucleophilic Co(I) species
of the B12 derivative dechlorinates DDT to form an
alkylated complex. The Co–C bond of the alkylated
complex is cleaved by visible light irradiation to form
a radical species and 1. The radical species mainly
abstracts hydrogen from TEOA to form DDD. The
turnover numbers based on 2 was 186 (Entry 1 in Table
1). The UV-vis spectrometric analyses revealed that 89%
of 2 was unchanged after the dechlorination of DDT.
Fig. 3. Stern–Volmer plot of fluorescence quenching of 2 (1.0 ×
10-6 M) by TEOA at 25 °C. lex = 530 nm, lem = 568 nm; F0 =
original fluorescence intensity, F = fluorescence intensity after
addition of TEOA
Fig. 4. Proposed mechanism of the dechlorination of DDT mediated by B12 model complex-Rhodamine B system
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K. TAHARA ET AL.
This result confirms the good photoredox stability of
Rhodamine B in the present system. The use of such
a photostable sensitizer enabled the efficient electron
transfer from the electron donor (TEOA) to the final
acceptor (DDT) to afford good turnovers relative to 2.
Thus, we have successfully replaced [Ru(bpy)3]2+ in the
previous system [25] (Entry 8 in Table 1) by an organic
sensitizer without a decrease in the catalytic activity. The
DDD formed from DDT is further dechlorinated by the
Co(I) species of the B12 derivative to form an alkylated
complex. According to a previous mechanistic study on
the reaction of vitamin B12 with DDD [46], the alkylated
complex reacts via a cobalt chloride a-elimination to yield
DCS. This is analogous to the reaction of organic gem-
dihalide with copper [47]. The a-elimination generates a
carbenoid type intermediate which will readily rearrange
to the product. DDMU and DDMS are formed by the
b-elimination and the hydrogen abstraction of the radical
species resulting from the homolysis of the alkylated
complex, respectively [36].
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In conclusion, a new catalytic system composed of a
vitamin B12 derivative and Rhodamine B dechlorinated
DDT to DDD via a noble-metal-free and visible-light-
driven process. Furthermore, the present B12 model
complex-Rhodamine B system can be used for the
prolonged photocatalysis to further dechlorinate DDD
to form the tri-dechlorinated compound as the major
product.
Acknowledgements
This work was partially supported by a Grant-in-Aid
for Scientific Research on Innovative Areas “Molecular
Activation toward Straightforward Synthesis” (No.
23105537) from the Ministry of Education, Culture,
Sports, Science and Technology (MEXT) of Japan and a
Grant-in-Aid for Challenging Exploratory Research (No.
24655134) from the Japan Society for the Promotion
of Science (JSPS), SEKISUI “Innovations Inspired by
Nature” Support Program, and Kyushu University P&P
Program.
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