Visible-light-induced photocatalytic benzene/cyclohexane cross-coupling utilizing a ligand-to-metal charge transfer benzene complex adsorbed on titanium oxides

Article abstract of DOI:10.1039/c7cy02566a

The cross-coupling reaction of benzene and cyclohexane molecules proceeded selectively over Pd-modified titanium dioxide photocatalysts under visible light. A ligand-to-metal charge-transfer (LMCT) complex of benzene adsorbed on titanium oxide was proposed as the key species for the selective formation of the cross-coupling product.

Full text of DOI:10.1039/c7cy02566a

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Visible-light-induced Photocatalytic Benzene/Cyclohexane Cross-
coupling Utilizing a Ligand-to-metal Charge Transfer Benzene
Complex Adsorbed on Titanium Oxides
Received 00th January 20xx,
Accepted 00th January 20xx
ab
a
ab
DOI: 10.1039/x0xx00000x
A. Yamamoto,* T. Ohara, and H. Yoshida*
www.rsc.org/
5
The cross-coupling reaction of benzene and cyclohexane reported, only a few studies have dealt with non-chemically
b
9
molecules proceeded selectively over Pd-modified titanium bonded molecules (e.g., benzene) onto a TiO
2
surface.
dioxide photocatalysts under visible light. A ligand-to-metal Moreover, the mechanism in these cases is unclear, possibly
charge transfer surface complex of benzene adsorbed on a owing to the weak interactions. Herein, we demonstrate a
titanium oxide was proposed as the key species for the selective selective cross-coupling reaction between benzene and
formation of the cross-coupling product.
cyclohexane molecules via the C–H bond activation using the
LMCT surface benzene complex on a TiO photocatalyst. In
2
Titanium dioxide (TiO ) photocatalysts promote various
2
addition, the origin of the selectivity improvement was
discussed in terms of the C–H bond dissociation energy (BDE).
1
reactions such as water splitting, the decomposition of
2
harmful organic and inorganic molecules, and synthesis of
3
organic compounds. However, in several cases, organic
Metal co-catalysts were photodeposited on a TiO sample
2
2 –1
JRC-TIO-8, anatase, 338 m g ).† The catalyst is referred to as
(
synthesis using TiO2 photocatalysts exhibits poor selectivity,
possibly because photo-generated holes in the TiO2 valence
band, owing to their deep oxidation potential, oxidize
molecules indiscriminately. Thus, improvement of selectivity in
photocatalytic reactions remains challenging.
M/TiO (M = Rh, Pt, Au, Pd, Ag, Ni, and Co). The reaction was
2
carried out in a closed reactor under Ar atmosphere at room
temperature with a 300 W xenon lamp using a long pass filter
(light wavelength, λ > 350 or 400 nm) (ESI).†
The coupling reaction of benzene and cyclohexane over metal
Recently, photocatalytic reactions for the selective formation
4
of chemical compounds have been reported. One of these
(M)-modified TiO photocatalysts (M = Rh, Pt, Au, Pd, Ag, Ni,
2
and Co; 0.1 wt%) under UV-light irradiation afforded both
cross-coupling [phenylcyclohexane (PCH)] and homo-coupling
[bicyclohexyl (BCH) and biphenyl (BP)] products (Table 1). The
reaction did not proceed in the dark or in the absence of a
photocatalyst. Moreover, no product was generated with a
Pd/Al O sample under visible light. These results indicate that
successful approaches employs ligand-to-metal charge transfer
(
LMCT) from the adsorbed molecule to the TiO conduction
2
5
band using visible light (in-situ doping). Using this approach,
selective photocatalytic reactions were reported, for example,
7
photooxidation of alcohols and amines, photoactivation of
6
8
ammonia, where molecules adsorbed onto the photocatalyst
2
3
the reaction proceeded with the aid of TiO2 photocatalysis.
The formation of the three products (Table 1, entry 3) suggests
that cyclohexyl and benzyl radicals were generated under
surface by chemical bonding exhibited high selectivity towards
the desired products under visible light.
1
0
Although several LMCT surface complexes have been
these conditions and the coupling afforded the three
products (eq. 1–6). By comparison between the pristine TiO2
and M/TiO2 samples, noble metal co-catalysts improved the
photocatalytic activity to PCH (entries 1–9). The Rh/TiO and
2
Pt/TiO samples displayed the high activity leading to the PCH
2
formation after 1 h. However, comparable amounts of the
homo-coupling products were also formed. Conversely, the
Pd/TiO2 sample exhibited relatively high selectivity towards
PCH formation, where BCH formation was drastically
suppressed. Thus, Pd was selected as the co-catalyst for this
reaction. Unfortunately, the homo-coupling reactions also
proceeded to some extent, even in the Pd/TiO2 sample. In
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addition, compared to the total amount of PCH, BCH, and BP, a To investigate the light-absorbing species under visible light,
large amount of hydrogen evolution was observed in the UV-Vis diffuse reflectance spectra (DRS) were recorded in the
Pt/TiO
2
, Au/TiO
2
and Pd/TiO
2
samples (Table 1, entry 3–5). This presence of benzene and cyclohexane (Fig. 1). An edge shift
sample; on
low mass-balance between the hydrogen and the coupling was observed after benzene was added to the TiO
2
products suggests that unfavorable reactions (e.g., the other hand, this shift was not observed when cyclohexane
dehydrogenative polymerization) would occur in parallel under was added instead of benzene. The upper panel illustrates the
UV light.
difference spectrum (b-a), and a clear band appeared by the
addition of benzene. These results indicate that the emerged
absorption after the benzene addition was due to the benzene
a
Table 1 Photocatalytic coupling reaction of cyclohexane and benzene .
9
a
2
species adsorbed onto the TiO surface. Similar phenomena
were also reported for several molecules such as catechol,
8
alcohol, amine, ammonia. In these studies, the molecules
b
c
Selec. (%)
t
Product amount / μmol
were adsorbed via chemical bonding, and the resultant
Entry
Catalyst
/
h
PCH
0.7
5.7
5.6
4.9
3.7
2.2
0.5
0.3
0.6
2.3
3.4
1.1
0.3
BCH
4.2
2.4
3.6
3.3
0.5
1.7
0.7
0.3
BP
n.d.
0.6
H
2
S
C
7.4
53
40
42
78
38
13
35
>99
>99
81
65
55
S
B
>99
83
absorption bands were attributed to LMCT excitation from the
12
d
e
1
2
3
4
5
6
7
8
9
TiO
2
1
06
05
adsorbed molecules to the TiO conduction band. On the
2
d
Rh/TiO
2
1
1
1
1
1
1
1
1
3
6
6
6
other hand, it was reported that the absence of dissociative
reactivity between the benzene molecules and the pristine
TiO (110) surface due to the little hybridization between TiO
d
Pt/TiO
2
0.3
34
90
d
d
d
Au/TiO
2
1.0
26
71
2
2
Pd/TiO
2
1.1
23
64
13
and benzene electronic states. Furthermore, the emerged
band position was close to that of an electron donor-acceptor
Ag/TiO
2
0.2
03
83
d
e
e
e
e
e
e
e
Ni/TiO
2
n.d.
n.d.
n.d.
n.d.
n.d.
n.d.
n.d.
01
>99
>99
>99
>99
>99
>99
>99
complex of benzene (π electron donor) and TiCl (electron
4
d
f
e
Co/TiO
2
n.d.
02
1
acceptor), where the complex was converted to the radical
4
e
Pd/TiO
Pd/TiO
Pd/TiO
2
2
2
n.d.
n.d.
0.4
0.3
0.1
+
pair [ArH· , TiCl · ] form by LMCT excitation with visible light.
-
f
e
4
1
1
1
1
0
1
3
4
02
f
Thus, the adsorption band could be attributed to the π-
01
f
interaction between the benzene complex and the TiO2
Pt/TiO
2
01
f
e
surface (eqs. 9, 10), which was also proposed in toluene-Nb O
2 5
TiO
2
n.d.
9
system recently.
b
Before revision
-
+
TiO
+
2
+ hν ➝ e cb + h vb
(1)
+
h
+ C H ➝ TiO + ·C H + H
(2)
(3)
(4)
(5)
(6)
(7)
(8)
vb
6
6
2
6
5
+
+
h
vb + C
6
H
12 ➝ TiO
2
+ ·C
6
H
11 + H
·
C H + ·C H ➝ C H –C H (BP)
6
5
6
5
6
5
6
5
·
C
6
H
5
+ ·C
6
H
11 ➝ C
6
H
5
–C
6
H
11 (PCH)
·
C6H11 + ·C H ➝ C H –C H (BCH)
6
11
6
11
6 11
-
+
e
cb + H ➝ ·H
·
H ➝ 1/2 H2
We next performed the reaction experiment using a different
wavelength using the Pd/TiO sample, which is known to affect
2
1
1
the activity and selectivity of the reaction. As illustrated in
Table 1, a higher selectivity towards PCH was observed under
visible light (λ >400 nm, entries 9–11) than UV-light (λ >350 nm,
entry 3)
. Surprisingly, BP formation was completely
suppressed by limiting the light wavelength. The state of Pd
co-catalysts after the reactions under UV-visible and visible
light were similar each other by X-ray adsorption fine structure
(XAFS) spectroscopy as shown in Fig. S1 (ESI).† Thus, the
deference in selectivity strongly suggests that the reaction
proceeded via a different mechanism when only visible light
was applied.
2
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+
+
C6H6 + C H ➝ C H + ·C H + H
(12)
(13)
6
6
6
6
6
5
+
+
C
6
H
6
+ C
6
H
12 ➝ C
6
H
6
+ ·C
6
H
11 + H
Our previous studies demonstrated that Pd co-catalysis
promoted the addition of photo-generated radical species to
an aromatic benzene ring over the Pd-modified TiO
1
2
0b, 18
photocatalyst.
The significant promotion effect of the Pd
2 2
co-catalyst, compared to pristine TiO and Pt/TiO , was also
observed (entries 11–13) in the present study. It is likely that
the Pd co-catalyst promotes the attack of the cyclohexyl
radical to the benzene molecule. Isotope experiments were
carried out to evidence the radical addition mechanism (Table
1
2
2
). When cyclohexane-d was employed, the k /k value was
H D
determined as 1.0 and kinetic isotope effect (KIE) was not
observed while slightly lower than unity values were obtained
2
Fig. 1 UV-Vis DR spectra of the TiO sample without adsorbate (a), with
6
with benzene-d (inverse KIE). These results indicate that the
benzene (b), and with cyclohexane (c), and the action spectrum (green circle,
left axis). Upper panel shows the difference spectrum (b-a).
dissociation of the C–H bond of cyclohexane and benzene was
not the rate-determining step of the reaction. The inverse KIE
suggests that the reaction proceeds via a cyclohexyl radical
addition into benzene (eq. 14) and the addition step is the
rate-determining step. The radical attacks result in
C
6
H
6
+ TiO
2
➝ C
6
H
6
-TiO
2
(surface complex)
+
(9)
-
C H -TiO (surface complex) ➝ C H + TiO (e )
(10)
6
6
2
6
6
2
2
3
hybridization of benzene carbon from sp to sp , and the
change would lead to the inverse kinetic effect due to the
To investigate the reaction mechanism, we next measured the
apparent quantum yield (AQY) for the reaction by applying eq.
1
change of these zero point energies, and the phenomenon
9
1
8a
was also observed in our previous papers. The consideration
of the rate-determining step is also supported by the positive
effect of Pd loading on the activity because the Pd co-catalyst
11 using various monochromatic lights.†
TotalꢃamountsꢃofꢃPCH, BCH, andꢃBP
AQYꢀ%ꢁ ꢂ
(11)
10b, 18
would accelerate the radical addition to benzene.
Numberofꢃincidentꢃphotons
Moreover, a small amount of the homo-coupling product of
cyclohexane was also generated in the Pd/TiO sample under
2
The AQY was 1.5% at 360 nm, and decreased with the
wavelength of the light as shown in Fig.1B. The trend, i.e., the
action spectrum, coincided with the absorption spectrum of
visible light, which indicating that cyclohexyl radical formation
(eq. 13) and its homo-coupling (eq. 6) occurred during the
reaction under visible light. These reactions are consistent with
the proposed mechanism. On the other hand, the photo-
generated electron reduces the proton on the Pd site into the
hydrogen atom (eq. 7), and the hydrogen atoms formed in eqs.
the adsorbed benzene molecules on the TiO
supporting the LMCT mechanism from the adsorbed benzene
molecule to the TiO conduction band (eq. 10).
2
surface,
2
The formation of BP was markedly suppressed under visible 7 and 15 desorb as a molecular hydrogen (eq. 8).
light when compared to UV light (entries 5 and 11, Table 1).
·C
6
H11 + C
6
H
6
➝ ·C
6
H
6
–C
6
H
11
(14)
(15)
The formation of benzene radical cation intermediates
provides us a reasonable explanation of the suppression of BP
6
·C H –C H ➝ C H –C H (PCH) + H·
6
6
12
6
5
6 11
1
formation based on the C–H BDEs of benzene (472.2 kJ mol )
5
-1
-1
and cyclohexane (416.3 kJ mol ). The change in Gibbs energy
a
Table 2 Isotope experiment in the photocatalytic coupling reaction.
○
ΔG =19 kJ mol ) of the benzyl radical formation by the
-1
(
b
Reactants
Product amount / μmol
k
H
/k
D
benzene radical cation (eq. 12) was calculated from the BDE
and the one-electron oxidation potential of benzene (2.48 V vs
Entry
PCH
0.80
0.78
1.10
BCH
BP
n.d.
n.d.
n.d.
H
2
1
6
17
b
b
b
b
SCE) and hydrogen radicals (-1.87 V vs SCE) (ESI)†. The
positive value for benzene indicates that the reaction hardly
proceeds at room temperature because of the thermodynamic
limitation. Conversely, the reaction between the benzene
1
2
3
C
C
C
H
6 12
D
6 12
H
6 12
C H
6 6
C H
6 6
C D
6 6
n.d.
n.d.
n.d.
0.95
1.00
0.56
–
b
b
1.00
0.75
radical
cation
and
cyclohexane
(eq.
13)
was
○
-1
thermodynamically favorable (ΔG = -37 kJ mol ). Thus, the
formed benzene radical cation activates cyclohexane more
easily than benzene.
In summary, reaction mechanisms for the cross-coupling
reaction between benzene and cyclohexane under UV and
visible light are proposed (Fig. 2). In the UV-irradiated Pd/TiO
system (Fig. 2a), holes in the TiO valence band react with
2
2
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d) T. Shishido, K. Teramura and T. Tanaka, Catal. Surv. Asia., 2011, 15, 240; e) H.
Yuzawa, S. Yoneyama, A. Yamamoto, M. Aoki, K. Otake, H. Itoh and H. Yoshida,
Catal. Sci. Technol., 2013, 3, 1739; f) X. Lang, X. Chen and J. Zhao, Chem. Soc. Rev.,
2014, 43, 473; g) X. Lang, J. Zhao and X. Chen, Angew. Chem. Int. Ed., 2016, 55,
benzene and cyclohexane to form the corresponding radicals.
The radical coupling provides three products: PCH, BCH, and
BP. On the other hand, visible light excitation of the LMCT
4
697; h) J. Kou, C. Lu, J. Wang, Y. Chen, Z. Xu and R. S. Varma, Chem. Rev., 2017,
17, 1445; i) A. Tyagi, A. Yamamoto, T. Kato and H. Yoshida, Catal. Sci. Technol.,
2
complex of benzene adsorbed on TiO (Fig. 2b) and the
1
resulting benzene radical cation selectively activates
cyclohexane to form cyclohexyl radical. The cyclohexyl radical
attacks benzene molecule via the addition-elimination route to
form PCH (eqs. 14, 15). The selective formation of cyclohexyl
radical completely suppresses the homo-coupling of benzene.
Furthermore, acceleration of the addition of the cyclohexyl
2017, 7, 2616.
5
6
.
.
a) T. Shishido, K. Teramura and T. Tanaka, Catal. Sci. Technol., 2011, 1, 541−551;
b) G. Zhang, G. Kim and W. Choi, Energy Environ. Sci., 2014, 7, 954−966; c) M.
Fukui, A. Tanaka, K. Hashimoto and H. Kominami, Chem. Commun., 2017, 53,
4
215.
a) T. Shishido, T. Miyatake, K. Teramura, Y. Hitomi, H. Yamashita and T. Tanaka, J.
Phys. Chem. C, 2009, 113, 18713−18718; b) S. Higashimoto, N. Suetsugu, M.
Azuma, H. Ohue and Y. Sakata, J. Catal., 2010, 274, 76; c) S. Higashimoto, K.
Okada, T. Morisugi, M. Azuma, H. Ohue, T.-H. Kim, M. Matsuoka and M. Anpo,
Top. Catal., 2010, 53, 578; d) S. Furukawa, T. Shishido, K. Teramura and T.
Tanaka, ACS Catal., 2011, 2, 175−179; e) S. Furukawa, Y. Ohno, T. Shishido, K.
Teramura and T. Tanaka, Chemphyschem, 2011, 12, 2823; f) S. Furukawa, T.
Shishido, K. Teramura and T. Tanaka, Chemphyschem, 2014, 15, 2665.
a) X. Lang, W. Ma, Y. Zhao, C. Chen, H. Ji and J. Zhao, Chem. Eur. J., 2012, 18,
2624; b) S. Furukawa, Y. Ohno, T. Shishido, K. Teramura and T. Tanaka, J. Phys.
Chem. C, 2013, 117, 442.
radical to benzene by
a Pd co-catalyst suppresses the
formation of BCH. Thus, the selective formation of cross-
coupling products was achieved via the surface-benzene-
complex-mediated LMCT mechanism with the aid of Pd metal
catalysis.
7
.
8
9
.
.
S. Yamazoe, K. Teramura, Y. Hitomi, T. Shishido and T. Tanaka, J. Phys. Chem. C,
2
007, 111, 14189−14197.
a) A. Ramakrishnan, S. Neubert, B. Mei, J. Strunk, L. Wang, M. Bledowski, M.
Muhler and R. Beranek, Chem. Commun., 2012, 48, 8556−8558; b) K. Tamai, K.
Murakami, S. Hosokawa, H. Asakura, K. Teramura and T. Tanaka, J. Phys. Chem. C,
2
017, 121, 22854.
0. a) H. Yuzawa, J. Kumagai and H. Yoshida, J. Phys. Chem. C, 2013, 117,
1047−11058; b) H. Yoshida, Y. Fujimura, H. Yuzawa, J. Kumagai and T. Yoshida,
1
1
Chem. Commun., 2013, 49, 3793.
1
1
1. S. Fukuzumi and K. Ohkubo, Chem. Sci., 2013, 4, 561.
2. a) Y. Wang, K. Hang, N. A. Anderson and T. Lian, J. Phys. Chem. B, 2003, 107,
9
1
434−9440; b) S. Varaganꢀ and G. Ramakrishna, J. Phys. Chem. C, 2010, 114,
3917−13925.
1
1
1
3. J. Zhou, S. Dag, S. D. Senanayake, B. C. Hathorn, S. V. Kalinin, V. Meunier, D. R.
Mullins, S. H. Overbury and A. P. Baddorf, Phys. Rev. B, 2006, 74, 125318.
4. K. Brueggermann, R. S. Czernuszewicz and J. K. Kochi, J. Phys. Chem., 1992, 96,
4
405.
5. Y.-R. Luo, in Comprehensive Handbook of Chemical Bond Energies, CRC Press,
007, pp. 19.
2
1
1
6. P. B. Merkel, P. Luo, J. P. Dinnocenzo and S. Farid, J. Org. Chem., 2009, 74, 5163.
7. a) E. Baciocchi, T. Del Giacco and F. Elisei, J. Am. Chem. Soc., 1993, 115, 12290; b)
E. Baciocchi, T. Del Giacco, O. Lanzalunga, P. Mencarelli and B. Procacci, J. Org.
Chem., 2008, 73, 5675.
1
1
8. a) A. Tyagi, T. Matsumoto, T. Kato and H. Yoshida, Catal. Sci. Technol., 2016; b) E.
Wada, T. Takeuchi, Y. Fujimura, A. Tyagi, T. Kato and H. Yoshida, Catal. Sci.
Technol., 2017, 7, 2457.
Fig. 2 Schematic illustration of the reaction mechanism under visible light
and UV-light.
9. A. Streitwieser, R. H. Jagow, R. C. Fahey and S. Suzuki, J. Am. Chem. Soc., 1958,
8
0, 2326.
Acknowledgement
This work was supported by JSPS KAKENHI Grant Number
JP16K14477 as Grant-in-Aid for Challenging Exploratory
Research. The XAFS experiments were performed under the
approval of the Photon Factory Program Advisory Committee
(Proposal No. 2016G643).
Conflicts of interest
The authors declare no competing financial interest.
Notes and references
1
2
.
.
A. Fujishima and K. Honda, Nature, 1972, 238, 37.
a) A. Fujishima, T. N. Rao and D. A. Tryk, J. Photochem. Photobiol., C, 2000, 1,
1
−21; b) T. Ochiai and A. Fujishima, J. Photochem. Photobiol. C, 2012, 13, 247.
3
4
.
.
a) M. Fagnoni, D. Dondi, D. Ravelli and A. Albini, Chem. Rev., 2007, 107, 2725; b)
D. Friedmann, A. Hakki, H. Kim, W. Choi and D. Bahnemann, Green Chem., 2016,
1
8, 5391.
a) Y. Shiraishi and T. Hirai, J. Photochem. Photobiol. C, 2008, 9, 157−170; b) H.
Yoshida, H. Yuzawa, M. Aoki, K. Otake, H. Itoh and T. Hattori, Chem. Commun.,
2
008, 4634; c) H. Yuzawa and H. Yoshida, Chem. Commun., 2010, 46, 8854−8856;
4
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Table of Contents
High selectivity was achieved in photocatalytic cross-coupling of
benzene and cyclohexane by photoexcitation of benzene surface complex
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