Phosphine Oxidation with Water and Ferrocenium(III) Cation Induced by Visible-Light Irradiation

Article abstract of DOI:10.1002/chem.201805129

Stoichiometric oxidation of phosphines with water and ferrocenium(III) cation as the oxygen atom source and the oxidizing reagent, respectively, was achieved in acetonitrile under visible-light irradiation by using 2,6-lutidine as the proton acceptor. The reaction required light irradiation, under which fluorescence was observed for the acetonitrile solution of the ferrocenium(III) cation.

Full text of DOI:10.1002/chem.201805129

A Journal of
Accepted Article
Title: Phosphine Oxidation with Water and Ferrocenium(III) Cation
Induced by Visible Light Irradiation
Authors: Yoshiaki Nishibayashi, Yoshiaki Tanabe, and Kazunari
Nakajima
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Phosphine Oxidation with Water and Ferrocenium(III) Cation Induced
by Visible Light Irradiation
Yoshiaki Tanabe, Kazunari Nakajima, and Yoshiaki Nishibayashi*
Abstract: Stoichiometric oxidation of phosphines with water and
ferrocenium(III) cation as an oxygen atom source and an oxidizing reagent,
respectively, in acetonitrile under the irradiation of visible light has been
achieved by using 2,6-lutidine as a proton acceptor. The reaction requires
irradiation of light, where fluorescence behavior is observed for the
acetonitrile solution of ferrocenium(III) cation.
Very recently, our group has investigated photoinduced catalytic
water oxidation to produce proton sources for the catalytic nitrogen
fixation under ambient reaction conditions.[9] During our investigation,
we have happened to discover that the ferrocenium(III) cation [FeCp2]+
can work as a photoinduced oxidizing reagent in aqueous acetonitrile
solution under the irradiation of visible light. In this reaction, phosphine
is oxidized with water and [FeCp2]+ as an oxygen atom source and an
oxidizing reagent, respectively, to afford the corresponding phosphine
oxide under the irradiation of visible light (Chart 1b). Without the
irradiation of visible light, redox reaction of phosphine with water and
[FeCp2]+ did not take place, while irradiation of UV or higher energy
light were not necessary. Here, we wish to report this basic but
unexpected photoredox reaction induced by visible light.
Ferrocene (FeCp2, Cp = η5-C5H5) has been well utilized as convenient
one-electron reducing reagents,[1] and its photochemical properties has
been also well investigated toward catalytic reactions.[2] However,
FeCp2 has shown additional spectral and photochemical features only
when forming photoactive ground-state donor–acceptor complex in
good electron-accepting media such as halogenated hydrocarbons,[3]
activated alkenes,[4] or alcohols,[5] and has been rather considered to be
photochemically inert, exhibiting only radiationless deactivation.[6]
However, neither fluorescence nor phosphorescence except for those
due to impurities or photolysis products of FeCp2.[2]
Consequently, the photochemistry of ferrocenium(III) cation
([FeCp2]+), the oxidized form of FeCp2, has been investigated,[7] where
[FeCp2]+ is shown to work as a photosensitizer that can lead to one-
electron oxidation of reagents.[8] For example, photoreduction of
[FeCp2]2(SO4) to [FeCp2] or its derivatives in aqueous solution has been
observed under the irradiation of γ-ray with presumable formation of O2
via water oxidation.[8a] Studies on absorption spectra has suggested that
the photoreduction of [FeCp2]Cl in aqueous solution occurs at its strong
absorption band at 254 nm,[8b] which has been assigned as one of the
allowed ligand-to-metal charge-transfer transition in the UV light region.
Accordingly, irradiation of near-UV light to an acetonitrile solution of
[FeCp2]PF6 and alcohols (such as PhCH2OH) leads to the formation of
FeCp2 and oxidized substrates (such as PhCHO) (Chart 1a), which are
not obtained under the irradiation of visible light (λ > 366 nm),
demonstrating that several LMCT transition excitations of [FeCp2]+ in
the UV light region leads to the redox reaction.[8c] So far, all the reported
photoreactions where [FeCp2]+ acts as an oxidizing reagent as well as a
photosensitizer have been shown to require irradiation of UV or higher
energy light.[8] Irradiation of visible light to the solution of FeCp20/+ is
also known to induce some redox reactions,[3–5] which has been rather
considered as owing to the photoexcitation of FeCp2 derivatives.[2]
Chart 1. Photoinduced oxidation with [FeCp2]+.
When a mixture of triphenylphosphine (Ph3P), water, [FeCp2]OTf
(OTf = trifluoromethanesulfonate), and 2,6-lutidine (Lut) in acetonitrile
was irradiated by visible light (λ > 380 nm) at room temperature for 3
hours under an argon gas atmosphere, stoichiometric formation of a
mixture of triphenylphosphine oxide (Ph3PO), FeCp2, and 2,6-
lutidininium trifluoromethanesulfonate ([LutH]OTf) was observed by
1H and 31P NMR spectra, all of which could be isolable by further
purification (Scheme 1).
[*]
Dr. Y. Tanabe, Prof. Dr. Y. Nishibayashi
Department of Systems Innovation
School of Engineering, The University of Tokyo
Hongo, Bunkyo-ku, Tokyo 113-8656 (Japan)
E-mail: ynishiba@sys.t.u-tokyo.ac.jp
Prof. Dr. K. Nakajima
Frontier Research Center for Energy and Resources
School of Engineering, The University of Tokyo
Hongo, Bunkyo-ku, Tokyo 113-8656 (Japan)
Supporting information and the ORCID identification number(s) for
the author(s) of this article can be found under:
https://doi.org/10.1002/anie.201xxxxxx.
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Scheme 1. Photoinduced oxidation of Ph3P with H2O and [FeCp2]+.
acetonitrile or aqueous acetonitrile has been valued to be ca. +0.93 to
+1.13 V vs SCE,[12a,c–e] corresponding to +0.55 to +0.75 V vs
FeCp2 ,
0/+ [16] oxidation of Ph3P cannot be performed by [FeCp2]+ without
Oxidation of Ph3P did not occur without the addition of
[FeCp2]OTf or water, or in dark without the irradiation of any light,
while reduction of [FeCp2]OTf did not occur without the addition of
Ph3P, thus the addition of Ph3P, water, [FeCp2]OTf, and the irradiation
of visible light are all necessary for this redox reaction. Addition of Lut
as the proton acceptor was only necessary to accelerate the reaction;
Ph3P worked as a proton acceptor to afford [Ph3PH]+[10] when Lut was
not added to the reaction mixture, where the redox reaction did not
complete within 24 h even under the irradiation of visible light. In
addition, slightly more than a stoichiometric amount of Ph3P are
necessary to complete the reaction within 3 h. When 18O-enriched water
(97 atom%) was used instead of normal degassed pure water for the
reaction, Ph3PO with 18O enrichment of 85 atom% was obtained, thus it
is water but not contaminant dioxygen that is the oxygen source for the
formation of phosphine oxide.[11]
irradiation of light, while the photoexcited species formed in acetonitrile
with the estimated oxidation potential of +3.3 V vs FeCp2 based on
the fluorescence measurements is high enough to oxidize Ph3P.
0/+
500
The UV-visible absorption spectrum of [FeCp2]OTf in acetonitrile
at room temperature as shown in Figure 1a exhibits five electronic
absorption bands including four shoulders in visible light region, where
five bands at 616 (band I), 570 (band II), 529 (band III), 474 (band IV),
and 379 nm (band V) have been assigned as the lowest lying ligand-to-
metal charge transfer for band I or spin-allowed d–d transitions for bands
II to V,[7a] which correspond to excitations from the low-spin ground
2Δ(σ2 δ3) level to the groups of levels Φ, Π (for band II); Φ, Π, H
(for band III); 2Π (for band IV); and 2Φ, 2Π (for band V), respectively.[7c]
On the other hand, no absorption band is observed for Ph3P and Lut in
visible light region, ruling out their possibility to work as
photosensitizers. Photoinduced redox reactions by [FeCp2]+ previously
reported have been argued to be induced by the LMCT bands in UV light
region (< 300 nm),[8b,c] thus the present reaction of [FeCp2]+ induced by
0
350
800
2
1
0
2
2
2
2
2
visible light is unprecedented, adding
a new feature to the
photochemistry of [FeCp2]+, which should be consulted more in detail.
To explore the dependency of photoexcitation wavelengths on the
photoinduced oxidation of phosphines, irradiation of visible light was
further carried out with different sharp-cut glass filters. Indeed, 3 h
irradiation of visible light with λ > 500 nm afforded Ph3PO only in 1%
NMR yield, while the yield of Ph3PO was as low as 30% or 77% under
the irradiation of visible light for 3 h with λ > 440 nm or λ > 400 nm,
respectively, suggesting that the visible light irradiation with higher
energy is more effective, and that especially the absorption band V at
379 nm in Figure 1a is likely responsible for the photooxidation of
300
500
Figure 1. Absorption and fluorescence spectra of [FeCp2]OTf.
The reaction rate at the irradiation of a specific wavelength (410
nm) under the reaction conditions same with Scheme 1 except for the
range of irradiation light could be determined to be 1.11 ×10–6 mol L–1
s–1 with a typical zero-order reaction profile using the time-dependent
decay of the absorption at 616 nm (band I of [FeCp2]OTf in Figure 1a).
As the irradiated light intensity in the reactor was estimated to 3.01 ×
10–7 E s–1 at 410 nm by using potassium ferrioxalate as a chemical
actinometer,[17] the quantum yield of this redox reaction is given as Φ =
0.018,[11] which is lower than that observed for the photoreduction of
[FeCp2]Cl in water induced by the UV light at 254 nm (Φ = 0.16).[8b]
In order to get more information on reaction pathways, kinetic
studies were performed on various reaction conditions changing from
the typical reaction conditions as shown in Scheme 2. Logarithmic plot
of the consumption rates of [FeCp2]OTf within an hour against initial
concentrations of [FeCp2]OTf (0.024 to 0.048 mol/L) has suggested that
the reaction is zero order in the concentration of [FeCp2]OTf as is
observed for the chemical actinometric measurement at 410 nm. The
reaction rate has been also shown to be proportional to the zeroth power
of the concentration of the reactants such as water (initial concentration
of 0.12 to 1.92 mol/L) and Lut (initial concentration of 0.012 to 0.192
phosphines.
More precisely, fluorescence measurements were
performed for bands I to V of [FeCp2]OTf in acetonitrile, where
emission spectra were only obtained for the excitation of band V. Indeed,
three clear emission peaks at 380, 402, and 426 nm have been observed
by the excitation at 350 nm (Figure 1b). In contrast, three fluorescence
excitation peaks have been observed at 376, 356, and 339 nm by fixing
the emission wavelength at 400 nm (Figure 1b), demonstrating that the
excited state carries ca. 3.3 eV of energy that corresponds to 378 nm
based on the Planck–Einstein relation.
It must be noted that the triphenylphosphine radical cation Ph3P•+
obtained by the electrochemical oxidation of Ph3P has been known to
react with water or other adducts to afford Ph3PO[12] or other
organophosphorus compounds,[13] and has been also known to quench
photosensitizers through single-electron transfers.[14] Ph3P itself has
been reported to act even as an photosensitizer due to an absorption band
at around 260 nm under the irradiation of UV light, while such
photosensitization does not occur for Ph3P under the irradiation of
visible light (λ > 380 nm).[15] As the oxidation potential of Ph3P in
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mol/L), but to the first power of the concentration of Ph3P (initial
concentration of 0.015 to 0.06 mol/L), suggesting that the electron
transfer from Ph3P to the photoexcited species is the rate-determining
step.[11]
phosphorus atom due to the introduction of electron-donating
substituents on the para positions promote the rate-determining electron
transfer from the photoexcited species to the phosphorus atom to give
rise to the formation of the radical cation (p-RC6H4)3P•+.
+1
0
Scheme 2. Kinetic studies of the oxidation of Ph3P with H2O and [FeCp2]+.
-1
-0.4
0
+0.4
The photoinduced oxidation with H2O and [FeCp2]OTf was
further studied for various phosphines as summarized in Table 1, where
conversion of phosphines based on the amount of [FeCp2]OTf were
determined by 31P NMR spectra.[11] When Cl as an electron-
withdrawing group was introduced to the para positions of Ph groups of
Ph3P, reaction was not completed within 3 h (Table 1, entry 2), or even
in elongated reaction time (Table 1, entry 3). On the other hand, when
an electron-donating group (MeO, Me) was introduced to the para
position of Ph groups of Ph3P, reaction was perfectly finished within 3
h (Table 1, entries 4 and 5), similarly to the result in case of Ph3P
(Scheme 1 = Table 1, entry 1). Similar stoichiometric reaction also
occurred when MePh2P and Cy3P were used as reactants (Table 1, entries
6 and 7), while irradiation of visible light was not required for the
reaction with Me2PhP, where the color of the reaction mixture began to
change immediately, and the reaction was completely finished within 30
min (Table 1, entry 8).
Figure 2. Hammett plot of the reaction rates against substituent constant (σp)
for the photoinduced oxidation of p-substituted triarylphosphines (p-RC6H4)3P
(R = MeO, Me, H, or Cl).
Based on the fluorescence and kinetic studies, the reaction
pathway of this reaction can be proposed as shown in Chart 2.
Ferrocenium(III) cation [FeCp2]+ in acetonitrile works as
a
photosensitizer to absorb a photon with λ ~ 380 nm to form a
photoexcited fluorescent species, the oxidation potential of which is ca.
0/+
+3.3 V vs FeCp2
. Here, the photoexcited species is expressed as
[FeCp2]*+ in Chart 2. Then, the rate-determining electron transfer
occurs from the photoexcited species to Ph3P to give the reduced
ferrocene FeCp2 and the triphenylphosphine radical cation Ph3P•+. In the
presence of water, Ph3P•+ is known to be readily attacked by water,
where secondary oxidation and deprotonation accelerated by Lut
smoothly take place to afford the triphenylphosphine oxide Ph3PO.[12]
Here, the secondary oxidation by [FeCp2]+ species does not likely
require photoexcitation, for previous cyclic voltammetric studies have
demonstrated that the two-electron oxidation process occurs in the
presence of water at almost the same oxidation potentials with those
observed for one-electron oxidation process to afford cationic radical
species Ph3P•+,[12] with the secondary redox potential estimated to be
highly negative for electron transfer.[19]
+
Table 1. Photoinduced oxidation of R3P with H2O and FeCp2
.
entry R3P
time (h)
yield of R3PO
1
2
3
4
5
6
7
8 a
Ph3P
3
3
24
3
3
3
0.12 mmol (100%)
0.003 mmol ( 2%)
0.050 mmol ( 41%)
0.12 mmol (100%)
0.12 mmol (100%)
0.12 mmol (100%)
0.12 mmol (100%)
0.12 mmol (100%)
(p-ClC6H4)3P
(p-ClC6H4)3P
(p-MeC6H4)3P
(p-MeOC6H4)3P
MePh2P
Cy3P
Me2PhP
3
0.5
a Without irradiation of visible light.
Kinetic studies on the introduction of substituents to the para
position of the aryl groups of triarylphosphines have revealed the linear
correlation between the reaction rate and Hammett substituent constants
(Figure 2),[18] demonstrating that the increasing electron density on the
Chart 2. Plausible reaction pathway.
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In conclusion, photoinduced oxidation of phosphines by
ferrocenium(III) cation has been achieved, where ferrocenium(III)
cation in acetonitrile works as a fluorescent photosensitizer with the
assignment of highest excitation and lowest emission wavelengths at
376 and 380 nm, respectively. While ferrocenium(III) cation has been
known to work as a photosensitizing oxidant, products have been only
assigned spectroscopically without any isolation, where irradiation of
UV light or higher energy radiation has been required.[8] Thus this work
provides the new fact that the ferrocenium(III) cation can be
photoexcited even by visible light, where all the products are fully
characterized for the first time. Here, the oxidation of triarylphosphines
by ferrocenium(III) cation is only possible under the irradiation of
visible light.
Meanwhile, the estimated oxidation potential of
0/+
photoexcited fluorescent species at ca. +3.3 V vs FeCp2 is highly
enough to oxidize H2O into O2, but such oxidation of H2O was not
observed for the aqueous solution of [FeCp2]+ under the irradiation of
visible light. Thus, scope and limitation of substrates for the
photooxidation with [FeCp2]+ is of great interests, the research of which
is now under way. Ferrocenium(III) cation is the basic compound that
has been widely used as a reference electrode even in photochemical
experiments. Thus, this result that ferrocenium(III) cation or its derived
species in acetonitrile also works as a fluorescent photosensitizer with
excitation and emission wavelengths at around 380 nm to give rise to the
unexpected oxidation reactions that cannot be produced without the
irradiation of light should be widely informed to take caution with the
use of FeCp20/+ redox pair for the photochemical experiments.[20]
[19] Reported first reduction potentials of Ph3PO in acetonitrile and [Ph3POMe]OTf
(rapidly hydrolyzed into [Ph3POH]OTf and meth-anol in the presence of residual
water) in methanol are both ca. –2.0 V vs SCE. See a) K. S. V. Santhanam, A. J.
Bard, J. Am. Chem. Soc. 1968, 90, 1118–1122; b) A. V. Il'yasov, Yu. M. Kargin,
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M. Lutz, K. Lammertsma, J. C. Slootweg, Z. Anorg. Allg. Chem. 2017, 643, 916–
921.
Acknowledgements
The present project is supported by CREST, JST (JPMJCR1541). We
acknowledge Grants-in-Aid for Scientific Research (Grant Numbers
JN17K05803 to Y.T., JP16KT0160 to K.N., and JP17H01201,
JP15H05798, and JP18K19093 to Y.N.) from JSPS and MEXT.
[20] CCDC 1865529 contains the supplementary crystallographic data for this paper.
These data can be obtained free of charge from The Cambridge Crystallographic
Data Centre.
Conflict of interest
The authors declare no conflict of interest.
Keywords: ferrocenium • fluorescence • oxidation • phosphine •
photosensitizer • water
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Entry for the Table of Contents
COMMUNICATION
Stoichiometric oxidation of
Yoshiaki Tanabe, Kazunari Nakajima,
Yoshiaki Nishibayashi*
phosphines with water and
ferrocenium(III) cation as an
oxygen atom source and an
oxidizing reagent, respectively, in
acetonitrile under the irradiation of
visible light has been achieved by
using 2,6-lutidine as a proton
acceptor. The reaction requires
irradiation of light, where
2
1
0
Page No. – Page No.
Phosphine Oxidation with Water
and Ferrocenium(III) Cation
Induced by Visible Light Irradiation
300
500
fluorescence behavior is observed
for the acetonitrile solution of
ferrocenium(III) cation.
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