Synthesis, structure, and reactivity of [Cu(phen)2]ClO 2: Aerobic oxidation of Cl- to ClO2- at room temperature

Article abstract of DOI:10.1002/ejic.201301287

An unusual 4e^- oxidation of Cl^- into ClO ₂^- occurred during the reaction between CuCl and phenanthroline (phen) in air to form a [Cu(phen)₂]ClO₂ complex, which is capable of oxidizing catechol into the highly substituted pentenone derivative methyl 1-hydroxy-2-oxo-4,5,5-trimethoxycyclopent-3-ene-1- carboxylate through contraction of the aromatic ring by extradiol C-C bond cleavage concomitant with the further formation of a C-C bond. Copyright

Full text of DOI:10.1002/ejic.201301287

SHORT COMMUNICATION
DOI:10.1002/ejic.201301287
Synthesis, Structure, and Reactivity of [Cu(phen)2]ClO2:
Aerobic Oxidation of Cl– to ClO2 at Room Temperature
–
Md. Munkir Hossain,[a] Mei-Chun Tseng,[a] Chi-Rung Lee,[b] and
Shin-Guang Shyu*[a]
Keywords: Oxidation / Chlorine / Anions / Copper
An unusual 4e– oxidation of Cl– into ClO2 occurred during
the reaction between CuCl and phenanthroline (phen) in air
to form a [Cu(phen)2]ClO2 complex, which is capable of oxid-
izing catechol into the highly substituted pentenone deriva-
tive methyl 1-hydroxy-2-oxo-4,5,5-trimethoxycyclopent-3-
ene-1-carboxylate through contraction of the aromatic ring
by extradiol C–C bond cleavage concomitant with the further
formation of a C–C bond.
–
ambient conditions has not been reported. Herein, we re-
port the synthesis and single-crystal X-ray diffraction stud-
ies of the copper [Cu(phen)2]ClO2 (1, phen = phenanthrol-
ine) complex, an unprecedented 4e– oxidation of Cl– to
Introduction
Enzymes with a copper cofactor are ubiquitous in nature.
The predominant roles of most Cu enzymes are O2 acti-
vation and subsequent substrate oxidation. It is a great
challenge to mimic these reactions by using simple model
compounds with the aim to better understand biological
reactions and also to develop methods to synthesize bioin-
spired molecules. In biomimetic studies, a number of Cu–
O2 adducts have been synthesized and characterized with
various spectroscopic methods, and their reactivities in the
oxidation of organic substrates have been extensively inves-
tigated.[1] A prevalent important key reaction step is the
apparent interaction of O2 with a CuI site to yield a Cu–O2
species, which is then involved in O–O bond activation or
in the attack of organic substrates and subsequent oxi-
dation, both intramolecularly[2] and intermolecularly.[3] Al-
though copper-containing enzymes are able to oxidize or-
ganic substrates by incorporating two oxygen atoms (by di-
oxygenases such as quercentin 2,3-dioxygenase)[4] or only
one oxygen atom (by monooxygenases such as DβM, PHM,
and tyrosinase)[5] to afford the products, to the best of our
knowledge, the oxidative conversion of inorganic halides to
oxyanions by copper enzymes or copper complexes similar
to iron peroxidase[6] has not been reported.
–
form ClO2 through incorporation of two oxygen atoms.
Unique aerobic oxidation of catechol to the highly substi-
tuted pentenone derivative methyl 1-hydroxy-2-oxo-4,5,5-
trimethoxycyclopent-3-ene-1-carboxylate (4) together with
the catechol-oxidized product 4,5-dimethoxy-1,2-benzo-
quinone (3) by using complex 1 at room temperature is also
reported.
Results and Discussion
Stirring of a dichloromethane solution of CuCl and
phenanthroline at room temperature in air for 30 min re-
sulted in an orange solution. The orange residue, after evap-
oration of dichloromethane, was dissolved in methanol to
form
a
concentrated solution. After recrystallization
was obtained
through ether diffusion, complex
1
(Scheme 1) in high yield (ca. 93%). Copper phenantholine
complexes with different structures obtained through reac-
tions of CuCl and phenantholine in air and nitrogen have
been reported.[9]
Anodic oxidation of chloride ions into hypochlorite ions
in aqueous solution has been widely studied.[7] However,
oxidation of chloride ions in a chemical system under mod-
erate conditions is rare.[8] Aerobic oxidation of Cl– under
[a] Institute of Chemistry, Academia Sinica,
Taipei 11529, Taiwan, Republic of China
E-mail: sgshyu@chem.sinica.edu.tw
http://www.chem.sinica.edu.tw
[b] Department of Chemical Engineering, Minghsin University of
Science and Technology,
Scheme 1. Synthesis of complexes 1 and 2.
Taiwan, Republic of China
Supporting information for this article is available on the
WWW under http://dx.doi.org/10.1002/ejic.201301287.
To identify the structure of 1, single-crystal X-ray diffrac-
tion was performed. The target compound forms in the or-
Eur. J. Inorg. Chem. 2014, 36–40
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SHORT COMMUNICATION
thorhombic space group Fddd. The cationic moiety is
[Cu(phen)2]+. Copper is four-coordinate with two phen-
anthroline ligands and sits in the 222 special position. The
torsion angle between the two phenanthroline planes is
44.3°. For the anion part, the chemical formula is ClO–,
and a chlorine atom is located in a twofold axis that is par-
allel to the c axis. The oxygen atom is partially occupied in
a general position in the unit cell. Structural determination
by X-ray diffraction is due to global phenomena and does
not focus on special domains. For consistency with the
atomic ratio of the anion, the fragments can be grouped
–
into two types: one is ClO– and the other is Cl– + ClO2 .
To clarify the structure of 1, ESI mass spectrum of iso-
lated 1 was recorded. Signals at m/z = 423 in the ESI(+)
mass spectrum (Figure S1, Supporting Information) and at
m/z = 67, 132, 168, and 232 in the ESI(–) mass spectrum
(Figure S2, Supporting Information) were observed. Ac-
cording to mass accuracy and isotopic distribution of the
signals, the signal at m/z = 423 (Figure S3, Supporting In-
Figure 2. Molecular structure of 1 (thermal ellipsoids at 50% prob-
ability level). Hydrogen atoms are omitted for clarity. Selected dis-
tances [Å] and angles [°]: Cu1–N1 2.072(3); Cl1–O1 1.443(8); N1–
Cu–N1 107.42(18); N1–Cu–N1 80.17(17); O1–Cl1–O1 96.2(10).
formation) is assigned to the cationic [Cu(phen)2]+ part of stored in air at room temperature for months. However, 1
–
1, and the signal at m/z = 67 is assigned to the ClO2
was converted into the known green complex [Cu(phen)2-
counteranion (Figure 1, b). These results indicate that Cl]Cl·CH2Cl2·4H2O (2)[16] in 47% yield upon stirring its
ClO2– exists in the structure. On the basis of the above argu- dichloromethane solution at room temperature for 48 h in
–
ments, the structure of this ClO2 complex is assigned as air (Scheme 1). Formation of 1 and 2 indicates an overall
–
[Cu(phen)2]ClO2 and its structure is shown in Figure 2.
oxidation–reduction process of chlorine from Cl– to ClO2
and vice versa. Copper catalyzes the 4e– oxidation of the
chloride ion along with the 4e– reduction of oxygen and the
–
generated ClO2 ion. To the best of our knowledge, this is
the only example of aerobic metal-catalyzed oxidation of
chloride to chlorite.
In the case of iron peroxidase and the oxidation of the
chloride ion to HOCl by H2O2, the halide adds to the oxy-
gen atom of the FeO intermediate to form a transient ferric
hypohalous complex (Fe–OX, X = halide), and this then
dissociates into the ferric enzyme and free hypohalous
acid.[6] It was reported that HOCl can disproportionate into
–
ClO2 and Cl–. In our case, aerobic oxidation of the chlor-
ide ion to chlorine, which reacts with water to form HOCl
Figure 1. (a) Simulated and (b) experimental isotopic distribution
–
and which further disproportionates into ClO2 and Cl–, is
of [ClO2]– from pure 1. (c) In situ ESI-MS analyses.
unlikely, as the reaction (Scheme 1) is not performed in a
–
The ClO2 ion is a weak ligand and can coordinate basic aqueous solution.[17] It is not easy to propose the reac-
–
through the hard oxygen atom or through the soft chorine tion path for the formation of ClO2 in 1, but a possible
atom. The existence of labile chlorite complexes was pos- intermediate for chloride ion oxidation may be similar to
tulated in several redox reactions of the chlorite ion in solu- that of organic substrate oxidation catalyzed by copper
–
tion.[10] The formation of labile complexes of ClO2 with model complexes, that is, through the formation of a Cu–
FeIII [11] CuII,[12] UVIO2,[13] and HgII[14] ions was reported, O2 adduct.[18]
,
but these complexes were not isolated. Among the oxy-
To investigate the reaction path, in situ ESI-MS analyses
–
anions, the perchlorate ion (ClO4 ) is highly involved in were performed to identify the possible reaction intermedi-
complex formation as an outer-sphere counteranion as well ates in the reaction mixtures. ESI-MS measurements for the
as an inner-sphere ligand. Complexes with ClO3– are scarce, reaction mixture were performed in both the positive ion
–
and for ClO2 , the only isolated and crystallographically re- mode (Figure 3) and the negative (Figure 4) ion mode.
ported complex is [(NH3)5Co(ClO2)]2+[15] Thus, complex 1
The signals at m/z = 423, 243, 212, and 181 (Figure 3)
–
is the second example of a ClO2 complex. This is also the in the ESI(+) mass spectrum are assigned to [Cu(phen)2]+,
first isolated and crystallographically characterized transi- [Cu(phen)]+, [Cu(phen)2]2+, and [phen + H]+, respectively,
tion-metal complex with a chlorite ion as an outer-sphere on the basis of their measured accurate mass and isotopic
counterion. Furthermore, formation of 1 is unique in that distribution (Figures S4–S6, respectively, Supporting Infor-
the low-valent CuI in 1 is stabilized by the potential oxidant mation). The signal at m/z = 67 in the ESI(–) mass spectrum
chlorite ion as the counter anion. In solid form, 1 can be (Figure 4) is consistent with the formulation [ClO2]– accord-
Eur. J. Inorg. Chem. 2014, 36–40
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SHORT COMMUNICATION
Scheme 2. Oxidation of catechol.
but it seems to us that it is initiated by extradiol C–C bond
breaking of catechol to afford 2-hydroxymuconaldehyde fol-
lowed by contraction of the aromatic ring with further C–
C bond formation to yield 4 (Scheme 3).[20]
Figure 3. ESI(+)-MS of the reaction mixture.
Figure 4. ESI(–)-MS of the reaction mixture.
Scheme 3. Catechol cleavage by 1.
Although a few nonenzymatic oxidation reactions re-
sulting in C–C bond cleavage of catechol derivatives by mo-
lecular oxygen have been reported,[21] that of catechol itself
is rare.[19] Thus, the dual oxidative activity of 1, that is, oxi-
dation of catechol and insertion of O2 resulting in cleavage
of the C–C bond of catechol, is noteworthy.
ing to the measured accurate mass and isotopic distribution
(Figure 1, c).
Upon stirring a methanol solution of catechol and 1 at
room temperature for 40 h in air, catechol was oxidized to
4,5-dimethoxy-1,2-benzoquinone (3) and the unexpected
compound methyl 1-hydroxy-2-oxo-4,5,5-trimethoxycyclo-
pent-3-ene-1-carboxylate (4) in 51 and 14% yield, respec-
tively (Scheme 2). In a control reaction among CuCl, phen-
anthroline, and catechol in methanol under identical reac-
tion conditions, catechol was oxidized into 3 without the
Conclusions
In conclusion, the synthesis of CuI complexes is challeng-
formation of 4 (Scheme 2). This indicates that the oxidant ing, as disproportionation of CuI into Cu0 and CuII occurs
in the control reaction is not in situ formed 1. The chlorite under different thermodynamic conditions.[22] Thus, the iso-
ion is involved in the formation of 4 during the reaction lation of 1, which is composed of low-valent CuI and a
between catechol and 1. Compound 4 is a highly substi- chlorite ion as an outer-sphere counteranion, is really a
tuted pentenone derivative and it results from the contrac- unique occurrence. In other words, copper can not only cat-
tion of the aromatic ring of catechol through C–C bond- alyze the aerobic oxidation of organic substrates, but it can
–
breaking and bond-making reactions.
also catalyze the aerobic oxidation of Cl– into ClO2 . Com-
Oxidative C–C bond breaking of catechol is one of the pound 1 is the first example of a transition-metal complex
most important reactions catalyzed by dioxygenases.[19] Two containing outer-sphere chlorite as a counterion, and it is
types of ring cleavage of catechol by dioxygenases have been also the second crystallographically characterized chlorite
identified: one is intradiol, which cleaves the C–C bond be- ion complex. With regard to reactivity, because of the simi-
tween the two hydroxy groups (ortho cleavage) to yield mu- larities between molecular oxygen and the chlorite ion as
conic acid as the product, and the other is extradiol, which oxidants during their 2e– and 4e– reduction reactions (2H+
–
cleaves the C–C bond adjacent to one of the hydroxy groups + O2 + 2e– ǞH2O2, 2H+ + ClO2 + 2e– ǞClO– + H2O;
–
(meta cleavage) to afford 2-hydroxymuconaldehyde as the 4H+ + O2 + 4e– Ǟ2H2O, 4H+ + ClO2 + 4e– ǞCl–
+
product (Scheme 3).[20] The precise mechanism for the 2H2O),[23] the stable transition-metal complex [Cu(phen)2]-
transformation of catechol into 4 by 1 remains uncertain, ClO2 containing the ClO2 ion may be exploited as an oxi-
–
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SHORT COMMUNICATION
1.00 mmol) in methanol (30 mL). The resulting solution was stirred
for 40 h at room temperature in air. The workup of the reaction
was similar to the above reaction and afforded only 3 in 31%
(0.024 g) yield.
dant. The oxidative reactivity of 1, including anaerobic oxy-
genation of hydrocarbons and natural peroxidative-type
chlorination of organic substrates, is currently in progress.
Single-Crystal Structure Determination: A crystal of dimensions
0.26ϫ0.19ϫ0.10 mm was used to collect low-temperature Mo-Kα
X-ray diffraction data with an Oxford Atlas-CCD diffractometer
equipped with a nitrogen-vapor stream device. The gas stream tem-
perature was maintained at 100 K. Data collection, frame integra-
tion, and data reduction were performed with the CrysAlisPro
package. Structural refinement was performed by the SHELXL97-
2 program with full-matrix least-squares on F2. All calculations
were performed with the WinGX package. Crystal data for 1:
C24H16ClCuN4O, M = 475.40, orthorhombic, space group Fddd, a
= 3.7563(2) Å, b = 28.8194(10) Å, c = 37.7065(14) Å, V =
4081.9(3) Å3, T = 100(1) K, Z = 8, Dcalcd. = 1.547 Mgm–3, reflec-
tions collected = 6424, unique = 1128 [R(int) = 0.0238], R1 =
0.0499 [IϾ2.0σ(I)], R1 = 0.0530 (all data).
Experimental Section
General: All chemicals were obtained from commercial sources and
used without further purification. Methanol and ether were dried
prior to use. Microanalyses were performed by using a Perkin–
Elmer 2400 CHN analyzer. NMR spectra were measured in CDCl3
with a Bruker 200.1 MHz. High-resolution ESI mass spectra were
measured with a Waters LCT Premier XE with a dual ionization
ESCi at the Mass Spectrometry Facility in the Institute of Chemis-
try, Academia Sinica. Leucine Enkephalin 556.277 [M + H]+ was
used as a reference standard.
Synthesis of 1: A solution of cuprous chloride (0.05 g, 0.50 mmol)
and phenanthroline (0.18 g, 1.00 mmol) in dichloromethane
(30 mL) was stirred at room temperature for 0.5 h in air. The re-
sulting orange solution was filtered under a nitrogen atmosphere,
and the solvents were evaporated to dryness. The residue was dis-
solved in a minimum amount of methanol. Ether diffusion into the
CCDC-960231 (for 1) contains the supplementary crystallographic
data for this paper. These data can be obtained free of charge from
The Cambridge Crystallographic Data Centre via www.ccdc.cam.
ac.uk/data_request/cif.
methanol solution afforded
C24H16ClCuN4O (475.41): calcd. C 60.63, H 3.39, N 11.78, O 3.37;
found C 60.31, H 3.62, N 11.59, O 3.49.
1
in 93% (0.229 g) yield.
Supporting Information (see footnote on the first page of this arti-
cle): ESI mass spectra and selected crystallographic data.
Synthesis of 2 from 1: A solution of 1 (0.1 g, 0.21 mmol) in di-
chloromethane (30 mL) was stirred at room temperature for 48 h
in air. The green powder of 2 was filtered off in 47% (0.049 g) yield.
[Cu(phen)2Cl]Cl·CH2Cl2·4H2O (651.86): calcd. C 46.01, H 4.02, N
8.59; found C 46.12, H 3.63, N 8.79. Crystal system, monoclinic;
space group, C2/c; a = 20.5041(5) Å, b = 13.0967(3) Å, c =
20.3638(5) Å; β = 111.07(10)°.
Acknowledgments
Financial support from the National Science Council of the Repub-
lic of China (NSFC) and Academia Sinica is gratefully acknowl-
edged.
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tion of cuprous chloride (0.05 g, 0.50 mmol) and phenanthroline
(0.18 g, 1.00 mmol) in dichloromethane (30 mL) was stirred at
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and catechol (0.04 g, 0.37 mmol) in methanol (30 mL) was stirred
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1
1
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1
Data for 4: H NMR (200.1 MHz, CDCl3): δ = 5.54 (s, 1 H), 3.96
(s, 3 H), 3.80 (s, 3 H), 3.47 (s, 3 H), 3.40 (s, 3 H) ppm. The green
residue was crystallized from methanol solution and identified as
known compound 2 with methanol as a solvent of crystallization,
[Cu(phen)2Cl]Cl·CH3OH. Crystal system, monoclinic; space group,
P21/n; a = 14.3687(3) Å, b = 10.6661(3) Å, c = 14.8377(4) Å; β =
99.9460(10)° (see Figure S10 and Table S1, Supporting Infor-
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Methanol: Catechol (0.05 g, 0.46 mmol) was added to a solution of
cuprous chloride (0.05 g, 0.50 mmol) and phenanthroline (0.18 g,
Eur. J. Inorg. Chem. 2014, 36–40
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Received: October 2, 2013
Published Online: December 3, 2013
Eur. J. Inorg. Chem. 2014, 36–40
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