Lipophilic M(α,α′-OC5H11)8phthalocyanines (M = H2 and Ni(II)): Synthesis, electronic structure, and their utility for highly efficient carbonyl reductions

Article abstract of DOI:10.1039/c5dt03256c

A lipophilic and electron-rich phthalocyanine (α,α′-n-OC₅H₁₁)₈-H₂Pc and its nickel(ii) complex (α,α′-n-OC₅H₁₁)₈-Ni(ii)Pc have been synthesized and characterized. Detailed analyses of the electronic structure were carried out by spectroscopy, electrochemistry, spectroelectrochemistry, and TD-DFT calculations. A series of experiments demonstrate that the (α,α′-n-OC₅H₁₁)₈-Ni(ii)Pc complex can be used as a catalyst for highly efficient carbonyl reductions.

Full text of DOI:10.1039/c5dt03256c

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DOI: 10.1039/C5DT03256C
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ARTICLE
Lipophilic M(α,α’-OC H ) Phthalocyanines (M = H and Ni(II)):
5
11 8
2
Synthesis, Electronic Structure, and their Utility for Highly Efficient
Carbonyl Reductions
Received 00th January 20xx,
Accepted 00th January 20xx
a
a
a*
b*
b
b
DOI: 10.1039/x0xx00000x
Yu Jiang, Minzhi Li, Xu Liang, John Mack, Martin Wildervanck, Tebello Nyokong, Mingfeng
a
a*
Qin , Weihua Zhu
www.rsc.org/
A lipophilic and electro-rich phthalocyanine (α,α’-n-OC
5
H
11 8
) -H
2
Pc and its nickel(II) complex (α,α’-n-OC
5
H
11
) -Ni(II)Pc have
8
been synthesized and characterized. Detailed analysis of the electronic structure were carried out by spectroscopy,
electrochemistry, spectroelectrochemistry, and TD-DFT calculations. A series of experiments demonstrate that the (α,α’-
n-OC
5
H
11 8
) -Ni(II)Pc complex can be used as catalysts for highly efficient and selective carbonyl reductions.
most important and basic chemical transformations in organic
chemistry. It is an important step in the synthesis of natural
Introduction
products,[ bulk and fine chemicals.
11]
[12]
Phthalocyanines (Pcs) have been the subject of
considerable research interest over the past few decades in
Numerous methods have been developed to achieve this
transformation selectively in the presence of other reducible
[1]
[2]
various fields, such as solar cells, molecular electronics and
functionalities[ using trialkyl boranes with ionic liquid, and
13]
[14]
[
3]
[4]
[5]
photonics, nonlinear optics, photodynamic therapy (PDT),
metal such as gold , manganese , iridium[17], platinum[18]
ruthenium[19], rhodium[20], osmium[21]
[15]
[16]
,
[
6]
and also catalysis. The main advantages of phthalocyanine in
this regard is that its π-system can absorb and emit strongly in
the red/near-infrared (NIR) due to the relatively high molar
extinction of the lowest energy π→π* band (usually referred
to as the Q band), which is considerably more intense than the
corresponding bands in the spectra of porphyrins and
.
Use of costly metals,
stoichiometric amounts of additives and poor selectivity limits
their scope. Nickel is abundantly available and found to be
effective for carbonyl reduction due to its cost effectiveness
over other frequently used transition metals. Although
Ni(II)Pcs have been studied as catalysts for carbonyl reduction
previously,[ Ni(II)Pcs with electron rich π-systems are likely
to form better catalysts for their reduction. Phthalocyanines
with electron-donating substituent groups at the non-
peripheral positions have red-shifted Q bands, since there are
large MO coefficients at these positions in the HOMO of the π-
[
7]
tetraazaporphyrins.
thermally stable and have relatively low reactivity due to their
Also, phthalocyanines are highly
22]
heteroaromatic π-systems, and have been reported to have
[8]
low toxicity. The major drawback faced with most metallo-
phthalocyanine (MPc) complexes is that the Q band lies in the
6
50
IR region are usually preferred. A red-shift of the Q band
reflects a decrease in the HOMO LUMO gap, and hence is
680 nm region, while complexes with a band in the near
system and the destabilization of this MO results in a
23]
significant narrowing of the HOMO

LUMO gap.[
Several

aryl-substituted carbonyl derivatives are lipophilic thus
reactions in high-polar solvent such as methanol or PEG-400
may not be suitable for many of these derivatives. So, Ni(II)Pcs
with long alkyl-substituents and deformed structure merit
consideration for the carbonyl reductions of lipophilic
associated with changes in the oxidation and reduction
potentials. Although the band can be shifted to longer
wavelength through fused-ring-expansion with benzene rings
[
9]
to form naphthalocyanine (Nc) and then anthracocyanine
10]
(
Ac),[ the marked destabilization of HOMO level makes these
compounds.
n-Pentoxy substituents were selected for
compounds unstable and in the absence of peripheral
substituents there are also issues with solubility. On the other
hand, the reduction of carbonyl functionalities is one of the
incorporation at the α,α’-positions, since long alkyl-chains and
deformed structures significantly enhance the solubility
compared with the regular phthalocyanines.[
24]
In this manuscript, the synthesis, characterization,
spectroscopy, electrochemistry, spectroelectrochemistry,
a.School of Chemistry and Chemical Engineering, JiangSu University, Zhenjiang
theoretical calculations of lipophilic M(α,α’-n-OC
and Ni(II)) and its utility for applications on highly efficient
carbonyl reductions will be detailed described
5 11 8
H ) -Pcs (M
2
13200, P. R. China. E-mail: sayman@ujs.edu.cn(W. Zhu); liangxuujs@126.com(X.
=
H
2
Liang).
b.
Department of Chemistry, Rhodes University, Grahamstown 6140, South Africa. E-
mail: j.mack@ru.ac.za
†
Electronic Supplementary Information (ESI) available: structural characterization
and theoretical calculation data. See DOI: 10.1039/x0xx00000x
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DOI: 10.1039/C5DT03256C
Scheme 1 Synthesis of α, α’-(C
5
H11O)
8
-phthalocyanine
were used to simplify the calculations. Slightly saddled
structures were predicted with N N angles in the central
cavity of below 10 for 3a (3.4 and 3.7 ). TD-DFT calculations
2 and its Nickel(II) complex 3a.
M
Experimental
General
1H NMR spectra were recorded on a Bruker AVANCE 500
or Bruker AVANCE 400 spectrometer (operating at 500.13 MHz
°
°
by using CAM-B3LYP functional, which includes a long-range
correction of the exchange potential by incorporating an
increasing fraction of Hartree-Fock (HF) exchange as the
interelectronic separation increases, was used for
2 and 3a.
or 400.03 MHz) using the residual solvent as an internal
1
This makes it more suitable for studying compounds where
there is significant charge transfer in the electronic excited
states as is likely to be the case with Pc complexes substituted
by bulky n-alkoxy substituents at the α, α’-positions.
reference for H (δ = 7.26 ppm for CDCl
3
, δ = 5.32 ppm for
2 2
CD Cl ). All reagents and solvents were of commercial reagent
grade and were used without further purification except
where noted. Cyclic voltammetry was performed in a three-
electrode cell using Chi-730D electrochemistry station.
A
Synthesis and Characterizations
Synthesis of 1,4-n-OC H11-2,3-phthalonitrile. 1,4-(OH) -2,3-
5 2
phthalonitrile (1.6 g, 10 mmol) was added to 20 mL of a dry acetone
solution containing 1-iodopentane (4.4 g, 22 mmol, 2.2 eq.) and
2 3
K CO (5.5 g, 40 mmol, 4.0 eq). The resulting mixture was gradually
glassy carbon disk electrode was utilized as the working
electrode while a platinum wire and a saturated calomel
electrode (SCE) were employed as the counter and reference
electrodes, respectively. An “H” type cell with a fritted glass
layer to separate the cathodic and anodic sections of the cell
was used for bulk electrolysis. The working and counter heated to 60°C, and the temperature was maintained for 4 h. After
electrodes were made from platinum mesh and the reference removal of the solvent, the reaction mixture was purified by silica
electrode was an SCE. Both the working and reference gel column chromatography with CHCl3 as the eluent.
electrodes were placed in one compartment while the counter Recrystallization from CHCl and MeOH provided 1,4-n-OC H -2,3-
3
5 11
electrode was in other compartment of the cell. UV-visible
spectroelectrochemical measurements were performed with a
home-made optically transparent thin-layer cell with Pt mesh
as the working electrode. The potential was applied using a
Chi-730D potentiostat. Time-resolved UV-visible spectra were
recorded with a HP 8453A diode array spectrophotometer. All
electrochemical and spectroelectro-chemical measurements
were carried out under a nitrogen atmosphere. An Agilent
HP6890 GC gas chromatography system with a HP5975-MSD
detector was used to separate and identify the products of
catalytic Carbonyl Reductions. Magnetic circular dichroism
phthalonitrile as a white solid compound in 88% yield (2.64 g). 1H
NMR (400 MHz, CDCl ): δ = 7.15 (s, 2H; β-phenyl), 4.04 (t, J = 8.0 Hz,
H; -OCH -), 1.84 (dd, J =12.0 Hz, J = 8.0 Hz, 4H; -CH -), 1.491.35
m, 8H, -CH CH -), 0.93 (t, J = 8.0 Hz, 6H; -CH ).
Synthesis of H -α,α’-n-(OC -phthalocyanine (H
mg, 8.0 mmol) was added to 6 mL of freshly distilled 1-butanol, and
the solution was stirred and heated at 150°C under an N
atmosphere until the lithium was completely dissolved. 1,4-OC
,3-phthalonitrile (300 mg, 1.0 mmol) was then added and the
3
4
(
2
1
2
2
2
2
3
2
5 11
H )
8
2
Pc). lithium (56
2
5 11
H -
2
resulting mixture was gradually heated at 160°C, and the
temperature was maintained for 2 h. After removal of the solvent,
the reaction mixture was purified by silica gel column
(MCD) spectra were recorded on
a
JASCO J-815
spectrodichrometer equipped with a JASCO electromagnet,
which produces magnetic fields of up to 1.6 T (1 T = 1.0 tesla)
chromatography with CHCl
with both parallel and antiparallel fields. The conventions of Recrystallization from CHCl
3
:MeOH (100:3) as the eluent.
3
and MeOH provided the target
Piepho and Schatz are used to describe MCD intensity and the compound 2, as a green solid in 63% yield (2.64 g). MALDI-TOF-MS:
[
25]
98 8 8
m/z = 1203.78 (Calcd. for C72H N O
[M+H] = 1203.70); H NMR
1
Faraday terms.
(
2
2
500 MHz, CD Cl ): δ = 7.49 (m, 8H; β-phenyl), 4.82 (m, 16H; -OCH -),
2
2
2
Computational methods
The Gaussian 09 software package[26] was used to carry
out DFT geometry optimizations for
.19 (m, 16H; -CH
4H; -CH
2
-), 1.641.48 (m, 32H, -CH
2
CH
2
-), 1.090.85 (m,
). UV/vis (toluene): λmax [nm] (ε [M1 cm ]) = 781
1
3
2 and 3a-c by using the
(
123000), 735 (61500), 691 (45400), 428 (28400), 324 (34300).
B3LYP functional with 6-31G(d) basis sets. Ethoxy substituents
2
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Figure 1 MCD (top) and UV/visible absorption spectra (bottom) of 2 in toluene and 3a in CHCl
3
. Calculated TD-DFT spectra are plotted
against a secondary axis. The CAM-B3LYP functional was used for the 2 and 3a calculations with SDD basis sets. Larger red diamonds
are used to highlight the Q and B1 bands, while smaller purple, gray, green and black diamonds denote bands associated with
transitions involving the 3d orbitals, the four frontier π-MOs localized primarily on the peripheral benzo groups, nπ* and the remaining
ππ* states, respectively.
Synthesis of Ni(II)-α,α’- (OC
98 mg, 4.0 mmol, 4.0 eq) and H
dissolved in 4 mL of anhydrous DMF, and the solution was stirred the free base phthalocyanine with metal acetate salt and the
and heated at 180°C for 20 min under an N
atmosphere. The complexes were isolated by silica gel or alumina column
5 11 8
H ) Pc (Ni(II)Pc). Ni(CH
3
COO)
2
∙4H
2
O
alkyl substituents and deformed molecular structure. The
(
2
Pc (120 mg, 1.0 mmol) were Ni(II)Pc 3a was obtained through metal insertion reactions of
2
reaction mixture was poured into ice-water (30 mL) once it had chromatography.
cooled to the room temperature. After filtration, the green solid
Optical spectra and TD-DFT calculations.
.
compound was collected and further purified by silica gel column
chromatography with CHCl :MeOH (100:3) as the eluent. The
3
The optical spectra of metal free phthalocyanine 2 were
target compound 3a was obtained in 88% yield. MALDI-TOF-MS: measured in toluene, while those of nickel(II) phthalocyanine
[M] = 1260.30); 1H NMR 3a were measured in CHCl
m/z = 1260.41 (Calcd. for C72
400 MHz, CD Cl
OCH -), 2.20 (m, 16H; -CH
.10~0.98 (m, 24H; -CH ). UV/vis (CHCl
44 (133000), 667 (30200), 454 (11500), 327 (39600).
H
N
96 8
NiO
8
3
(Figure 1). In its simplest
perimeter model description,[
27,28]
the optical spectroscopy of
(
2
2
): δ = 7.49 (br s, 8H; β-phenyl), 4.78 (br s, 16H; -
radially symmetric MPc complexes can be described based on
a consideration of perturbations to the molecular orbitals
2
2
-), 1.631.50 (m, 32H, -CH
2
CH
2
-),
): λmax [nm] (ε [M1 cm ]) =
1
1
7
3
3
2

(
MOs) arising from the C16
of the inner ligand perimeter. The MOs of the parent
perimeter are arranged in an M = 0, ±1, ±2, ±3, ±4, ±5, ±6, ±7,
sequence in ascending energy. The highest occupied
molecular orbital (HOMO) has an M value of ±4 while the
H16 parent hydrocarbon perimeter
L
8
Results and discussions
Synthesis.
L
L
lowest occupied molecular orbital (LUMO) has an M value of
was obtained in a good yield (68%) following with ±5. Michl[ referred to two frontier π-MOs derived from the
28]
H
2
Pc
the so-called lithum method
phthalonitrile in freshly distilled 1-butanol. The 1H NMR
signals of
in Figure S1 (see ESI) are split due to non-planar corresponding MOs which lie on antinodes are referred to as
conformations caused by steric hindrance between the large the and -s MOs (Figure 2). This terminology facilitates the
α,α’-substituents.
, is highly soluble in the common organic comparison of complexes with differing symmetries. The spin
solvents, such as CHCl
2
[
1a]
HOMO and LUMO of the parent perimeter with nodal planes
that lie on the y-axis as and -a, respectively, while the
5
by reacting 1,4-OC H11-2,3-
a
2
s
2
3
, CH
2
Cl
2
, ethylacetate, due to the long- allowed transitions between the
a
,
s
,
-a and -s MOs forms the
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Figure 3 MO energies of 2 (left) and 3a (right) during B3LYP
geometry optimizations with SDD basis sets. Small black
diamonds are used to denote occupied MOs. Thicker gray and
green lines are used to highlight the four frontier π-MOs
associated with Gouterman’s 4-orbital model[26] and the 3d
orbitals of the central metal ion of 3a, respectively. Blue lines
are used to highlight four occupied frontier π-MOs, with MO
coefficients largely localized on the four peripheral benzo-
moieties, which are destabilized by the presence of the
Figure 2 The frontier π-MOs of H
s MOs of Michl’s perimeter model[21] with M
2
Pc 2 showing the a, s, -a and -
= ±4 and ±5
L
nodal patterns (TOP). The s and -s MOs have antinodes aligned
with the y-axis, while the a and -a MOs have nodal planes. The
nodal patterns of the corresponding MOs are shown (Center)
along with those of four occupied frontier π-MOs (Bottom) that
are primarily localized on the peripheral benzo groups and are
destabilized by the incorporation of electron-donating
substituents at the α,α’-positions.
electron-donating alkoxy-substituents.
Large dark gray
diamonds are used to highlight the HOMOLUMO gaps and are
plotted against a secondary axis.
basis of Gouterman’s 4-orbital model,[
29]
destabilization of the HOMO of the Pc
narrowing of the HOMO LUMO gap, due to the presence of
large MO coefficients at these positions (Figures 2 and , and
Table S1 as ESI). In contrast, in the spectra of 3a, there are
terms or pseudo- terms at 741, 735 and 825 nm,
respectively, correspond to the absorption bands at 744, 738
and 826 nm. The marked differences in the Q band
wavelengths of the transition metal complexes of
phthalocyanines can be readily explained by the effects of
-system and hence a
which predicts an

allowed B transition (
L
M = ±1) and a forbidden Q transition
3
(M
L
= ±9) arising from the four spin-allowed one-electron
[30]
A
1
HOMO → LUMO transitions. The Stillman group used the
simultaneous spectral band deconvolution of the electronic
absorption and magnetic circular dichroism (MCD) spectra of
phthalocyanines to identify the presence of a second intense
absorption band close in the B band region, so the band
nomenclature for phthalocyanines was modified to, in
A
1
mixing between the doubly degenerate LUMO of the Pc π-
ascending energy, the Q (ca. 670 nm), B
1
(ca. 370 nm), B
2
(ca.
system and the 3d MOs.[
29]
The B1 bands of the three metal
3
30 nm), N (ca. 275 nm), L (ca. 245 nm) and C (ca. 210 nm)
[29,30b]
complexes 3a can be readily assigned on the basis of the
presence of terms or pseudo- terms in the MCD spectra
bands.
The additional information provided by the MCD
[
1a,31]
A
1
A
1
technique
spectral features, the Faraday
Derivative-shaped Faraday
most D4h symmetry metal porphyrin and phthalocyanine
complexes. These are replaced by coupled pairs of
oppopsitely-signed Gaussian-shaped Faraday terms, when
is derived from three highly characteristic
terms.[31-33]
at 326, 322 and 349 nm, respectively, slightly to the red of
where they are predicted to lie in the TD-DFT calculations
A
1
,
B
0
and C
0
1
A terms dominate the MCD of
(
Figure 1 and Table 1). These MCD bands correspond closely
to the absorption bands at 327, 322 and 351 nm. The B band
of the free-base phthalocyanine is predicted to lie
2
B
0
significantly further to the red at 428 nm. In the TD-DFT
calculations, a much larger separation is predicted between
there is no three-fold or higher axis of symmetry.
As would normally be anticipated for
a
free-base
2

[
1a]
MOs derived from the HOMO of the
hydrocarbon perimeter, since there are large MO coefficients
on the pyrrole nitrogens of the lower energy MO (Figures 1
and ). In contrast, these atoms lie on nodal planes in the
higher energy MOs, so metal complexation has a smaller
effect. The bands that lie between the and bands in the
spectrum of , are probably associated with ππ* states that
C
16
H
16
parent
phthalocyanine, the Q band of
of oppositely-signed Faraday terms in the MCD spectrum at
78 and 730 nm correspond closely to the absorption bands
2 is symmetry-split. The pair
B
0
s
7
2
observed at 781 and 735 nm, and there is a shoulder of
vibrational intensity at 691 nm. The significant red-shift of the
main absorption band can be attributed to the introduction of
electron donating substituents at the α, α’-positions, since it
has been demonstrated previously that there is
a
Q
B
1
[1a]
2
are destabilized by the incorporation of the alkoxy substituents
a
4
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Figure 4 DPV and CV data for 2 in o-dichlorobenzene (left) and DMF (right) containing 0.1 M TBAP, scan rate = 100 mV/s.
Figure 5 DPV and CV data for 3a in o-dichlorobenzene (left) and DMF (right) containing 0.1 M TBAP, scan rate = 100 mV/s.
(
Figures 2 and 3a).[34] In TD-DFT calculations, four occupied based on earlier studies of the reduced species of transition
frontier π-MOs that are localized primarily on the peripheral metal Pcs,[ and the predicted energies of the 3d orbitals in
36]
benzo groups are destabilized relative to the
s MO that is Figure 3. In o-dichlorobenzene, Ni(II)Pc 3a has two reversible
associated with the B band in the 300 400 nm region. In the oxidation processes at E
spectrum of the metal complex 3a, the differences of the assigned as a ligand oxidation (Pc /Pc ) and (Pc /Pc ). Two
electronic structures are mainly related to the decrease in the reduction processes were also observed in o-dichlorobenzene

½
=

0.38 and

1.01 V, which can be
2



0
2

3

3

4

½ ½
HOMOLUMO gap, due to the introduction of the electron assigned to E = 0.85 V (Pc /Pc ), E = 1.31 V (Pc /Pc ).
donating n-OC
5
H
11 substituents.
The significant difference observed in the voltammograms and
in the potential values indicate that there is a large solvent
effect on the electronic structure of the electron-rich Ni(II)Pc
Electrochemistry
3a.
When electron-donating substituents are introduced on
the phthalocyanine ligand there is an increase in the electron
density of the phthalocyanine π-system thereby leading to
more difficult ring-reduction and easier ring-oxidation.
Spectroelectrochemistry
Thin-layer spectroelectochemistry measurements were
Additionally, both CV and DPV measurements were also carried out to develop a better understanding of the redox and
carried out in non-polar o-dichlorobenzene, similar optical properties of Pc and Ni(II)Pc 3a The
electrochemistry curves were observed in the voltammograms, measurements were carried out in o-dichlorobenzene (Figure 6,
but the E potential values change significantly due to the left side) and DMF (Figure 6, right side) to study the impact of
large effect of solvent polarity on the electronic structure of solvent polarity. A marked decrease in intensity of the most
the free base phthalocyanine . The cyclic voltammogram (CV) intense absorption band in the Q band region of H Pc 2 is observed
of H Pc in non-polar o-dichlorobenzene contains two in both solvents. Although similar spectral changes are observed in
reversible oxidation processes at E 0.57 and 0.76 V, and both solvents, they are more pronounced in o-dichlorobenzene. A
1.37, 1.64 and large solvent effect is also observed during the oxidation of 2.
H
2
2
.
½
2
2
2
2
½
=


three reversible reduction processes at E
½
=


st

1.99 V. The gap between the 1 oxidation and reduction Although loss of the intensity of the Q bands is observed in both
Ox1
Red1
potentials (E

E
) is ΔE = 2.06 V. When DMF is used to solvents, an increase in intensity of a band at 845 nm is only
provide a more polar solvation environment, Ni(II)Pc 3a has an observed in o-dichlorobenzene. In contrast in DMF, the main
oxidation peak at E 0.38 V (Figure 5, right), which can be band in the NIR region lies at 778 nm. The optical
assigned as a ligand oxidation (Pc /Pc ), and the three spectroscopy of the anion radical species of free base
reduction peaks can be readily assigned to E 0.85 V phthalocyanine is an area that merits further in depth study.
½
= 

2

1
½
= 
2

3

3

4

4

5

(
Pc /Pc ), E
½
=

1.31 V (Pc /Pc ) and E
½
=

1.97 V (Pc /Pc )
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The ring reduction nature of the first reduction of Ni(II)Pc 3a was geometry of the anion radical species, which is known in the
View Article Online
DOI: 10.1 [03 73 ]9 /C5DT03256C
confirmed by thin-layer spectroelectrochemistry. The spectra absence of a rigid geometry related to axial ligation to be subject
obtained for the α,α’-alkoxy-substituted Ni(II)Pc 3a are broadly to a static Jahn-Teller effect that removes the main four-fold axis of
similar to those reported previously for the unsubstituted nickel symmetry,[38] could account for this. Markedly different spectra

phthalocyanine parent complex when the red-shift of the Q and B have been reported for [M(II)Pc(3)] species on this basis.
bands of the neutral complex is taken into consideration.[36a,b,f]
Upon oxidation, significant solvent effects are also observed. The
Almost identical spectral changes are observed in the Q band region diagnostic loss of intensity in the Q band region to form the

at 744 nm in o-dichlorobenzene (Figure 7, left side) and DMF oxidized [Ni(I)Pc] species of 3a is observed in both solvents. Only
(
5
Figure 7, right side), but significant differences are observed in the in the case of the o-dichlorobenzene measurements, is there a
00600 nm region and in the emergence of bands in the NIR significant increase in the absorption bands in the near-infrared
region at λ = 980 and 860 nm for 3a in o-dichlorobenzene and DMF, region at λ = 800 nm and 940 nm. In contrast in DMF, the main
respectively. The emergence of bands in this spectral region is band lies at 744 nm. This may be due to a solvent and

usually diagnostic for the formation of [Ni(II)Pc(3)] and temperature dependent monomer-dimer equilibrium similar
Ni(II)Pc(4)]2 species.

[36a,b,f]
It is possible that differences in the to that reported previously for [Mg(I)Pc] , which was found to

[
have Q bands at 717 nm for the monomeric and dimeric
species, respectively, when analyzed in depth using EPR
spectroscopy and a simultaneous spectral band deconvolution
analysis of the UV-visible absorption and MCD spectra.[
39]
Application on Carbonyl Reduction
The use of Ni(II)Pc 3a for the catalysis of carbonyl
reduction reactions has been studied in depth. The use of
sodium borohydride (NaBH
4
) in the absence of any metal
under solvent free conditions has been reported.[ However,
40]
the long reaction time and the use of excess NaBH
scope of this approach.[
4
limits the
40a]
Scheme 2 Optimization of Carbonyl Reduction conditions.
Figure 6 Thin-layer spectroelectrochemistry of 2 in o-
dichlorobenzene (left side) and DMF (right side) containing
Table 1 Optimized reaction conditions a
.
0
.1M TBAP.
No.
1
2
3
4
5
6
7
8
Catalyst
---
Hydrogen Source
Yield
n.d.
n.d.
n.d.
n.d.
65%
63%
65%
45%
>99%
n.d.
n.d.
n.d.
n.d.
---
---
---
---
NiCl
NiSO
Ni(CH COO)
NiCl
NiSO
Ni(CH COO)
2
4
3
2
2
2
NaBH
NaBH
NaBH
NaBH
NaBH
4
4
4
4
4
4
3
---
9
Ni(II)Pc 3a
Ni(II)Pc 3a
Ni(II)Pc 3a
Ni(II)Pc 3a
Ni(II)Pc 3a
10
11
12
13
NaHCO
NH NH
3
2
2
2
H O
CH COOH
3
Reactions were carried out by using 1.0 mmol of substrate,
catalyst] ratio = 0.1 % mol yield: GC-yield, Reaction time, 2 h
[
;
.
Following the synthetic procedure described in Scheme 2
,
1
.0 mmol carbonyl derivatives, 0.1% mol Ni(II)Pc as the
3
Figure 7 Thin-layer spectroelectrochemistry of 3a in o-
dichlorobenzene (left side) and DMF (right side) containing
catalyst (0.1% eq), and 0.5 mmol sodium borohydride (0.5 eq)
were mixed in 2.0 mL 1-pentanol. The reaction solution was
stirred at room temperature and the progress of the reaction
0
.1M TBAP.
6
| J. Name., 2012, 00, 1-3
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ARTICLE
was monitored periodically by TLC (silica; petroleum GC-MS. Studies of Ni(II)Pc 3a catalyzed carbonVyielw rAertdicluecOtniolinne
ether/ethylacetate) and GC-MS.
Upon completion, the initially focused on the optimization oDfOrI:e1a0c.1t0io3n9/Cc5oDnTd0i3t2io56nCs
reaction mixture was extracted with diethyl ether (3 mL). The Scheme 2 Table 1). Facile and mild conditions would make
(
,
combined diethyl ether fractions were dried under reduced 3a suitable for use in applications. Several catalysts and
pressure and the crude product was directly characterized by proton sources were tested to confirm that Ni(II)Pc 3a reveal
highly efficient carbonyl reduction. As expected, only NaBH
4
can be used as hydrogen source under current reaction
conditions, and the yield of the carbonyl reduction is higher
than 99% based on the GC-MS analysis.
Scheme 3 Optimization of Carbonyl Reduction conditions.
Table 2 Solvent effect of Carbonyl Reduction.
The effect of solvent polarity on the carbonyl reductions
(
Scheme 3
lipophilic
,
Table 2), was also tested in several kinds of
solvent including toluene, chloroform,
tetrahydrofuran (THF) and 1,4-dioxane. No reaction occurred
in lipophilic solvents. Instead, we tried to use methanol,
ethanol, PEG-400 and others, and the most satisfactory result
was obtained in 1-pentanol and 1-octanol. This is because
Ni(II)Pc 3a contains long n-alkyl-chains at the α,α’-positions.
The increase in the length of the alkyl-substituents of the
No.
1
Catalyst
Proton Source
Solvents
CHCl
Yield
n.d.
Ni(II)Pc 3a
Ni(II)Pc 3a
Ni(II)Pc 3a
Ni(II)Pc 3a
Ni(II)Pc 3a
Ni(II)Pc 3a
Ni(II)Pc 3a
Ni(II)Pc 3a
Ni(II)Pc 3a
Ni(II)Pc 3a
NaBH
NaBH
NaBH
NaBH
NaBH
NaBH
NaBH
NaBH
NaBH
NaBH
4
4
4
4
4
4
4
4
4
4
3
2
3
PhMe
THF
n.d.
n.d.
alcohol enhances the solubility of 3a
.
More usefully, 1-
4
5
6
7
8
9
1,4-dioxane
MeOH
n.d.
pentanol is much cheaper than PEG-400 and can be recycled
by distillation, and it is better than the most satisfied result
described previously.
After optimization of the carbonyl reduction conditions was
complete, several aryl-aldehydes were tested to confirm the
65%
63%
65%
45%
>99%
95%
EtOH
iPrOH
PEG-400
1-pentanol
1-octanol
10
Reactions were carried out by using 1.0 mmol of substrate;
catalyst ratio = 0.1 % mol; Yield: GC-yield; Reaction time: 20
min.
Scheme 4 Optimization of Carbonyl Reduction conditions.
Table 3 Substituent effect of Carbonyl Reduction.
No.
1
R-aldehyde
Time
Temp.
Yielda
92%
No
.
7
R-aldehyde
Time
(min)
30
Temp.
Yielda
93%
o
o
(
min)
( C)
( C)
o
o
30
25 C
25 C
2
3
4
5
25
25
25
25
25oC
25oC
25oC
25oC
90%
88%
85%
87%
8
9
30
30
40
40
25oC
25oC
25oC
25oC
91%
87%
89%
88%
10
11
6
20
25oC
92%
12
30
25oC
85%
Reactions were carried out by using 1.0 mmol of substrate catalyst ratio = 0.1 % mol; Yield: isolated yield.
This journal is © The Royal Society of Chemistry 2015
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Kobayashi, Chem. Eur. J., 2014, 20, 4822; (c) S. SVhieiwmAirztiucl,eYO.nIlitnoe,
substituent effect of the starting materials (Scheme 4).
Halogen substituted aldehydes with electron-withdrawing
abilities were efficiently reduced to the corresponding alcohols
in good to excellent yields with no dehalogenation. Methyl,
methoxy, dimethylamino, nitrile and acid functionalities
remain unaffected during the reduction of the corresponding
aldehydes (Table 3, entries 4–8). There is no significant
change upon changing the electron-donating or withdrawing
substituents. The carbonyl reduction results are summarized
K. Oniwa, S. Hirokawa, Y. Miura, O. Matsushita, N. Kobayashi,
DOI: 10.1039/C5DT03256C
Chem. Comm., 2012, 48, 3851; (d) J. Mack, L. Sosa-Vargas, S.
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1, 1845.
1
1
Conclusions
3
A lipophilic and electron-rich phthalocyanine (α,α’-n-
OC H ) -H Pc and its nickel(II) complex (α,α’-n-OC H ) -
5 11 8 2 5 11 8
(
1
1
4 G. W. Kabalka, R. R. Malladi, Chem. Commun. 2000, 22, 2191.
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J. Yu, X. B. Lou, Y. Cao, H. Y. He, K. N. Fan, Chem. Commun.
Ni(II)Pc have been synthesized and characterized. The
electronic structures have been studied using optical
spectroscopy including the UV-visible absorption and MCD
techniques, electrochemistry including the use of CV and DPV,
spectroelectrochemistry, and TD-DFT calculations. A series of
experiments clearly demonstrate that the (α,α’-n-OC H ) -
5 11 8
Ni(II)Pc complex can be used as a catalyst to carry out highly
efficient carbonyl reductions.
2
010, 46, 1553; d) L. He, J. Ni, L. C. Wang, F. J. Yu, Y. Cao Y, H.
Y. He, K. N. Fan, Chem. Eur. J., 2009, 15, 11833.
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Acknowledgements
Financial support was provided by the NSFC of China (No.
1
1
8 K, Balazsik, K. Szori, G. Szollosi, M. Bartok, Chem. Commun.,
2
1171076) to WZ and an NRF of South Africa CSUR grant
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DOI: 10.1039/C5DT03256C
5 11 8 2 5 11 8
This paper described the electronic structure (α,α’-n-OC H ) -H Pc, (α,α’-n-OC H ) -Ni(II)Pc and
highly efficient carbonyl reductions catalyzed by Ni(II)Pc.