C-P bond construction catalyzed by NiII immobilized on aminated Fe3O4@TiO2 yolk-shell NPs functionalized by (3-glycidyloxypropyl)trimethoxysilane (Fe3O4@TiO2 YS-GLYMO-UNNiII

Article abstract of DOI:10.1039/c9nj00352e

Ni^II immobilized on aminated Fe₃O₄@TiO₂ yolk-shell NPs functionalized by (3-glycidyloxypropyl)trimethoxysilane (Fe₃O₄@TiO₂ YS-GLYMO-UNNi^II) was prepared as a stable, h

Full text of DOI:10.1039/c9nj00352e

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Jason B. Benedict et al.
The role of atropisomers on the photo-reactivity and fatigue of
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C-P bond construction catalyzed by NiII immobilized on aminated
Fe3O4@TiO2 yolk-shell NPs functionalized by (3-
(Fe3O4@TiO2 YS-GLYMO-
Received 00th January 20xx,
Accepted 00th January 20xx
glycidyloxypropyl)trimethoxysilane
UNNiII) in green media
DOI: 10.1039/x0xx00000x
Maryam Sadat Ghasemzadeh a and Batool Akhlaghinia,*a
www.rsc.org/
NiII immobilized on aminated Fe3O4@TiO2 yolk-shell NPs functionalized by (3-glycidyloxypropyl)trimethoxysilane
(Fe3O4@TiO2 YS-GLYMO-UNNiII) was prepared as a stable, highly efficient, and reusable magnetic nanostructured catalyst
for the C-P cross coupling reaction. A variety of spectroscopic and microscopic techniques such as Fourier transform
infrared (FT-IR) spectroscopy, X-ray diffraction (XRD) analysis, transmission electron microscopy (TEM), field emission
scanning electron microscopy (FE-SEM), energy-dispersive X-ray spectroscopy (EDS), EDS-map, thermogravimetric analysis
(TGA), vibrating sample magnetometry (VSM), inductively coupled plasma atomic emission spectroscopy (ICP-AES) and
CHNS analysis were used to characterize the synthesized nanostructured catalyst. The characterizations determined that
the nanostructured catalyst is superparamagnetic in nature, structured as core-shell and its average particle size is 30-32
nm. The catalytic activity of this new magnetic nanostructured catalyst (Fe3O4@TiO2 YS-GLYMO-UNNiII) was examined in
the C-P cross coupling reaction of aryl halides/ aryl boronic acids/ styrene/ phenylacetylene with diethylphosphite/
triethylphosphite in the presence of WERSA so that arylphosphonates/ vinylphosphonate/ alkynylphosphonate could be
prepared in a short period of time. In all the cases, the nanostructured catalyst could be easily recovered magnetically for
at least seven runs and a simple work-up procedure was used to isolate the obtained products. The present methodology
proved to be quite suitable for scale-up and commercialization.
despite the fact that the reported traditional synthetic entries
into carbon-phosphorus (C-P) bond-forming reactions are
1. Introduction
Among the plethora of organic compounds, organophosphorus
compounds occupy a significant position. Over the recent
decades, much attention has been paid to research dedicated
to the development of versatile methods for the synthesis of
organophosphorous compounds1-3 owing to their widespread
applications in medicinal chemistry,4-6 materials chemistry,7,8
organic synthesis9,10 and catalysis.11,12 The transition metal
(including Ni, Cu, Mn, Rh, Ag, Zn, Zr, Fe and Pd) catalyzed
carbon-phosphorus (C-P) bond-forming reactions between
Csp2-X, B(OH)2, H/or Csp-H and diethylphosphite /or
triethylphosphite are the first powerful, reliable and the most
widely-used methods for the synthesis of various types of
organophosphorus compounds.13-40 Based on the ideology of
green chemistry, much attention has been concentrated on
the development of these classic methods via the modification
and improvement of the catalyst,41,42 and reaction
conditions38,40 to meet the requirements of contemporary
synthetic organic demands which calls energy efficiency,
operational simplicity and environmental safety. Nevertheless,
suitable, some of them still have limitations and suffer from
severe problems related to the separation, recovery, and
instability of the homogeneous catalysts (result in undesirable
metal contamination of the products) as well as use of volatile
and hazardous organic solvents,31,39,43 the requirement of
expensive ligands,44,45 aggressive reagents (caused a lack of
tolerance for functional groups), microwave oven33 and long
reaction times to give good conversions. Therefore, effort to
elaborate a new catalytic method of industrial applicability
with (a) insensitivity to air, (b) recyclability, (c) sustainability
from an environmental point of view, (d) versatility, and (e)
potential scalability for the easy preparation of
organophosphorus compounds via direct C-P bond forming
reactions could be the subject of intense research in this
area.46-55 With respect to the principle of green chemistry in
organic synthesis, heterogenization of homogeneous catalyst
through the immobilization of homogeneous catalyst on a
suitable insoluble supporting material enables efficient
removal and recycling of the catalyst and minimizes the
amount of waste as well. In addition, magnetic nanoparticles
(MNPs) are being applied as attractive solid supports for the
immobilization of homogeneous catalysts due to their simple
handling, low cost, super magnetic susceptibility, easy
recovery with an external magnetic field, high catalytic activity
and high stability in various organic transformations.56
aDepartment of Chemistry, Faculty of Science, Ferdowsi University of Mashhad,
Mashhad 9177948974, Iran. E-mail: akhlaghinia@um.ac.ir; Fax: +98-51-3879-
5457; Tel: +98-51-3880-5527
Electronic Supplementary Information (ESI) available: General information, and
spectral data of organic compounds. See DOI: 10.1039/x0xx00000x
This journal is © The Royal Society of Chemistry 20xx
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Moreover, Fe3O4 NPs have drawn the most attention owing to 100 KV. FE-SEM images, EDS and EDS-map were recorded
View Article Online
their strong magnetic responsiveness, low toxicity, excellent using a TESCAN, Model: MIRA3 scanning electron microscope
DOI: 10.1039/C9NJ00352E
stability, biocompatibility, large surface-to-volume ratio and operating at an acceleration voltage of 30.0 kV and resolution
their potential applications.57,58 The magnetite NPs tend to of about 200 and 500 nm (manufactured in the Czech
aggregate due to anisotropic dipolar attraction, and thereby Republic). TGA analysis was carried out on a Shimadzu
lose their catalytic activity and dispersibility. These problems Thermogravimetric Analyzer (TG-50) in the temperature range
can be untangled by coating with a sustainable layer such as of 25-900 °C at a heating rate of 10 °C min-1 under air
polymer,59 metal oxide (MO),60 carbon61 and silica,62 as the atmosphere. The magnetic properties of the catalyst were
stabilizer, to form a core-shell and/or yolk-shell structures. measured using a vibrating sample magnetometer (VSM,
Yolk-shell nanostructures (YSNPs) have diverse applications Magnetic Danesh Pajoh Inst.). Inductively coupled plasma
including catalysis,63 microwave absorber,64 sensors65 and atomic emission spectroscopy (ICP-AES) was carried out with a
biomedicine.66 However, YSNPs have drawn significant Varian VISTA-PRO, CCD (Australia). All yields refer to isolated
attention in recent years because of their unique properties products after purification by thin layer chromatography.
such as low density, large surface area and ease of interior
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core functionalization in spite of core-shell structures.67 Metal- 2.2. Preparation of magnetite nanoparticles Fe3O4 NPs (I)
organic frameworks (MOFs) have been the focus of increasing Under Ar atmosphere at room temperature, FeCl2.4H2O (10
attention during the past decade.68 MOF-based structures show mmol, 1.99 g) and FeCl3.6H2O (12 mmol, 3.25 g) were
several advantages such as high surface areas, adjustable pore dissolved in deionized water (30 mL). Subsequently, to the
sizes, and the simplicity of processability.69,70 In addition, MOFs and stirring mixture, NH4OH solution (0.6 M, 200 mL) was then
functionalized- or modified-MOFs have been applied as solid added dropwise to reach the reaction pH of 11. The resulting
catalysts in Sonogashira,71 alkene epoxidation,72 Knoevenagel,73,74 black dispersion was continuously stirred for 1 h at room
Friedel-Crafts alkylation and acylation,75 Suzuki,76 Biginelli77 and aza- temperature, and then refluxed for 1 h. The magnetic
Michael reactions.78Considering the importance of developing a nanoparticles were separated with a magnetic field and
new procedure using a heterogeneous nanocatalyst for the C-P washed with deionized water until it was neutralized. Fe3O4
bond formation, and in continuation of our recent studies on NPs (I) was then dried at 50 °C for 24 h.
the introduction of sustainable chemistry and heterogeneous
nanocatalyst,79-100 herein, NiII immobilized on aminated 2.3. Preparation of Fe3O4@SiO2 (II) core-shell
Fe3O4@TiO2
yolk-shell
NPs
functionalized
by
(3- The as-prepared Fe3O4 NPs (I) (3.5 g) were dispersed in a
glycidyloxypropyl)trimethoxysilane (Fe3O4@TiO2 YS-GLYMO- mixture of ethanol (160 mL), water (40 mL), and NH4OH (0.6
UNNiII) was synthesized according the synthetic process M, 3.5 mL). Subsequently, TEOS (0.009 mmol, 2.0 mL) was
illustrated in Scheme 1. In this line, functionalization of added dropwise, and the reaction was allowed to proceed for
Fe3O4@TiO2
YSNPs
was
carried
out
by
(3- 24 h under stirring at 40 °C. The resulting Fe3O4@SiO2 (II) was
glycidyloxypropyl)trimethoxysilane and further reaction with washed with ethanol, separated by magnetic decantation and
UiO-66(Zr)-NH2 (V') to produce aminated Fe3O4@TiO2 yolk- dried at 60 °C for 12 h under vacuum.
shell NPs. Then, immobilization of NiII was performed via a
reaction of Fe3O4@TiO2 YS-GLYMO-UN with ethanolic solution 2.4. Preparation of Fe3O4@SiO2@TiO2 (III)
of Ni(OAc)2.4H2O. Afterwards, the catalytic activity of The obtained Fe3O4@SiO2 (II) (3 g) were first calcined at 300 °C
Fe3O4@TiO2 YS-GLYMO-UNNiII (VII) was subsequently in static air for 2 h and then dispersed in isopropyl alcohol
investigated toward the C-P cross coupling reaction, in green (41.47 mL), followed by the addition of NH4OH (0.6 M, 3.0 mL).
media (see Scheme 2).
After stirring for 5 min, tetra-n-butyl orthotitanate (TNBT) (5.8
mmol, 2 g) was added to the reaction mixture. The resulting
mixture was then transferred into a Teflon-lined stainless steel
autoclave with a capacity of 100 mL and kept at 200 °C for 24 h
to obtain Fe3O4@SiO2@TiO2 (III).101
2. Experimental
2.1. General
All chemical reagents and solvents were purchased from
Merck and Sigma-Aldrich chemical companies and were used
as received without further purification. The purity
determinations of the products were accomplished by TLC on
silica gel polygram STL G/UV 254 plates. The melting points of
the products were determined with an Electrothermal Type
9100 melting point apparatus. The FT-IR spectra were
recorded on an Avatar 370 FT-IR Therma Nicolet spectrometer.
Elemental analyses were performed using a Thermo Finnegan
Flash EA 1112 Series instrument. The NMR spectra were
obtained in Brucker Avance 300 and 400 MHz instruments in
CDCl3. Mass spectra were recorded with a CH7A Varianmat
Bremem instrument at 70 eV electron impact ionization, in
m/z (rel %). The crystal structure of catalyst was analyzed by
XRD using Model PW1730 (manufactured in the Netherlands)
diffractometer Dectvis operated at 40 kV and 30 mA utilizing
Cu Kα radiation (λ= 0.15056 A°). Transmission electron
microscopy (TEM) was performed with a Zeiss-EM10C
(manufactured in Germany) with an accelerating voltage of
2.5. Preparation of Fe3O4@TiO2 (IV) yolk-shell
Fe3O4@SiO2@TiO2 (III) (2 g) was mixed with an aqueous
solution of KOH (0.2 M, 40 mL) that was heated in a water
bath at 50 °C for 24 h. The resulting mixture was washed with
ethanol (4× 20) and dried at 60 °C under vacuum overnight.
Finally, the powder was calcined at 400 °C under Ar
atmosphere for 2 h with a heating rate of 5 °C min-1 to obtain
the Fe3O4@TiO2 (IV) yolk-shell.101
2.6. Preparation of Fe3O4@TiO2 YS-GLYMO (V)
Fe3O4@TiO2 (IV) (2.0 g) was dispersed in dry toluene (40 mL)
by
sonication
for
1
h.
Next,
(3-
glycidyloxypropyl)trimethoxysilane (GLYMO) (4.5 mmol, 1 mL)
was added to the resulting mixture and slowly heated to reflux
for 24 h. The obtained Fe3O4@TiO2 YS-GLYMO (V) was
separated by an external magnet and washed in turn by
diethyl ether (2× 30 mL), CH2Cl2 (3× 30 mL) and dried at 80 °C
2 | J. Name., 2012, 00, 1-3
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for 12 h under vacuum. Elemental analysis and TGA showed the solution was transferred to a 100 mL Teflon-lined stainless
View Article Online
that the loading amount of C atom was 0.4 mmol per gram of steel autoclave. The autoclave was sealed and heated in an
DOI: 10.1039/C9NJ00352E
catalyst.
oven at 120 °C for 48 h. The mixture was washed with
methanol (4×15) to eliminate the occluded DMF. The UiO-
66(Zr)-NH2 (V') was obtained by drying under vacuum at 100 °C
2.7. Preparation of UiO-66(Zr)-NH2 (V')
ZrCl4 (1.0 mmol, 0.23 g) and 2-aminoterephthalic acid (H2ATA) for 24 h.102
(1.0 mmol, 0.18 g) were dissolved in DMF (50 mL), and then
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FeCl3.6H2O
FeCl2.4H2O
NH4OH
Ar, r.t
(1) KOH (aq)
(1) Calcination (300 °C)
(2) NH4OH, TNBT
TEOS
(2) 50 °C, 24 h
(3) Calcination (Ar, 400 °C)
Fe3O4@TiO2 yolk-shell (IV)
Fe3O4@SiO2 (II)
Fe3O4 NPs (I)
Fe3O4@SiO2@TiO2 (III)
GLYMO, Toluene, Reflux
NH2
O
O
O
O
Si
O
Fe3O4@TiO2 YS-GLYMO (V)
Toluene, Reflux, Ar
ZrCl4
NH2
DMF, 120 °C, 48 h
H2
N
H2
N
2-Amino 1,4-benzenedicarboxylic acid
UiO-66(Zr)-NH2 (V')
O
O
O
Si
O
O
OH
HO
O
HN
Si
O
O
OH
NH
N
O
H
O
Si
NH
O
O
O
HO
Si
O
O
O
Ni(OAc)2, EtOH, Reflux
Fe3O4@TiO2 YS-GLYMO-UN (VI)
O
O
O
Si
AcO
Ni
AcO
Ni
O
OAc
OAc
HO
NH2
O
HO
O
O
Si
O
NH
H
N
O
HO
O
Si
O
Ni
OAc
O
HN
AcO
HO
OAc
OAc
Ni
O
Si
O
O
O
Fe3O4@TiO2 YS-GLYMO-UNNiII (VII)
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Scheme
1
Preparation of NiII immobilized on aminated Fe3O4@TiO2 yolk-shell NPs functionalized by
View Article On(li3ne-
glycidyloxypropyl)trimethoxysilane (Fe3O4@TiO2 YS-GLYMO-UNNiII (VII)).
DOI: 10.1039/C9NJ00352E
5
6
7
8
2.8. Preparation of Fe3O4@TiO2 YS-GLYMO-UN (VI)
Diethyl (4-methoxyphenyl)phosphonate (1d).35 Oil; isolated yield:
The prepared Fe3O4@TiO2 YS-GLYMO (V) (1.5 g) was sonicated 90%; 1H NMR: δH (400 MHz; CDCl3; Me4Si) 1.29-1.25 (t, JHH= 7.2 Hz,
in dry toluene (50 mL) for 1 h. Then, UiO-66(Zr)-NH2 (V') (0.7 g) 6 H), 3.80 (s, 3 H), 4.09-3.97 (m, 4 H), 6.93 (dd, JHH= 8.8 Hz, JHH=
was added to the dispersed Fe3O4@TiO2 YS-GLYMO (V) in 3.2 Hz, 2 H), 7.71 (dd, JHH= 12.8 Hz, JHH= 8.8 Hz, 2 H); 13C NMR: δC
toluene under Ar atmosphere and stirred under reflux (100 MHz, CDCl3) 16.2 (d, JCP= 6.0 Hz), 55.2, 61.8 (d, JCP= 6.0 Hz),
conditions for 24 h. The resulting Fe3O4@TiO2 YS-GLYMO-UN 113.9 (d, JCP= 16.0 Hz), 119.3 (d, JCP= 193.0 Hz), 133.7 (d, JCP= 12.0
(VI) was separated by an external magnet and washed with dry Hz), 162.8 (d, JCP= 4.0 Hz); MS, m/z 244 (M+, 8%).
toluene (4× 25) and dried at 80 °C for 24 h under vacuum.
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Diethyl p-tolylphosphonate (1e).35 Oil; isolated yield: 90%; 1H NMR:
δH (300 MHz; CDCl3; Me4Si) 1.35-1.31 (t, JHH= 6.9 Hz, 6H), 2.42 (s,
Elemental analysis and TGA showed that the loading amount
of N atom was 0.58 mmol per gram of catalyst.
3H), 4.21-4.01 (m, 4H), 7.29 (dd, JHH= 8.1 Hz, JHH= 3.3 Hz, 2H), 7.72
(dd, JHH= 13.2 Hz, JHH= 8.1 Hz, 2H); 13C NMR: δC (75 MHz; CDCl3;
Me4Si) 16.1 (d, JCP= 6.7 Hz), 16.3 (d, JCP= 6.7 Hz), 21.6, 61.9 (d, JCP=
5.2 Hz), 124.9 (d, JCP= 188.2 Hz), 129.2 (d, JCP= 15.0 Hz), 131.8 (d,
JCP= 9.7 Hz), 142.9 (d, JCP= 3.0 Hz); MS, m/z 228 (M+, 5%).
2.9. Preparation of Fe3O4@TiO2 YS-GLYMO-UNNiII (VII)
To a solution of Ni(OAc)2.4H2O (6 mmol, 1.48 g) in dry ethanol
(50 mL), the obtained Fe3O4@TiO2 YS-GLYMO-UN (VI) (2 g) was
added and refluxed for 24 h. The resulting Fe3O4@TiO2 YS-
GLYMO-UNNiII (VII) was separated with an external magnet
and washed with ethanol (3 × 30 mL) before drying at 60 °C
under vacuum (24h).
35
Diethyl (4-nitrophenyl)phosphonate (1h).
Oil; isolated yield:
90%; 1H NMR: δH (300 MHz; CDCl3; Me4Si) 1.36-1.32 (t, JHH= 6.9 Hz,
6H), 4.27-4.06 (m, 4H), 8.00 (dd, JHH= 12.7 Hz, JHH = 8.7 Hz, 1H),
8.3(dd, JHH= 8.7 Hz, JHH = 3.3 Hz, 1H); 13C NMR: δC (75 MHz; CDCl3;
Me4Si) 16.1 (d, JCP= 6.7 Hz), 16.3 (d, JCP= 6.0 Hz), 62.7 (d, JCP= 5.2
Hz), 123.3 (d, JCP= 15.0 Hz), 133.0 (d, JCP= 10.5 Hz), 135.8 (d,
JCP=185.2 Hz), 150.2 (d, JCP= 3.7 Hz); MS, m/z 257 (M+, 6%).
2.10. Typical procedure for the preparation of diethyl
phenylphosphonate in the presence of Fe3O4@TiO2 YS-
GLYMO-UNNiII (VII)
Fe3O4@TiO2 YS-GLYMO-UNNiII (0.4 mol%, 0.3 g) was added to a
stirring solution of iodobenzene (1.0 mmol, 0.203 g),
diethylphosphite (2.1 mmol, 0.28 g)/or triethylphosphite (2.1
mmol, 0.34 g) and water extract of rice straw ash (WERSA) (2.5
mL) at 90 °C. After completion of the reaction (2.10/1.15 h)
which was monitored by TLC, the reaction mixture was cooled
to room temperature. The catalyst was separated by a
magnetic field, washed with EtOAc (3 × 20 mL), dried and
reused for a consecutive run under the same reaction
conditions. The reaction mixture was then extracted with ethyl
acetate (3 × 15 mL) and the combined organic layer was dried
over anhydrous Na2SO4. After evaporation of the solvent, the
crude product was purified by thin layer chromatography using
ethylacetate/ methanol (10 : 3) to afford the pure diethyl
phenylphosphonate (0.140 g, 95% yield).
3. Results and discussion
3.1. The characterization of Fe3O4@TiO2 YS-GLYMO-UNNiII
(VII)
The novel magnetic nanostructured catalyst denoted as
Fe3O4@TiO2 YS-GLYMO-UNNiII (VII) was prepared via stepwise
procedure according to Scheme 1. The Fe3O4 MNPs were
prepared by coprecipitation of Fe (III) and Fe (II) salts in the
presence of NH4OH solution under Ar atmosphere at room
temperature. Next, Fe3O4 NPs (I) was coated with a layer of
silica through stirring Fe3O4 NPs (I) suspension in ethanol/
deionized water with tetraethyl orthosilicate. The as-prepared
Fe3O4@SiO2 (II) core-shell was first calcined in static air,
followed by addition of NH4OH and tetra-n-butyl orthotitanate
to achieve Fe3O4@SiO2@TiO2 (III). The obtained
Fe3O4@SiO2@TiO2 (III) was treated with KOH (aq) and then
calcinated under Ar atmosphere to produce Fe3O4@TiO2 (IV)
yolk-shell. After preparing the Fe3O4@TiO2 (IV) yolk-shell, the
obtained nanoparticles were subsequently reacted with (3-
glycidyloxypropyl)trimethoxysilane and then UiO-66(Zr)-NH2
(V') to form Fe3O4@TiO2 YS-GLYMO-UN (VI). Finally, NiII was
immobilized on the surface of Fe3O4@TiO2 YS-GLYMO-UN (VI)
through the reaction of Fe3O4@TiO2 YS-GLYMO-UN (VI) with
ethanolic solution of Ni(OAc)2.4H2O under reflux.
2.11. Preparation of water extract of rice straw ash (WERSA)
Dried rice straws were burnt to ashes to prepare the water
extract of rice straw ash (WERSA). 5 g of the ash was
suspended in deionized water (50 mL) and stirred for 30 min at
room temperature. The mixture was then filtered and the
filtrate was used as WERSA. WERSA consists of SiO2 (74.31 %),
A12O3 (1.40 %), Fe2O3 (0.73 %), TiO2 (0.02%), CaO (1.61 %),
MgO (1.89 %), K2O (11.30 %), Na2O (1.85 %) and P2O5 (2.65%).
Finally, litmus test was used to determine the pH of WERSA
and it was found to be 12.103
Characterization of NiII immobilized on aminated Fe3O4@TiO2
yolk-shell
NPs
functionalized
by
3-
glycidyloxypropyl)trimethoxysilane (Fe3O4@TiO2 YS-GLYMO-
UNNiII (VII)) was studied using some microscopic and
spectroscopic techniques including Fourier transform infrared
(FT-IR) spectroscopy, X-ray diffraction analysis (XRD),
transmission electron microscopy (TEM), field emission
scanning electron microscopy (FE-SEM), energy-dispersive X-
ray (EDS), EDS-map, thermogravimetric analysis (TGA),
vibrating sample magnetometry (VSM), inductively coupled
plasma atomic emission spectroscopy (ICP-AES) and elemental
analysis (CHNS) analysis.
2.12. Spectral data
Diethyl phenylphosphonate (1a).35 Oil; isolated yield: 95%; 1H
NMR: δH (400 MHz; CDCl3; Me4Si) 1.32-1.29 (t, JH,H= 6.8 Hz, 6 H),
4.16-4.05 (m, 4 H), 7.47-7.42 (m, 2 H), 7.53-7.51 (m, 1 H), 7.80 (dd,
JH,H= 13.2, JH,H= 8.4, 2 H); 13C NMR: δC (100 MHz; CDCl3; Me4Si)
16.3 (d, JCP= 7.0 Hz), 62.0 (d, JCP= 5.0 Hz), 131.7 (d, JCP= 10.0 Hz),
128.3 (d, JCP= 186.0 Hz), 128.4 (d, JCP= 15.0 Hz), 132.3 (d, JCP= 3.0
Hz); MS, m/z 214 (M+, 5%).
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FT-IR spectroscopy was used to confirm the presence of of UiO-66(Zr)-NH2 (V') consists of an inner Zr6O4(OH)4 core
View Article Online
corresponding functional groups at different steps involved in where the triangular faces of the DOZIr: 1-0o.c10ta39h/eCd9rNoJn003a52reE
6
the preparation of the nanostructured catalyst (Scheme 1). alternatively capped by μ3-O and μ3-OH groups (Ref. Code: 04-
Figure 1 demonstrates the FT-IR spectra of (a) Fe3O4@SiO2 (II), 005-5596).105 Furthermore, the average crystalline size of
(b) Fe3O4@SiO2@TiO2 (III), (c) Fe3O4@TiO2 yolk-shell (IV), (d) Fe3O4@TiO2 YS-GLYMO-UNNiII (VII) which was calculated using
Fe3O4@TiO2 YS-GLYMO (V), (e) UiO-66(Zr)-NH2 (V'), (f) Debye-Scherrer equation (d = Kλ/(βcosθ)) was estimated to be
Fe3O4@TiO2 YS-GLYMO-UN (VI), (g) Fe3O4@TiO2 YS-GLYMO- around 31 nm.
UNNiII (VII). As it is evident in Figure 1a, the broad absorption Transmission electron microscopy (TEM) was used to
band around 586 cm-1 can be attributed to Fe-O vibration. In determine the size and morphology of Fe3O4@TiO2 YS-GLYMO-
addition, two broad absorption bands around 3400 and 1084 UNNiII (VII) as illustrated in (Figure 3). The morphology of the
cm-1 can be ascribed to the hydroxyl groups (ν OH) and Si-O-Si prepared nanoparticles is shown to be spherical in shape and
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bond in Fe3O4@SiO2 core-shell (II), respectively.
structured as core-shell. In addition, the size of particles is also
The characteristic band in the region 800-500 cm-1 is related to about 30-32 nm. Distribution histogram of Fe3O4@TiO2 YS-
the stretching vibration mode of Ti-O which covered the broad GLYMO-UNNiII (VII) also revealed that the average diameter of
absorption band of Fe-O at 641-575 cm-1. In addition, the nanoparticles is 30.9 nm, which corresponds closely with XRD
stretching vibration of Si-O-Si bond in Fe3O4@SiO2@TiO2 (III) results.
can be observed as a strong broad band at 1078 cm-1 (Figure Field emission scanning electron microscopy (FE-SEM)
1b). Figure 1c displays the absorption band at 800-579 cm-1 technique was used to illustrate the size and morphology of
allocates the stretching vibration of Ti-O, moreover, the Fe3O4@TiO2 yolk-shell (IV) and Fe3O4@TiO2 YS-GLYMO-UNNiII
stretching vibrational mode of Si-O-Si was eliminated. Grafting (VII). As it is evident in Figure 4, FE-SEM images of Fe3O4@TiO2
of (3-glycidyloxypropyl)trimethoxysilane on the surface of yolk-shell (IV) and Fe3O4@TiO2 YS-GLYMO-UNNiII (VII) reveal
Fe3O4@TiO2 (IV) yolk-shell NPs is confirmed by the presence of that the nanoparticles have spherical shapes with an average
a typical band at 2929 and 2871 cm-1 that are attributed to particle size of about 887101 and 31 nm, respectively.
stretching vibrations of alkyl chains (C-H), and also the
characteristic stretching vibration of Si-O bond appears at
1102 (Figure 1d). FT-IR spectrum of UiO-66(Zr)-NH2 (V')
represents the asymmetric and symmetric N-H stretching
modes at 3469, 3362 cm-1, also the stretching vibration at
1257 cm-1 shows CAr-N bond.104 Additionally, the appearance
of absorption band at 1657 cm-1 attributes to C=O of -COOH
groups which coordinated with Zr4+.104 Besides, the stretching
vibration band of C=C bond (aromatic rings), the asymmetric
and symmetric stretching modes of the -COO appear at 1570,
1436 and 1387 cm-1, respectively (Figure 1e).104
Correspondingly, as can be clearly observed in Figure 1e, the
strong absorption band at 768 cm-1 is related to the stretching
vibrations of the Zr-O group in Zr6O4(OH)4.104 Increasing the
intensity and frequency of the hydroxyl groups in the FT-IR
spectrum shows the successful ring opening of epoxy ring
which was performed by UiO-66(Zr)-NH2 (V') (Figure 1f). Upon
NiII coordination, the intensities of absorption bands of N-H,
CAr-N and Zr-O stretching vibrations are decreased (Figure 1g).
(See supporting information file)
Fig.
1
FT-IR spectra of (a) Fe3O4@SiO2 (II), (b)
Fe3O4@SiO2@TiO2 (III), (c) Fe3O4@TiO2 yolk-shell (IV), (d)
Fe3O4@TiO2 YS-GLYMO (V), (e) UiO-66(Zr)-NH2 (V'), (f)
Fe3O4@TiO2 YS-GLYMO-UN (VI), (g) Fe3O4@TiO2 YS-GLYMO-
UNNiII (VII) and (h) the 7th recovered Fe3O4@TiO2 YS-GLYMO-UNNiII
(VII) from the C-P cross-coupling reaction.
The crystallographic structures of (a) Fe3O4@TiO2 yolk-shell
(IV), (b) UiO-66(Zr)-NH2 (V'), (c) Fe3O4@TiO2 YS-GLYMO-UNNiII
(VII) and (d) the 7th recovered Fe3O4@TiO2 YS-GLYMO-UNNiII
(VII) from the C-P cross-coupling reaction are investigated by
the XRD technique. As is evident in Figure 2a, the XRD pattern
shows reflection peaks at 2Θ = 30.1°, 35.5°, 37°, 62.8° and 75°
which can be indexed to (2 1 1), (1 1 2), (2 2 0), (0 0 4) and (6 2
0) reflections of the orthorhombic structure of Fe3O4,
respectively (Ref. Code: 98-001-7122). Additionally, as can be
recognized from the XRD pattern of Fe3O4@TiO2 yolk-shell (IV),
the reflection peaks at 2Θ = 25.2°, 38.5°, 47.9°, 53.8°, 54.9°,
62°, 68.7° and 70.1° are related to (1 1 0), (2 1 1), (0 2 0), (5 1
0), (1 2 1), (3 2 1), (6 1 1) and (0 2 2) reflections of the
tetragonal structure of TiO2, respectively (Ref. Code: 98-010-
9333). Similarly, the XRD profile of Figure 2b displays that
diffraction peaks at 2Θ = 7.34°, 8.48°, 12°, 14°, 17°, 18°, 22°,
25°, 31.5°, 35.5° and 37.5° represent the (1 1 0), (2 0 0), (3 1 1),
(2 2 2), (4 0 0), (4 2 0), (5 1 1), (6 0 0), (6 4 0), (8 2 0) and (6 6 2)
planes of UiO-66(Zr)-NH2 (V') structure. However, the structure
6 | J. Name., 2012, 00, 1-3
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Fig. 2 XRD patterns of (a) Fe3O4@TiO2 yolk-shell V(IieVw)A, r(tibcl)e OUnilOine-
66(Zr)-NH (V'), (c) Fe O @TiO YS-GLYMO-UNNiII (VII) and (d)
DOI: 10.1039/C9NJ00352E
the 7th recovered Fe3O4@TiO2 YS-GLYMO-UNNiII (VII) from the
2
3
4
2
C-P cross-coupling reaction.
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(b)
(a)
(d)
(c)
Fig. 3 (a, b, c) TEM images and (d) particle size distribution histogram of Fe3O4@TiO2 YS-GLYMO-UNNiII (VII).
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DOI: 10.1039/C9NJ00352E
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Fig. 4 The FE-SEM images of (a, b) Fe3O4@TiO2 yolk-shell (IV) and (c, d) Fe3O4@TiO2 YS-GLYMO-UNNiII (VII).
The type of elements in Fe3O4@TiO2 YS-GLYMO-UNNiII (VII)
was investigated by recording the energy-dispersive X-ray
(EDS) spectrum (Figure 5). The presence of Ni, Fe, Ti, Zr, Si, O,
N, and C in the EDS spectrum confirmed the composition of
the as-synthesized nanostructured catalyst (Fe3O4@TiO2 YS-
GLYMO-UNNiII (VII)).
C
Fe
The uniform dispersal of Ni, Fe, Ti, Zr, Si, O, N, and C on the
surface of nanostructured catalyst is shown by the
corresponding EDS-map images of Fe3O4@TiO2 YS-GLYMO-
UNNiII (VII) (Figure 6).
N
O
Si
Ni
Zr
Ti
Fig. 5 The EDS analysis of Fe3O4@TiO2 YS-GLYMO-UNNiII (VII).
Fig. 6 EDS-map images of Fe3O4@TiO2 YS-GLYMO-UNNiII (VII).
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attributed to the extrusion of physically absorbeVdiewwAarttieclre.OTnlhinee
To investigate the thermal stability of (a) Fe3O4@TiO2 yolk- grafted UiO-66(Zr)-NH2 (V') and (3-
DOI: 10.1039/C9NJ00352E
shell (IV), (b) Fe3O4@TiO2 YS-GLYMO (V), (c) Fe3O4@TiO2 YS- glycidyloxypropyl)trimethoxysilane fragments on the surface
GLYMO-UN (VI), (d) Fe3O4@TiO2 YS-GLYMO-UNNiII (VII) and of Fe3O4@TiO2 yolk-shell (IV) are decomposed during the
the 7th recovered Fe3O4@TiO2 YS-GLYMO-UNNiII (VII), TGA second and third steps weight loss (11.4/ 13.2 %, from 150 to
analysis was performed under air atmosphere at a heating rate 330 / 340 to 530 °C), respectively. Thus, the amount of organic
of 10 °C min-1 from 25 to 900 °C (Figure 7). The TGA of the segments is estimated to be 0.55 and 0.65 mmol/g.
Fe3O4@TiO2 yolk-shell (IV) (Figure 7a) depicts a rather Room temperature magnetization curve of (a) Fe3O4@TiO2
negligible weight loss (2 %) from 100 to 180 °C verifies water yolk-shell (IV) (b) fresh Fe3O4@TiO2 YS-GLYMO-UNNiII (VII) and
evaporation. Figure 7b demonstrates two steps of weight loss the 7th recovered Fe3O4@TiO2 YS-GLYMO-UNNiII (VI) from the
in TGA thermogram of Fe3O4@TiO2 YS-GLYMO (V). The first C-P bond construction are shown in (Figure 8 (a, b and c)),
step (150-220 °C, 5 %) corresponds to the loss of physically respectively. As demonstrated in (Figure 8), the value of
adsorbed water on the surface of Fe3O4@TiO2 yolk-shell (IV). saturation magnetic moments of Fe3O4@TiO2 YS-GLYMO-
The second step (230-420 °C, 4.8%) is due to the loss of the (3- UNNiII (VII) is Ms= 15.33 emu g-1 which is lower than the value
glycidyloxypropyl)trimethoxysilane linker. Therefore 0.44 of Fe3O4@TiO2 yolk-shell (IV) particles Ms= 43.06 emu g-1.
mmol/g of organic segments is grafted on the surface of Saturation magnetization of Fe3O4@TiO2 YS-GLYMO-UNNiII
Fe3O4@TiO2 yolk-shell (IV). In addition, according to the (VII) was decreased as non-magnetic materials were present
elemental analysis data, the loading amount of organic on the surface of Fe3O4@TiO2 yolk-shell (IV).
segments supported on Fe3O4@TiO2 yolk-shell (IV) was 0.4
mmol/g based on carbon content (C= 14.90 %).
TGA thermogram of Fe3O4@TiO2 YS-GLYMO-UN (VI) revealed
two significant mass changes at different temperature ranges.
The first mass change of about 12 %, from 100 to 200 °C, could
be assigned to remove of the trapped physically adsorbed
water. The second and indeed the significant mass change,
which was started at around 210 to 550 °C can be attributed to
the elimination of organic functional groups attached on the
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surface of Fe3O4@TiO2 yolk-shell (IV) (24 %). According to the
results obtained from the TGA thermogram (Figure 7c), the
amount of organic linkers anchored on Fe3O4@TiO2 yolk-shell
(IV) was estimated to be 0.591 mmol/g. These results were
also in good agreement with the obtained elemental analysis
data (C= 16.90 %, N= 17.37). In the profile of Fe3O4@TiO2 YS-
GLYMO- UN (VI), the TGA thermogram (Figure 7c) depicted
three-step thermal decomposition. As can be observed in
Figure7c, the weight loss of about 5 % from 90 to 130 °C in the
first step is
Fig. 8 Magnetization curves of (a) Fe3O4@TiO2 yolk-shell (IV),
(b) Fe3O4@TiO2 YS-GLYMO-UNNiII (VII) and (c) the 7th
recovered Fe3O4@TiO2 YS-GLYMO-UNNiII (VI) from the C-P
cross-coupling reaction.
3.2. Catalytic performance of the Fe3O4@TiO2 YS-GLYMO-
UNNiII (VII) in the C-P cross-coupling reaction
In order to highlight the advantages of using this new
nanostructured catalyst in organic synthesis, we applied it as
the catalyst for C-P cross-coupling reaction after full
characterization of the Fe3O4@TiO2 YS-GLYMO-UNNiII (VII)
(Scheme 2). The reaction conditions were optimized
systematically in our initial screening experiments. The results
are presented in Table 1. The standard reaction of C-P cross-
coupling was performed using iodobenzene with
diethylphosphite as the initial study. The optimized reaction
conditions were obtained by investigating the effect of
different amounts of catalyst loadings, various molar ratios of
iodobenzene/ diethylphosphite, several bases and different
temperatures. In the absence of either the base (in solvent-
free conditions at 100 °C, Table 1, entry 1) or the catalyst (in
the presence of WERSA (2.5 mL) at 100 °C, Table 1, entry 2), no
reasonable yield of the C-P cross-coupling product was
Fig. 7 TGA thermograms of (a) Fe3O4@TiO2 yolk-shell (IV), (b)
Fe3O4@TiO2 YS-GLYMO (V), (c) Fe3O4@TiO2 YS-GLYMO-UN (VI),
(d) Fe3O4@TiO2 YS-GLYMO-UNNiII (VII) and the 7th recovered
Fe3O4@TiO2 YS-GLYMO-UNNiII (VII) from the C-P cross-coupling
reaction.
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obtained even after a long period of time. The influence of the reaction rate significantly (Table 1, entries 13-18)V.ieNweAxrttic,leinOntlhinee
catalyst loading on the reaction rate and yield was investigated C-P cross-coupling reaction, the unique catalytic behaviour of
DOI: 10.1039/C9NJ00352E
by applying 1 /1.9, 2 and 2.1 molar ratio of iodobenzene/ Fe3O4@TiO2 YS-GLYMO-UNNiII (VII) was shown by examining
diethylphosphite under the temperature range of 80-100 °C in the model reaction in the presence of Fe3O4 NPs (I),
the presence of water extract of rice straw ash (WERSA) (2.5 Fe3O4@SiO2 (II), Fe3O4@SiO2@TiO2 (III), Fe3O4@TiO2 YS (IV),
mL) (Table 1, entries 3-11).Furthermore, the reaction of Fe3O4@TiO2 YS-GLYMO (V), Fe3O4@TiO2 YS-GLYMO-UN (VI),
iodobenzene with diethylphosphite in the presence of 0.4 mol% of Ni(OAc)2 and UiO-66(Zr)-NH2 (V') (Table 1, entries 19-26).
nanocatalyst at 90 °C and ground water (Damavand Mineral Although reaction times were prolonged, no considerable yield
Water was used as a source of ground water) was done (Table 1, was produced in the model reaction.
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entry 12). As can be clearly observed, the reaction was better With suitable reaction conditions established (Table 1, entry
performed in the presence of WERSA rather than ground water.
9), we next proceeded to assess the scope of C-P cross-
It is evident that the best result in the C-P cross-coupling coupling reaction of various activated and inactivated aryl
reaction were achieved by carrying out the reaction by halides/ aryl boronic acids including those containing
applying 1/1.2 molar ratio of iodobenzene/ diethylphosphite, electron-donating or electron-withdrawing groups, styrene
WERSA (2.5 mL) and 0.4 mol% of nanocatalyst at 90 °C (Table and phenylacetylene with diethylphosphite/ triethylphosphite
1, entry 9). In addition, some different bases such as Et3N, in the presence of Fe3O4@TiO2 YS-GLYMO-UNNiII (VII), the
K2CO3, i-Pr2NH, NaOAc, morpholine, and NaOH were studied results of which are summarized in Table 2.
and it was found that they did not improve the yield or
O
P(OEt)3
or
HP(O)(OEt)2
II
VII
Fe3O4@TiO2YS-GLYMO-UNNi ( ) (0.4 mol%)
+
X
Ar
Ar
P(OEt)2
WERSA (2.5 mL), 90 °C
X= H, I, Br, Cl, B(OH)2
Ar = C6H5, 4-OMeC6H4, 4-MeC6H4, 4-CNC6H4, 4-CHOC6H4, 4-NO2C6H4, 4-ClC6H4, 1-naphthyl, 2-thienyl,
,
CH
C6H5C C C6H5CH
Scheme 2 Synthesis of arylphosphonates/ vinylphosphonate/ alkynylphosphonate via Csp2/sp-P cross coupling reaction catalyzed
by Fe3O4@TiO2 YS-GLYMO-UNNiII (VII).
Table 1 Optimization of reaction conditions for the C-P cross-coupling reaction of iodobenzene with diethylphosphite in the presence of
Fe3O4@TiO2 YS-GLYMO-UNNiII (VII).
O
II
VII
Fe3O4@TiO2YS-GLYMO-UNNi (
)
HP(O)(OEt)2
+
I
P(OEt)2
Molar ratios of
Iodobenzene:
catalyst (mol%) Diethylphosphit
e
Temperature
(°C)
Time
Amount of
Isolated
Yield (%)
Entry
Base
(h)
1
2
-
1:2
-
100
100
100
100
100
100
100
100
90
24
24
-
-
-
1:2
WERSA (2.5 mL)
WERSA (2.5 mL)
WERSA (2.5 mL)
WERSA (2.5 mL)
WERSA (2.5 mL)
WERSA (2 mL)
WERSA (3 mL)
WERSA (2.5 mL)
WERSA (2.5 mL)
WERSA (2.5 mL)
3
0.3
0.3
0.3
0.4
0.4
0.4
0.4
0.5
0.4
1:2
2.5/24
2.5/24
2.25
2.10
2.30
2.10
2.10
2.10
2.30
80/80
75/75
95
4
1:1.9
1:2.1
1:2.1
1:2.1
1:2.1
1:2.1
1:2.1
1:2.1
5
6
95
7
80
8
95
9
95
10
11
90
95
80
85
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Ground water
View Article Online
DOI: 10.1039/C9NJ00352E
12
0.4
1:2.1
90
24
75
(2.5 mL)
5
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13a
14a
15a
16a
17a
18a
19b
20c
21d
22e
23f
24g
25h
26i
0.4
0.4
1:2.1
1:2.1
1:2.1
1:2.1
1:2.1
1:2.1
1:2.1
1:2.1
1:2.1
1:2.1
1:2.1
1:2.1
1:2.1
1:2.1
Et3N
90
90
90
90
90
90
90
90
90
90
90
90
90
90
24
24
24
24
24
24
24
24
24
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24
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24
85
45
65
50
40
35
-
K2CO3
0.4
i-Pr2NH
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0.4
NaOAc
0.4
Morpholine
NaOH
0.4
0.3 g
0.3 g
0.3 g
0.3 g
0.3 g
0.3 g
0.3 g
0.3 g
WERSA (2.5 mL)
WERSA (2.5 mL)
WERSA (2.5 mL)
WERSA (2.5 mL)
WERSA (2.5 mL)
WERSA (2.5 mL)
WERSA (2.5 mL)
WERSA (2.5 mL)
-
trace
20
25
35
40
trace
The reaction was performed in the presence of a base (1.5 mmol), b Fe3O4 NPs (I), c Fe3O4@SiO2 (II), d Fe3O4@SiO2@TiO2 (III), e Fe3O4@TiO2
YS (IV), f Fe3O4@TiO2 YS-GLYMO (V), g Fe3O4@TiO2 YS-GLYMO-UN (VI), h Ni(OAc)2 and i UiO-66(Zr)-NH2 (V').
The results in Table 2 revealed that the catalytic reaction of styrene, and phenylacetylene with diethylphosphite/
aryl iodides with diethylphosphite/ triethylphosphite (isolated triethylphosphite (entries 12-16). It could be seen that aryl
yields 85-95%, entries1,4-9) proved to be more productive boronic acids with electron-withdrawing group (-Cl)
than aryl chloride and aryl bromides coupling reaction with participated in the C-P cross coupling reaction more quickly
diethylphosphite/ triethylphosphite (entries 2, 3, 10, 11). This than the aryl boronic acids with electron-donating group (-CH3)
might be due to the fact that in all of the cases, the reactions (Table 2, entries 13 and 14). As shown in Table 2, styrene
with aryl iodides are faster than that of aryl bromide or aryl reacted more quickly with diethylphosphite/ triethylphosphite
chloride as the result of lower C-I bond strength vs. C-Br and C- than phenylacetylene and afforded the desired products in
Cl bonds. Furthermore, aryl iodides reactions containing shorter reaction times (Table 2, entry 15 vs entry 16). As it can
electron-withdrawing groups such as -NO2, -Cl, -CN and -CHO be seen throughout the whole table, aryl halides, aryl boronic
were completed faster with excellent yields in comparison acids, styrene, and phenylacetylene react faster with
with those containing electron-donating substituents such as - triethylphosphite than diethylphosphite.
Me and -OMe (Table 2, entries 4-9). This method was also
applicable for the reaction of some other aryl boronic acids,
Table 2 C-P cross-coupling reaction of aryl halides/ aryl boronic acids/ styrene/ phenylacetylene with diethylphosphite/ triethylphosphite in
the presence of Fe3O4@TiO2 YS-GLYMO-UNNiII (VII) in green media.
O
P(OEt)3
or
HP(O)(OEt)2
II
VII
Fe3O4@TiO2YS-GLYMO-UNNi ( ) (0.4 mol%)
+
X
Ar
Ar
P(OEt)2
WERSA (2.5 mL), 90 °C
1a-p
Time (h) of HP(O)(OEt)2/
P(OEt)3
Isolated Yield
(%)
Entry
1
R
X
I
C6H5
2.10/1.15
95
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ARTICLE
Journal Name
1
2
3
4
5
6
7
8
9
2
3
C6H5
Br
3/2
5/3
90
85
90
90
85
85
90
85
70
75
85
85
85
80
80
View Article Online
DOI: 10.1039/C9NJ00352E
C6H5
Cl
4
4-OMeC6H4
4-MeC6H4
4-CNC6H4
4-CHOC6H4
4-NO2C6H4
4-ClC6H4
1-naphthyl
2-thienyl
C6H5
I
4.30/2.40
4/3
5
I
6
I
3.20/2.20
3.40/3.10
3/1.50
3.30/3
6/4.30
5/4
10
11
12
13
14
15
16
17
18
19
20
21
22
23
24
25
26
27
28
29
30
31
32
33
34
35
36
37
38
39
40
41
42
43
44
45
46
47
48
49
50
51
52
53
54
55
56
57
58
59
60
7
I
8
I
9
I
Br
10
11
12
13
14
15a
16a
Br
B(OH)2
B(OH)2
B(OH)2
H
4/3.20
4.30/3.50
6/5
4-ClC6H4
4-MeC6H4
C6H5CH=CH
C6H5C≡C
5.5/4.25
7.20/5.10
H
a Reaction condition: Fe3O4@TiO2 YS-GLYMO-UNNiII (VII) (0.6 mol %).
All of the synthesized compounds were known and isolated as oil external magnetic field was used to remove the nanostructured
products. Molecular ion peaks of all the prepared products showed catalyst and then no nanostructured catalyst was used for the latter
their respective m/z based on mass spectrometric data. part of the reaction. Thin layer chromatography was performed to
Furthermore, the structure of the selected compounds was further track the progress of the reaction. There was no further coupling
investigated by surveying their high-field 1H NMR and
C NMR reaction even after an extended time. As can be seen, an isolated
13
spectral data. The completion of the reaction, monitored by TLC, yield of 63 % was achieved for the C-P cross-coupling reaction. The
was confirmed when starting material began disappearing. (See reaction mixture was analyzed using ICP-AES and the results
supporting information file for details)
Scheme 3 shows the suggested mechanism for the C-P cross- Ni species was leached out from the surface of Fe3O4@TiO2 YS-
coupling reaction. In the first step, the mechanism proceeded GLYMO-UNNiII (VII) NPs which in turn indicates that the
through oxidative addition of aryl halide to Fe3O4@TiO2 YS-GLYMO- nanostructured catalyst is heterogeneous. The results of hot
UNNiII (VII) NPs which yielded intermediate I through the oxidation filtration test for the C-P cross-coupling reaction were also
of NiII to NiIV. Upon the coordination of diethylphosphite/ presented in (Figure 9), indicating a strong attachment of NiII to the
triethylphosphite to intermediate I, the intermediate II produced Fe3O4@TiO2 YS-GLYMO-UN (VI) NPs surface.
after the deprotonation under basic condition or an Arbuzov type
showed that during C-P cross-coupling reactions, only 0.02 ppm of
reaction that RX is eliminated from adduct I'. Finally, using the Poisoning test
reductive elimination of intermediate II with the simultaneous A poisoning test was carried out under the optimized reaction
release of Fe3O4@TiO2 YS-GLYMO-UNNiII (VII) for the next catalytic conditions in order to determine the homogeneity/heterogeneity of
cycle, the intended coupling product (III) of C-P cross-coupling the catalyst. Ethylenediamine tetraacetic acid (EDTA), due to its
reaction was obtained.106
high affinity to capture NiII ions causing the formation of a stable
complex (VI), was used as an excellent scavenger (Scheme 4).107 In
this point, the model reaction was performed in two separate flasks
while Fe3O4@TiO2 YS-GLYMO-UNNiII (VII) was present in both of
3.3. Heterogeneity studies
Hot filtration test
To investigate whether the reaction takes place at the surface of them and EDTA (250 mg) was present in one flask and absent in
solid Ni species as a truly heterogeneous reaction or any Ni-leached another. The progress of the reaction was monitored by TLC. Time-
species act as homogeneous catalyst, the hot filtration test was dependent correlation showed that the improvement of the
conducted under the optimal conditions. In this line, after half of product yield of the reaction did not experience any significant
the specified time for the C-P cross-coupling reaction passed, an
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changes while ethylenediamine tetraacetic acid (EDTA) was present This means that NiII did not leach during the cVoieuwrsAerticolefOntlhinee
(Figure 10).
reaction into the reaction media which in turn proved that the
DOI: 10.1039/C9NJ00352E
NiII
catalyst is truly heterogeneous. In view of industrial purposes
and green chemistry, reusability is one of the most important
properties of metal catalysis that should be considered.
Incidentally, the reusability of Fe3O4@TiO2 YS-GLYMO-UNNiII
(VII) was studied by consecutive C-P cross-coupling reaction of
iodobenzene with diethylphosphite under the optimized
reaction conditions. After the first catalytic run, the
nanostructured catalyst was separated by an external
magnetic field from the reaction mixture, washed with EtOAc
(3 × 10 mL) and dried at 70 °C for 24 h. Next, a new C-P cross-
coupling reaction of fresh reactants was started by the
recovered nanostructured catalyst. As can be clearly observed
in Figure 11, the nanostructured catalyst was reusable for up
to seven cycles through the catalytic reaction and an
insignificant decrease in the yields was detected in the 6th and
7th runs.
NiII
O
P
OR
OR
NiII
Ar
NiII
O
(III)
OR
Reductive Elimination
NiII
Ar
P
NiII
OR
NiII
O
(III)
OR
P
10
11
12
13
14
15
16
17
18
19
20
21
22
23
24
25
26
27
28
29
30
31
32
33
34
35
36
37
38
39
40
41
42
43
44
45
46
47
48
49
50
51
52
53
54
55
56
57
58
59
60
Reductive Elimination
OR
NiIV
ArX
Ar
(II)
Oxidative Addition
-RX
O
OR
OR
P
X
R
Ar
O
NiIV
(II)
OR
OR
NiIV
Ar
P
X
(I)
-HX
NiIV
(I')
Ar
Several techniques were used to confirm the great stability
and reusability of this nanostructured catalyst including
Fourier transform infrared (FT-IR) spectroscopy, X-ray
diffraction (XRD) analysis, thermogravimetric analysis (TGA),
vibrating sample magnetometry (VSM) and inductively coupled
plasma atomic emission spectroscopy (ICP-AES).
O
P
P(OR)3
OR
OR
base +
H
Scheme 3 Plausible mechanism for the C-P cross coupling
reaction in the presence of Fe3O4@TiO2 YS-GLYMO-UNNiII (VII).
Fig. 10 Product yield as a function of reaction time catalyzed by
Fe3O4@TiO2 YS-GLYMO-UNNiII (VII) in (a) the presence and (b)
the absence of EDTA.
Fig. 9 Hot filtration experiment in the model reaction of the C-
P cross-coupling reaction using Fe3O4@TiO2 YS-GLYMO-UNNiII
(VII).
O
O
O
O
O
O
Ni
O
O
N
N
Fig. 11 C-P cross-coupling reaction of iodobenzene with
diethylphosphite under the optimized reaction condition
catalyzed by the 7th recycled Fe3O4@TiO2 YS-GLYMO-UNNiII
(VII).
Scheme 4 The chemical structure of the Nickel(II) EDTA
complex (VI).
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2
3
4
5
6
7
8
9
In order to quantitatively analyse and determine the exact
View Article Online
th
There were no signs of any significant changes in the amount of nickel in the fresh and the 7 reused Fe O @TiO
DOI: 10.1039/C9NJ00352E
3
4
2
intensities, frequencies and shapes of absorption bands in the YS-GLYMO-UNNiII (VII), ICP-AES technique has been used. The
FT-IR spectra of the 7th recovered Fe3O4@TiO2 YS-GLYMO- freshly-prepared nanostructured catalyst was shown to
UNNiII (VII) from the C-P cross-coupling reaction, but it could contain 0.86 mmol of nickel per 1.000 g of Fe3O4@TiO2 YS-
be clearly pointed out that nickel ions were in a strongly GLYMO-UNNiII (VII), whereas the 7th recovered nanostructured
coordination with organic moieties on the surface of to the catalyst from C-P cross-coupling reaction contained 0.80 mmol
Fe3O4@TiO2 YS-GLYMO-UN (VI) NPs (Figure 1h). During the C-P of Ni per 1.000 g of the nanostructured catalyst after ICP-AES
cross-coupling reaction process, the nanostructured catalyst analysis. After seven runs, the results indicate that 93 % of NiII
was also revealed to undergo no changes when XRD was used could be found in the structure of the catalyst. The data also
to analyse the 7th recovered catalyst. Based on Debye-Scherrer revealed that an insignificant amount of nickel leached from
equation, the average crystalline size of the 7th recovered the surface of Fe3O4@TiO2 YS-GLYMO-UNNiII (VII). Based on
Fe3O4@TiO2 YS-GLYMO-UNNiII (VII) was 32 nm (Figure 2d). the above analysis, the strong chelating action of active sites
After seven runs from the C-P cross-coupling reaction, the on the surface of Fe3O4@TiO2 YS-GLYMO-UN (VI) NPs probably
stability of Fe3O4@TiO2 YS-GLYMO-UNNiII (VII) was analysed caused the high catalytic activity and excellent reusability of
using thermogravimetric analysis. It could be concluded that Fe3O4@TiO2 YS-GLYMO-UNNiII (VII).
10
11
12
13
14
15
16
17
18
19
20
21
22
23
24
25
26
27
28
29
30
31
32
33
34
35
36
37
38
39
40
41
42
43
44
45
46
47
48
49
50
51
52
53
54
55
56
57
58
59
60
insignificant differences were detected in the decomposition Finally, to prove how the advantages of the present method
pattern (compare Figure7d with 7e). However, the weight loss for the synthesis of arylphosphonates, vinylphosphonate and
of the grafted organic motif in second and third steps were alkynylphosphonate outweighs that of those reported in the
decreased from 11.4/13.2 % (in the fresh nanocatalyst) to literature for the synthesis of these important scaffolds (Table
10.4/12.2 % in the 7th recovered nanocatalyst. Accordingly, the 3), we compared the results of C-P cross-coupling reaction in
amount of the grafted UiO-66(Zr)-NH2 (V') and (3- the presence of various catalytic systems. Several factors were
glycidyloxypropyl)trimethoxysilane were decreased from studied including catalyst loading, solvent, temperature,
0.55/0.65 to 0.52/0.60 mmol/g after seven runs, which might reaction time, different kinds of phosphite ester, and the yield
be attributed to the diminutive leaching of organic fragments of the product. As opposed to other catalytic systems,
during recycling process.
Fe3O4@TiO2 YS-GLYMO-UNNiII (VII) is a palladium-free and
As shown in Figure 8c, the saturation magnetization values magnetic nanostructured catalyst, the separation of which is
(Ms) of the 7th recovered Fe3O4@TiO2 YS-GLYMO-UNNiII (VII) easily done using a magnetic field. Additionally, another merit
from C-P cross-coupling reaction is Ms= 7.88 emu g-1 which is of this nanostructured catalyst is that it is capable of working
relatively lower than the fresh nanostructured catalyst value in water extract of rice straw ash (WERSA) without needing
(Ms= 15.33 emu g-1). It is noteworthy to mention that after such additives as SDS (sodium dodecyl sulphate),23 TBAB
seven runs from the C-P cross-coupling reaction, the (tetrabutylammonium bromide),35 Zn,32 iso-propanol27 or
superparamagnetic behaviour of the recovered Fe3O4@TiO2 activation by microwave irradiation.33, 34, 40, 54, 55, 106
YS-GLYMO-UNNiII (VII) still holds true.
Table 3 Comparison of the catalytic activity of Fe3O4@TiO2 YS-GLYMO-UNNiII (VII) with some literature precedents for C-P cross-coupling
reaction.
Catalyst
loading
(mol%)
Phosphite
ester
Time
(h)
Yield
(%)
Entry
1
X
Catalyst
Conditions
Ref.
13
Cu2O/1,10-
phenanthroline
HP(O)(OEt)2
B(OH)2
10
5
(i-Pr)2NEt, CH3CN, r.t, air
24
24
47-96
18-89
HP(O)(OEt)2
HP(O)(OMe)2
HP(O)(OBu)2
HP(O)(OEt)2
HP(O)(OMe)2
HP(O)(i-OPr)2
Pd(OAc)2
TMACla, Ag2CO3, EtOH,
80 °C, N2
2
3
4
B(pin)
B(OH)2
Br
14
15
Copper (II)
complex
10
KOAc, THF, r.t
72
56-83
68-87
HP(O)(OEt)2
HP(O)(OBu)2
HP(O)(OBn)2
Pd(OAc)2
NEt3, EtOH, MW (110-
120-150 °C)
15-30
min
5-10
106
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2
3
4
HP(O)(Ph)2
View Article Online
DOI: 10.1039/C9NJ00352E
5
6
7
8
HP(O)(OEt)2
HP(O)(i-OPr)2
HP(O)(n-Bu)2
NEt3 or pyridine or n-
Bu3N, 90 or 100 °C,
toluene
12
min-
64 h
Pd(OAc)2, PdCl2, Pd
5
Br
2
3-98
108
(PPh3)4
9
10
11
12
13
14
15
16
17
18
19
20
21
22
23
24
25
26
27
28
29
30
31
32
33
34
35
36
37
38
39
40
41
42
43
44
45
46
47
48
49
50
51
52
53
54
55
56
57
58
59
60
HP(O)(OEt)2
2, 5, 10,
13, 15
6
7
8
Br
Pd(OAc)2/PPh3
PdCl2, NiCl2
PdCl2
NEt3
24-60 37-93
5 min 60-98
25
54
35
P(OEt)3
I, Br
10
MW (80-120 °C)
P(OEt)3
P(i-OPr)3
I, Br,
Cl
TBAB, n-Pr3N, H2O, 100
4.4
1-12
16
65-99
44-92
°C
HP(O)(OEt)2
Pd(OAc)2/
dpephosb
Ag[P(O)(OEt)2], THF, 25
°C
9
I
5
39
40
HP(O)(OEt)2
P(O)(OBu)2
HP(O)Ph2
4.8-
15
min
solvent-free, Et3N, MW
(150-200 °C)
10
Br
Pd(OAc)2
(5, 10)
41-95
57-98
46-91
I, Br,
Cl,
OTs,
Pd-imino-Py-γ-
Fe2O3
11
12
P(OEt)3
0.1
2
H2O, Et3N, 100 °C
1-15
4-15
37
23
B(OH)2
P(OEt)3,
HP(O)(OEt)2
HP(O)(OPh)2
P(OEt)3,
I, Br,
Cl,
OTs,
Pd-BIP-γ-
Fe2O3@SiO2
Et3N, 100 °C, solvent-
free
B(OH)2
HP(O)(OEt)2,
P(OPh)3,
I, Br,
Cl
Pd-DABCO-γ-
H2O, Et3N,
100 °C
0.07 -
0.1
13
HP(O)(Ph)2,
P(i-OPr)3,
OTs,
B(OH)2
Fe2O3
1-15
51-98
24
HP(O)(i-OPr)2
P(OPh)3
HP(O)(OEt)2
HP(O)(OPh)2
HP(O)(i-OPr)2
I, Br,
Cl,
OTs,
14
Pd-2-ATP-γ-Fe2O3
0.1
H2O, SDS, 100 °C
1.5-8
51-97
23
B(OH)2
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8
H2O, Zn, 2,2'- bipyridine,
View Article Online
DOI: 10.1039/C9NJ00352E
70 °C
15
16
HP(O)(Ph)2
HP(O)Ph2
I, Br
NiCl2.6H2O
Pd/C
10, 20
1
15-24 75-97
32
H2O, K2CO3, MW (180 °C)
I, Br,
Cl
1
18-87
33
9
Palladacyclec (II),
(1)/ Palladacycle
(I)/X-Phosd
10
11
12
13
14
15
16
17
18
19
20
21
22
23
24
25
26
27
28
29
30
31
32
33
34
35
36
37
38
39
40
41
42
43
44
45
46
47
48
49
50
51
52
53
54
55
56
57
58
59
60
HP(O)(i-OPr)2
53-99,
35-
99/65-
99
H2O, TBAB, KF, reflux, i-
I, Br,
Cl
PrOH, N2
17
HP(O)(Ph)2
1
16
27
I, Br,
OTf
1.5-
32
18
19
HP(O)(OEt)2
Pd(OAc)2/dppfe
Pd(PPh3)4
10
5
THF, Et3N, KOAc, 68 °C
63-98
72-96
22
33
HP(O)(OEt)2
HP(O)(OMe)2
HP(O)(O-iPr)2
THF, Cs2CO3 or Et3N, MW
(120 °C)
10
min
Br
1.8-
15
min
HP(O)(OEt)2
HP(O)Ph2
Solvent free, Et3N, MW
(150-200 °C)
20
I, Br
Pd(OAc)2
5, 10
27-93
34
I, Br,
OTf
DMF, 110 ºC or MeCN,
21
22
23
HP(O)(iPr)2
HPO(OEt)2
HP(O)(OEt)2
Pd(OAc)2/dppf
Pd(OAc)2/PPh3
1
2
2
24
16
27-92
80-93
51-90
27
38
55
reflux, (iPr)2NEt
EtOH, (cyclohexyl)2MeN,
reflux
Br
30
min
B(OH)2 Pd(OAc)2/dmphenf
DMF, P-BQ, MW (100 °C)
P(OEt)3,
I, Br,
Cl, H,
B(OH)2
Fe3O4@TiO2 YS-
GLYMO-UNNiII
(VII)
1.15-
7.20
Present
study
24
HP(O)(OEt)2
0.4, 0.6
WERSA, 90 °C
70-95
a
b
c
d
Tetramethylammonium chloride. Dpephos = (Oxydi-2,1-phenylene)bis(diphenylphosphine). Cyclopalladated ferrocenylimine. 2-
(Dicyclohexylphosphanyl)-2 ,4,6-tri-iso-propyl-1,1-biphenyl. e 1,1’-bis(diphenylphosphino)ferrocene. f 2,9-dimethyl-1,10-phenanthroline.
approach quite efficient for the preparation of
arylphosphonates/ vinylphosphonate/ alkynylphosphonate
acridinedione derivatives as an important class of
4. Conclusion
In summary, the synthesis of NiII immobilized on aminated
Fe3O4@TiO2
yolk-shell
NPs
functionalized
by
(3-
organophosphorus compounds.
glycidyloxypropyl)trimethoxysilane (Fe3O4@TiO2 YS-GLYMO-
UNNiII (VII)) was successfully done from readily available
starting materials. Spectroscopic and microscopic techniques
Conflicts of interest
were used to characterize Fe3O4@TiO2 YS-GLYMO-UNNiII (VII) There are no conflicts to declare.
and the results revealed that the new nanostructured catalyst
is spherical in shape, has an average particle size of 30-32 nm,
and shows superparamagnetic behaviour. In the next step, it
Acknowledgements
The authors gratefully acknowledge the partial support of this
study by Ferdowsi University of Mashhad Research Council
(Grant no. p/3/43366).
was applied as a magnetically recyclable heterogeneous
nanostructured catalyst for the C-P cross coupling reaction in
the presence of water extract of rice straw ash (WERSA). The
merits of the suggested methodology include but not limited
to the following features: eco-friendliness, simplicity, excellent
yields of products, short reaction times, mild reaction
conditions, high efficiency, easy separation of the catalyst with
the assistance of an external magnetic field and reusability of
the nanostructured catalyst for up to seven cycles without
significant degradation in activity. All these features make this
Notes and references
1
2
3
L. D. Quin, A Guide to Organophosphorus Chemistry;
Wiley Interscience, New York, 2000.
P. J. Murphy, Ed. Organophosphorus Reagents; Oxford
University Press: Oxford, U.K., 2004.
W. Tang and X. Zhang, Chem. Rev., 2003, 103, 3029-3070.
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New Journal of Chemistry
View Article Online
DOI: 10.1039/C9NJ00352E
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C-P bond construction catalyzed by NiII immobilized on aminated Fe3O4@TiO2
yolk-shell NPs functionalized by (3-glycidyloxypropyl)trimethoxysilane
(Fe3O4@TiO2YS-GLYMO-UNNiII) in green media
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Maryam Sadat Ghasemzadeh, a Batool Akhlaghinia*a
*Department of Chemistry, Faculty of Science, Ferdowsi University of Mashhad, Mashhad 9177948974, Iran
NiII
NiII
NiII
NiII
O
NiII
OEt
OEt
NiII
NiII
II
Ar P
UNNi
-
2YS-GLYMO
mol%)
P(OEt)
4@TiO
(0.4
O
Fe3
(VII)
°C
90
mL),
3
(2.5
X= H, I, Br, Cl, B(OH)2
Ar = C6H5, 4-OMeC6H4, 4-MeC6H4,
4-CNC6H4, 4-CHOC6H4,
WERSA
HP(O)(OEt)
or
Ar
4-NO2C6H4, 4-ClC6H4, 1-naphthyl, 2-thienyl,
C6H5CCH,C6H5CH=CH
X
2
An efficient, versatile and novel method for C-P cross-coupling reaction with high yield of products using
Fe3O4@TiO2YS-GLYMO-UNNiII as a magnetic nanostructured catalyst in the presence of WERSA was reported.