Synthesis of crab type Aminomethyldiphosphine-Oxovanadium(IV) complexes supported on magnetic Nano particles: Selective and recoverable catalysts in vitamin K3 synthesis

Article abstract of DOI:10.1002/aoc.4219

Nano Fe₃O₄ particles were obtained in microvawe oven using closed system. Oxovanadium(IV) complexes of Fe₃O₄@SiO₂@(aminomethylphosphine) type ligands were synthesized and characterized using SEM, EDX, TEM, UV-Visible, XRD, FT-IR and TG/DTA techniques. Catalytic properties of the synthesized pincer type oxovanadium(IV)-aminomethylphosphine complexes supported on magnetic nano structure were investigated in the synthesis of 2-methyl-1, 4-naphthoquinone (Vitamin K₃, menadione, 2MNQ) from 2-methyl naphthalene (2MN) in hydrogen peroxide, acetic acid and sulfuric acid. Magnetic-nano particle supported oxovanadium(IV)-aminomethylphosphine type complexes were very efficient catalysts with the 51.36-55.20 % selectivities in conversions of 89.78-95.01 %. Besides, the hetergeneous complexes were very active in five cycling tests on avarage evaluated in the reusability.

Full text of DOI:10.1002/aoc.4219

Received: 1 September 2017
DOI: 10.1002/aoc.4219
Revised: 10 November 2017
Accepted: 11 November 2017
F U L L P A P E R
Synthesis of crab type Aminomethyldiphosphine‐
Oxovanadium(IV) complexes supported on magnetic Nano
particles: Selective and recoverable catalysts in vitamin K3
synthesis
1
,2
2
2,3
Serhan Uruş
| Mahmut Çaylar | Ferudun Koçer
1
Chemistry Department, Faculty of
Science and Letters, Kahramanmaras,
Sütçü İmam University, 46100
Kahramanmaraş, Turkey
Nano Fe O particles were obtained in microvawe oven using closed system.
3
4
Oxovanadium(IV) complexes of Fe O @SiO @(aminomethylphosphine) type
3
4
2
ligands were synthesized and characterized using SEM, EDX, TEM, UV‐Visible,
XRD, FT‐IR and TG/DTA techniques. Catalytic properties of the synthesized
pincer type oxovanadium(IV)‐aminomethylphosphine complexes supported
on magnetic nano structure were investigated in the synthesis of 2‐methyl‐1,
2
Research and Development Centre for
University‐Industry‐Public Relations,
Kahramanmaras, Sütçü İmam University,
46100 Kahramanmaraş, Turkey
3
Bioengineering Sciences, Graduate
4
‐naphthoquinone (Vitamin K , menadione, 2MNQ) from 2‐methyl naphtha-
3
School of Natural and Applied Sciences,
lene (2MN) in hydrogen peroxide, acetic acid and sulfuric acid. Magnetic‐nano
particle supported oxovanadium(IV)‐aminomethylphosphine type complexes
were very efficient catalysts with the 51.36‐55.20 % selectivities in conversions
of 89.78‐95.01 %. Besides, the hetergeneous complexes were very active in five
cycling tests on avarage evaluated in the reusability.
Kahramanmaras, Sütçü İmam University,
46100 Kahramanmaraş, Turkey
Correspondence
Serhan Uruş, Chemistry Department,
Faculty of Science and Letters,
Kahramanmaras¸ Sütçü İmam University,
4
6100, Kahramanmaraş¸ Turkey; and
KEYWORDS
Research and Development Centre for
University‐Industry‐Public Relations,
Kahramanmaras, Sütçü İmam University,
3 4
catalysis, Fe O , nano, phosphine, vanadium
46100, Kahramanmaras¸ Turkey.
Email: serhanurus@yahoo.co.uk
Funding information
Kahramanmaraş Sütçü İmam University,
Grant/Award Number: Project No: 2013/6‐
33 M and 2015/2‐13 YLS 2015/2‐13 YLS
and 2013/6‐33 M
1
| INTRODUCTION
derivatives can be synthesized with the reaction of a phos-
phonium salt derivative like [R P(CH OH) ]Cl and a pri-
2
2
2
[
1–6]
Metal complexes of phosphines derivatives are used as
active catalysts in the synthesis of a lot of organic com-
pounds in the industry. Besides, the metal complexes of
aminophosphine derivatives synthesized by Mannich
reaction have opened new doors for catalytic applications.
P‐C‐N bonds containing aminomehtyldiphosphines are
synthesized by the reaction of formaldehyde a seconder
phosphine. (R PCH ) NR type aminoalkylphosphine
mary amine derivative.
Multidentate phosphines
ligands increase the stability of the metal complexes and
increase the catalytic activity in the most of the oxidation
or reduction reactions. Changing of the steric and elec-
tronic properties of phosphine‐metal complexes resulting
the higher catalytic activities. Chelated phosphine‐metal
complexes have more stable and more specific catalytic
properties than the complexes having monodentate
2
2 2
Appl Organometal Chem. 2018;e4219.
wileyonlinelibrary.com/journal/aoc
Copyright © 2018 John Wiley & Sons, Ltd.
1 of 8
https://doi.org/10.1002/aoc.4219

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URUŞ ET AL.
phosphine ligands. 6–16] Additionally to the excellent cata-
lytic properties of aminophosphine‐metal complexes,
supporting of them on the nano‐particles improve their
applicability in the catalytic reactions because of having
high surface area, easily supporting of various ligands on
them, good stability in severe chemical and physical con-
[
0.25 μm i.d.). The surface morphology and EDX analysis
of the nanocomposite ligands and the complexes were
analyzed using Zeiss Evo LS10 SEM attached with
Bruker Quantax EDS. TEM images were taken with
FEI Tecnai G2 Spirit BioTwin CTEM instrument. X‐ray
diffraction (XRD) patterns were recorded on the
PANalytical Xprt pro. UV‐Visible reflectance spectra
were recorded at solid state using Hitachi U‐3900
Spectrophotometer attached with solid state reflectance
apparatus. The microwave syntheses were done in
quartz vessels closed with teflon covers using Milestone
StartSynth instrument with temperature control. Mixed
calibration standarts of 2‐methylnaphthalene and 2‐
methyl‐1,4naphthoquinone in dichloromethane solutions
were prepared and injected to gas chromatography.
External calibrations drawn by the instrument software
with the obtained data for 2‐methylnaphthalene (2MN)
[17–22]
ditions, low synthesis price, low toxicity…etc.
ing of the magnetic nano particles with SiO provides
Coat-
2
the unique advantages, because, silica surface has chemi-
cally active surface for binding ligands and the metal com-
plexes and also have excellent stability even if severe
chemical and physical conditions.
‐methyl‐1,4‐naphthoquinone or menadione (vitamin
K ) is a member of vitamin K family produced syntheti-
cally in the industry. Vitamin K is is a nutritional supple-
ment especially in the feed of chickens and fishes used in
vitamin premixes and it can also be used for new‐
[23]
2
3
3
[24–28]
borns.
Industrial process of vitamin K production
and 2‐methyl‐1,4‐naphthoquinone (vitamin K , menadi-
3
3
is the oxidation of 2‐methyl naphthalene in dichromate/
sulphuric acid mixture by the selectivity of 30‐60%.
one, 2MNQ). All the chemicals and reagents were
purchased from Merck, Fluka, Sigma and Aldrich and all
the solvents were dried using established procedures and
immediately distilled under nitrogen atmosphere prior
to use. All the reaction steps of the complexes were
carried out under nitrogen atmosphere by Schlenk method.
[PPh (CH OH) ]Cl salt was obtained according to the
1
8 kg. chromium containing waste is thrown away in
the production of 1 kg vitamin K . The treatment of the
3
waste having chromium in the classical menadione pro-
[10,13,14,24–28]
duction is quite difficult.
Menadioneisgreenlyandcatalyticallysynthesizedwith
the oxidation of either 2‐methylnaphthalene or 2‐methyl‐1‐
naphthol in different solvents using a peroxide derivative
such as hydrogen peroxide.,However, the product selectiv-
ities are not high because of unable to control further
2
2
2
[
29]
literature.
Fe O @SiO @OSi(CH ) N(CH PPh ) and
3
4
2
2 3
2
2 2
Fe O @SiO @OSi(CH ) NHArN(CH PPh ) type ligands
3
4
2
2 3
2
2 2
[13,19–21]
were synthesized according to the literature.
Fe O @SiO supported (aminomethylphosphine)‐
3
4
2
[10,13,14,24–28]
oxidation.
In the study, selectivities reached
oxovanadium(IV) and different type complexes were
shown in Figure 1.
to 51.36‐55.20 % in the conversions of 89.78‐95.01 % using
Fe O @SiO @(aminomethylphosphine)‐oxovanadium(IV)
3
4
2
(core@shell@shell) type complexes.
2.2 | Synthesis of
Fe O @SiO @(aminomethylphosphine)‐
3
4
2
2
2
| EXPERIMENTAL
.1 | General
oxovanadium(IV) complexes
0.25
g
Fe O @SiO @(aminomethylphosphine) type
3 4 2
ligand was dispersed in 50 ml EtOH and ethanolic
FT‐IR spectra were obtained using KBr pellets with Perkin‐
solution of VOSO was added to the ligand in a Schlenk
4
−
1
Elmer Spectrum 400 system in the range 4000–400 cm .
The thermal properties of the ligands were investigated
on a SII thermal system under nitrogen atmosphere at a
heating rate of 10 °C /min in the range 30‐1000 °C. The oxi-
dation product amounts were obtained using a Shimadzu
GC‐2010 coupled with Flame Ionization Detector (FID)
with TRB‐5MS column (60 m x 0.25 mm x 0.25 μm i.d.).
GC Method, Injection block: 315 °C, carrier flow: 1.5 ml.
tube. The mixture was refluxed for 8 h under nitrogen
atmosphere and the obtained complex was filtered and
washed with EtOH. The precipitations were dried at
60 °C for 12 h.
2
.3 | Catalytic oxidation of 2MN to 2MNQ
(vitamin K3)
min‐ (He), FID: 320 °C, H : 40 ml.min , Air: 400 mL.
1
‐1
The same catalytic oxidation conditions were used for the
2
‐1
min . Oven program; initial temperature: 150 °C (1 min.
catalytic oxidation reaction of 2‐methylnaphthalene to 2‐
‐1
[13,14]
hold), increase to 310 °C with 30 °C.min rate and hold
min. Oxidized organic yields were characterized by
methyl‐1,4‐naphthoquinone (vitamin K3).
Fe O @
3 4
2
SiO @(aminomethylphosphine)‐oxovanadium(IV) type
2
Perkin Elmer Clarus 600 GC‐MS Electron Impact (70 eV)
with an Elite 5‐MS capillary column (60 m x 0.25 mm x
complex (0.01 mmol metal containing) were added to
some portion of acetonitrile and ultrasonicated for

URUŞ ET AL.
3 of 8
3 4 2
FIGURE 1 Fe O @SiO @VOL Type
Complexes

4
of 8
URUŞ ET AL.
1
0 min. and 1.466 g (10 mmol, 97%) 2‐methyl naphtha-
were tried in five cycle. The catalyst was filtered and
washed with acetonitrile and used again for the new cycle
in the same catalytic conditions.
lene, 2 ml glacial acetic acid, 0.5 ml H SO (98%) and
2
4
0
.5 ml H O (35 %) was added to the catalysis solution
2 2
were added to this dispersion and refluxed for 8 h. Cata-
lytic reaction compounds were characterized and verified
by GC‐MS. 2‐methyl naphthalene (2MN) converisons and
3
| RESULTS AND DISCUSSION
.1 | Synthesis
2‐methyl‐1,4‐naphthoquinone (2MNQ) selectivities were
3
found and calculated using GC‐FID calibrated prior to
analyses.
SiO coating of Fe O nano‐structure has been observed in
2
3 4
Catalytic recycling properties of Fe O @SiO @
aminomethylphosphine)‐oxovanadium(IV) type catalysts
FT‐IR spectra. Silanol‐OH and Si‐O stretches were
3
4
2
observed at about 3265 cm‐ and 1090 cm respectively
1
‐1
(
1
00.0
98
96
94
92
90
88
86
84
%T
82
8
7
7
7
7
7
6
6
0
8
6
4
2
0
8
6
6
4.0
4
000.0 3600
3200
2800
2400
2000
1800
1600
1400
1200
1000
800
600
400.0
cm-1
FIGURE 2 FT‐FAR spectra of Fe
3
O
4
@SiO
2
@VOL4
3 4 2
FIGURE 3 TGA curve of Fe O @SiO @VOL4

URUŞ ET AL.
5 of 8
for all the silica coated compounds. Aromatic and aliphatic
Fe O @SiO @(aminomethylphosphine)‐oxovanadi-
um(IV) complexes have four endothermic bands in TGA
3
4
2
‐
1
C‐H stretches were recorded at about 2980 cm and
‐1
‐1
‐1
2
910 cm . Weak peaks at about 3560 cm and 1621 cm
curves. Adsorbed water degradation from SiO surface
2
were because of secondary amine N‐H stretches and bend-
was desorbed from the ambient temperature to 100 °C.
The hydroxyl groups decomposition from silanol
structures on the surface of silica backbone were
recorded from 100 °C to about 250 °C with an endother-
mic band. From 250 to approximately 565 °C,
aminomethylphosphine ligands degradated with an
endothermic band. Metal oxide formation was observed
from 565‐900 °C. Totally, 20‐25 % degradations were
ings for the complexes. Aromatic C=C stretches were
‐
1
overlaied with N‐H bendings about 1621 cm . P‐Ph
stretches of the complexes were collected about 1437 cm‐
as weak peaks. New V=O and V‐O stretches of the different
structured V(IV) complexes were observed at about 947
1
‐
1
and 784 cm . V‐P stretches were recorded at about
‐1
[30,31]
4
48 cm (Figure 2).
(
a)
(b)
(
c)
(d)
(
e)
FIGURE 4 SEM and TEM images. a: SEM of Fe @SiO
3
O
4
2 3 4 2 3 4 2
@VOL1. b: SEM of Fe O @ SiO @VOL2. c: TEM of Fe O @ SiO @VOL3. d:
TEM of Fe @ SiO @VOL4. e: EDX of Fe @ SiO @VOL2
3
O
4
2
3
O
4
2

6
of 8
URUŞ ET AL.
calculated for Fe O @SiO @(aminomethylphosphine)‐
oxovanadium(IV) type complexes (Figure 3).
additionally to Fe, O and Si peaks in EDX spectra
(Figure 4). Sulfur peak was not seen in EDX spectra, thus,
it can be said that sulfato ligands did not coordinate to
metal centers or did not present outside of the coordina-
tion sphere. The observed peaks prove the different coor-
dination type supportings the complexes on the surface of
Fe O @SiO (Figure 1).
3
4
2
Different sized nano‐spherical structure was
observed in SEM and TEM images for Fe O @SiO @
3
4
2
(
aminomethylphosphine)‐oxovanadium(IV) type com-
plexes. The almost of the surface of Fe O @SiO
2
3
4
particles that have around 9‐10 nm diameter covered
by (aminomethylphosphine)‐oxovanadium(IV) complexes
with about 3‐5 nm thickness (Figure 4).
3
4
2
The
XRD
patterns
of
Fe O @SiO @
3 4 2
(aminomethylphosphine)‐oxovanadium(IV) type com-
plexes are given in Figure 5. Amorphous silica coverage
on spherical Fe O nano particles were seen at about 2θ
The obtained Fe O @SiO ‐bis(aminomethylphos-
3
4
2
phine)‐oxovanadium(IV) type complexes showed
3
4
phosphorus, carbon, nitrogen and vanadium peaks
≈ 20‐25°. The well known six diffraction peaks at 2θ ≈
0.12°, 35.45°, 43.14°, 54.40°, 57.22° and 62.64° which
belong to crystalline cubic inverse spinel structure Fe O
3
3
4
magnetic nano‐particles were observed between 2θ =
7° and 70° in X‐ray powder diffraction patterns. These
peaks were also observed at previously works in the liter-
2
[
13,32,33]
ature.
Supporting of bis (aminomethylphosphine)‐
oxovanadium(IV) type complexes on magnetic nano‐par-
ticles were observed as a new broad diffraction peak in
o
o
the range of 2θ ≈ 20 ‐ 30 on the surface of Fe O @SiO
3
4
2
seen for Fe O @ SiO @VOL2 and Fe O @ SiO @VOL3.
3
4
2
3
4
2
A new crytalline peak at 2θ: 25.97 was seen for Fe O @
3
4
SiO @VOL1 in XRD pattern (Figure 5).
2
3.2 | Catalytic activity
Synthesis and using of Fe O @SiO ‐bis(aminomethyl-
3
4
2
phosphine)‐oxovanadium(IV) type complexes as catalysts
in green synthesis of vitamin K are new in the literature.
3
According to the probable catalytic oxidation mechanism;
2‐methylnaphthalene oxidizes to 2‐methyl‐1‐naphthol in
a slow and first step, then this pre‐compound oxidizes to
[
13,14,24–28,34,35]
2‐methyl‐1,4‐naphthalenediol (Figure 6).
If the first step is controlled, the reaction selectivity can
be increased using a suitable catalysts in determined con-
ditions. In the possible mechanism, acetic acid is oxidized
to peroxy‐acetic acid in the oxidation mechanism and
activate the oxygen transportation to aromatic ring
[
13,14,24–28,34,35]
together with a suitable catalyst.
The optimum catalyst, oxidant and substrate amount
were determined as 1:100:1000 (catalyst (metal amount):
oxidant:substrate mmol) for 8 h reaction time. Glacial
acetic acid with a small amount of sulfuric acid were used
FIGURE 5 X‐ray patterns of the compounds
[34]
FIGURE 6 Possible oxidation mechanism of 2‐methyl naphthalene
.

URUŞ ET AL.
7 of 8
[13,14,24]
in order to obtain peroxy‐acetic acid.
All the
TABLE 1 Conversions and selectivities and Catalytic Recyclings
complexes show good activity compared to the
Catalytic Conversion Selectivity
[
13,14,24–28,34,35]
literature.
Selectivites reached to 51‐55 %
Catalyst
Cycle
(mol%)
(mol%)
Fe
Fe
Fe
Fe
3
3
3
3
O
O
O
O
4
4
4
4
@SiO
@SiO
@SiO
@SiO
2
2
2
2
@VOL1
@VOL2
@VOL3
@VOL4
1
2
3
4
5
90.22
85.87
81.22
78.72
71.99
51.36
50.10
48.32
40.29
35.56
1
2
3
4
5
95.01
90.14
87.89
82.65
78.42
55.20
52.14
50.05
45.53
40.78
1
2
3
4
5
92.14
89.76
83.55
78.87
75.69
53.64
50.67
47.41
43.29
37.29
1
2
3
4
5
89.78
86.50
80.02
76.26
71.89
52.50
49.94
47.54
44.61
38.83
with 90‐95 % conversions (Figure 7, Table 1). These values
are the new and very good in the synthesis of 2‐methyl‐1,4‐
naphthoquinone (vitamin K ) from 2‐methylnaphthalene
3
using (aminomethylphosphine)‐oxovanadium(IV) type
[
13,14,24–28,34,35]
complexes used as catalysts.
Recycling experiments were tried in five cycles using
Fe O @SiO @(aminomethylphosphine)‐oxovanadium(IV)
3
4
2
type complexes (Figure 5, Table 1). In the five cycle average,
Fe O @SiO @(aminomethylphosphine)‐oxovanadium(IV)
3
4
2
type complexes showed selective catalytic properties in the
oxidation of 2MN without missing an important activity
loss. The new nano‐supported complexes can be tried for
[
13,14,24–28,34,35]
industrial production of vitamin K3.
4
| CONCLUSIONS
The novel Fe O @SiO @(aminomethylphosphine) type
3
4
2
bidentate tertiary aminomethylphosphine ligands and
their oxovanadium(IV) complexes have been synthesized
with Schlenk technique and characterized succesively.
The catalytic properties of the complexes in the green
synthesis of 2‐methyl‐1,4‐naphthoquinone (vitamin K3)
were investigated first in the literature. All the
complexes showed very good catalytic activities. Besides,
the magnetic nano‐supported complexes can be used as
recyclable and applicable heterogeneous catalysts in the
synthesis of vitamin K3.
FIGURE 7 Conversions, selectivities and Recycling

8
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URUŞ ET AL.
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