Functionalized Phosphonium Ionic Liquids: Synthesis and Application

Article abstract of DOI:10.1080/10426507.2014.993759

A series of phosphonium salts with sterically hindered cation Bu^t₃P⁺(CH₂COOEt)X^- (X = Cl, BF₄, N(SO₂CF₃)₂) (1) was prepared for the first time. Palladium nanoparticles (PdNPs) stabilized by (1) showed moderate activity as catalyst in Suzuki cross-coupling reaction of bromoarenes and phenylboronic acid.

Full text of DOI:10.1080/10426507.2014.993759

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Functionalized Phosphonium Ionic
Liquids: Synthesis and Application
a
a
a
Daria Arkhipova , Vadim Ermolaev , Vasili Miluykov , Lilia
a
a
Nigmatullina & Oleg Sinyashin
a
Institute of Organic and Physical Chemistry A. E. Arbuzov KSC RAS,
A. Arbuzov Str. 8, 420088, Kazan, Russian Federation
Published online: 01 Jul 2015.
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To cite this article: Daria Arkhipova, Vadim Ermolaev, Vasili Miluykov, Lilia Nigmatullina & Oleg
Sinyashin (2015) Functionalized Phosphonium Ionic Liquids: Synthesis and Application, Phosphorus,
Sulfur, and Silicon and the Related Elements, 190:5-6, 899-901, DOI: 10.1080/10426507.2014.993759
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Phosphorus, Sulfur, and Silicon, 190:899–901, 2015
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Taylor & Francis Group, LLC
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ISSN: 1042-6507 print / 1563-5325 online
DOI: 10.1080/10426507.2014.993759
FUNCTIONALIZED PHOSPHONIUM IONIC LIQUIDS:
SYNTHESIS AND APPLICATION
Daria Arkhipova, Vadim Ermolaev, Vasili Miluykov,
Lilia Nigmatullina, and Oleg Sinyashin
Institute of Organic and Physical Chemistry A. E. Arbuzov KSC RAS, A. Arbuzov
Str. 8, Kazan 420088, Russian Federation
GRAPHICAL ABSTRACT
t
+
Abstract A series of phosphonium salts with sterically hindered cation Bu 3P (CH2COOEt)
−
X
(
(X = Cl, BF4, N(SO2CF3)2) (1) was prepared for the first time. Palladium nanoparticles
PdNPs) stabilized by (1) showed moderate activity as catalyst in Suzuki cross-coupling reaction
of bromoarenes and phenylboronic acid.
Keywords Phosphonium ionic liquids; palladium nanoparticles; Suzuki reaction
1
Nowadays the ionic liquids (ILs) have found a broad applications as ‘green’ reaction
2
3
4,5
media, effective electrolytes, phase transfer catalysts, extragents and other. Catalysis
and especially nanocatalysis remains one of the growing field of application of ILs in
various organic reactions.6 For this purpose a number ‘task-specific’ ILs
–8
9,10
containing
different functional groups has been prepared and used as stabilizers of metal nanoparticles
11
for effective catalysis. Although use of phosphonium salts for PdNPs stabilization in
catalysis is well known12 the applying of functionalized phosphonium salts containing
additional coordinating atom for stabilization of palladium nanoparticles is still not so
widespread.
To reveal this field, we have prepared phosphonium salts (1) containing 2-ethoxy-
1
3
2
-oxymethyl group on phosphorus atom using a common method, on the motive of one
14
report. Compounds (1) were characterized by NMR spectroscopy as well by elemental
analyses (see Table 1 and ESI).
PdNPs were obtained by reduction of Pd(OAc)2 in ethanol at the presence of phos-
phonium salt and characterized by TEM (Figure 1). The size of PdNPs is about 5 nm,
although some bigger aggregates were detected.
Received 12 September 2014; accepted 20 November 2014.
Address correspondence to Vadim Ermolaev, A.E. Arbuzov Institute of Organic and Physical Chemistry
KSC RAS, A. Arbuzov Str. 8, Kazan 420088, Russian Federation. E-mail: ermolaev@iopc.ru
Color versions of one or more of the figures in the article can be found online at www.tandfonline.com/gpss.
8
99

900
D. ARKHIPOVA ET AL.
Table 1 Physical properties of phosphonium ionic liquids (PILs) and their precursors
PIL
Chemical shift of
Chemical shift in
Melting point, α-protons in NMR NMR spectrum 1P,
3
◦
1
No.
Cation
Bu3P CH2COOCH2CH3
Anion
С
spectrum H, ppm
ppm
t
+
−
1
1
1
a
b
c
Cl
248
64–67
44–50
4.55
3.66
3.54
52.1
51.8
51.7
−
BF4
−
(CF3SO2)2N
Figure 1 TEM image of palladium nanoparticles.
Table 2 Conversion of bromoarenes in Suzuki cross-coupling reaction
∗
No.
Substrate
p-bromotoluene
m-bromotoluene
o-bromotoluene
p-bromoaniline
p-bromophenol
p-bromoanisole
2,4
bis(trifluoromethyl)bromobenzene
2,4,5-trifluorobromobenzene
2-bromothiophene
2-bromopyridine
1,4-dibromobenzene
1,3-dibromobenzene
1,2-dibromobenzene
Product
4-methylbiphenyl
3-methylbiphenyl
2-methylbiphenyl
4-phenylaniline
4-hydroxy-phenylbenzene
4-methoxybiphenyl
2,4 bis(trifluoromethyl)-1,1’-
biphenyl
2,4,5-trifluoro-1,1’-biphenyl
2-phenylthiophene
2-phenylpyridine
Conversion ,%
1
2
3
4
5
6
7
40
31
27
34
18
32
73
8
9
44
18
15
32
30
24
1
1
1
1
0
1
2
3
4-bromobiphenyl
3-bromobiphenyl
2-bromobiphenyl
∗
Conversion was determined by GC-MS. Typical experiment: Pd2(OAc)3 (0.45 mg, 0.002 mmol) and (2-
ethoxy-2-oxoethyl)tri-tert-butylphosphonium tetrafluoroborate (1b) (0.075 g, 0.2 mmol) dissolved in 10 mL
ethanol/water mixture (9:1). After PdNP’s formation bromoarene (2 mmol; 1 mmol in case dibromobenzene),
Na2CO3 (2–3 mmol, 1,5 eq.) and phenylboronic acid (2.6 mmol or 5.2 mmol in case dibromobenzene) were
◦
added. Reaction mixture stirred 16 hours at 30 С.

FUNCTIONALIZED PHOSPHONIUM IONIC LIQUIDS
901
Obtained nanoparticles were used as catalyst for Suzuki cross-coupling of phenyl-
boronic acid and different bromoarenes as well as heterocyclic bromides and dibromoben-
zenes (Table 2).
However, only moderate conversion of bromoarenes up to 40% was observed in
12c
contrast to tetraalkylphosphonium salts that demonstrated conversion up to 100%. This
fact could be explained by hydrolysis ester group of salt (1b) in basic reaction condition
that may provide additional contact to PdNP’s surface and suppress effective catalysis.
ACKNOWLEDGMENTS
The authors are grateful to Dr. Duncan Alexander (EPFL, Lausanne, Switzerland)
for TEM measurements.
FUNDING
Financial support of Ministry of Education and Science of Russian Federation (MK
4440.2013.3, 8415), Russian Foundation for Basic Research (13-03-12170), and Swiss
National Science Foundation are gratefully acknowledged.
SUPPLEMENTAL MATERIALS
Supplemental data for this article can be accessed on the publisher’s website at
http://dx.doi.org/10.1080/10426507.2014.993759
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