Synthesis and catalytic application of: N -heterocyclic carbene copper complex functionalized conjugated microporous polymer

Article abstract of DOI:10.1039/c6ra07786b

A N-heterocyclic carbene copper(i) complex functionalized conjugated microporous polymer (CMP-NHC-CuCl) was synthesized by palladium-catalyzed Sonogashira cross-coupling chemistry. The resulting CMP-NHC-CuCl proved to be a good heterogeneous catalyst in the hydrosilylation of functionalized terminal alkynes with boryldisiloxane to afford (β,β)-(E)-vinyldisiloxane with high stereoselectivity, and the catalyst could be used four times without obvious loss in catalytic activity. Moreover, CMP-NHC-CuCl was also efficient in catalyzing the hydrosilylation of CO₂ with triethoxysilane to form silyl formate under mild conditions.

Full text of DOI:10.1039/c6ra07786b

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Synthesis and Catalytic Application of N-Heterocyclic Carbene
Copper Complex Functionalized Conjugated Microporous Polymer
Hui Zhou*[a], Qing-Yong Zhang[a] and Xiao-Bing Lu*[a]
Received 00th January 20xx,
Accepted 00th January 20xx
DOI: 10.1039/x0xx00000x
N-Heterocyclic carbene copper(I) complex functionalized conjugated microporous polymer (CMP-NHC-CuCl) was
synthesized by palladium-catalyzed Sonogashira cross-coupling chemistry. The resulting CMP-NHC-CuCl proved to be good
heterogeneous catalyst in hydrosilylation of functionalized terminal alkynes with boryldisiloxane to afford (β,β)-(E)-
vinyldisiloxane with high stereoselectivity, and the catalyst could be used four times without obvious loss in catalytic
activity. Moreover, CMP-NHC-CuCl was also efficient in catalyzing the hydrosilylation of CO2 with triethoxysilane to form
silyl formate under mild conditions.
www.rsc.org/
Since N-heterocyclic carbene (NHC) copper complex was first group developed the silica-supported NHC-Cu(II) catalyst for
reported by Arduengo and co-workers in 1993,[1] their oxidative coupling of terminal alkynes with H-phosphonates,
applications have attracted broad attention in homogeneous and no significant loss in the catalytic reactivity was observed
catalysis,[2] especially for the hydrosilylation of carbonyl after recycling six times.[11] More recently, a 3-D diamondoid
compounds producing the corresponding silyl compounds,[3] metal organic framework using bis-NHC Cu(I) complex as a
carbene transfer reactions generating the three-membered building block was successfully applied to catalyze the
ring,[4] [3+2] cycloaddition of azides and alkynes enabling new hydroboration of CO2 to provide formamides.[12]
triazole ring reaction[5] and Miscellaneous reaction providing
Conjugated microporous polymers[13], as a new class of
the γ-selective allylic products[6]. Recently, the novel catalytic porous materials with high synthetic diversification, have been
applications of NHC-Cu(I) complexes are emerging in various used as promising solid supports in heterogeneous catalysis.[14]
[2e-2g]
transformation of CO2
such as the carboxylation of a Main method for creating catalytically active CMPs is to design
variety of substrates[7], reduction of CO2 into CO[8] or formic and synthesize the bridging ligands containing orthogonal
acid[9]
functional groups, as shown in Scheme 1. The primary
.
It is generally known that homogeneous catalytic processes functional groups could be linked by suitable nodes to form
usually suffer from some drawbacks, including the difficulty in extended networks, whereas the orthogonal secondary
the separation of catalysts, the purification of the product and functional groups can then be employed to generate catalytic
the recovery of the expensive catalysts. Additionally, the sites. Through this synthetic strategies, many CMPs containing
residual metal in the products probably causes serious Fe[14a], Re[14b], Rh[14b], Co[14e] and Zn[14f] complexes have been
problems for the applications of bioactive substrates, synthesized and applied for catalytic applications.
particularly for medical purpose. The immobilization of
homogeneous catalysts onto solid supports is an effective
method to solve the above problems. In 2010, Zhang and co-
workers successfully synthesized the novel poly-(NHC)CuCl, in
which the main-chains contain a great amount of (NHC)CuCl
units. The resultant poly-(NHC)CuCl was used to catalyze the
transformation of CO2 to carboxylic acids through C-H bond
activation of terminal alkynes.[10] Shortly afterwards, Wang
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In this study, we firstly report the synthesis of a copper-
Journal Name
coordinated conjugated microporous polymer (CMP-NHC-CuCl)
by linking NHC-CuCl with 1,3,5-triethynylbenzene. The CMP-
NHC-CuCl exhibits high activity towards the hydrosilylation of
functionalized terminal alkynes to selectively synthesize (β,β)-
(E)-vinyldisiloxane, as well as the chemical transformation of
CO2 to form silyl formate.
Results and Discussion
Due to its high air- and moisture-stability, IPrCuCl has the
potential to be used as secondary functional group to
construct copper complex functionalized CMPs.[15] Detailed
synthetic routes are showed in Scheme 2. CMP-NHC-CuCl was
synthesized
by
the
Sonogashira
cross
coupling
polycondensation of an iodo-NHC-CuCl
1
and 1,3,5-
triethynylbenzene in the presence of Pd (0) and CuI as catalyst
under alkaline conditions. According to the literature
procedures,[13,14] polycondensation in toluene in the presence
of triethylamine as base and Pd tetrakis-(triphenylphosphine)
palladium (0) as palladium source allows for the preparation of
CMP-NHC-CuCl
2 in an isolated yield of 86.7 %. The CMP-NHC-
CuCl was insoluble in all solvents tested. After repeated rinse
with water, CH2Cl2, methanol and acetone, CMP-NHC-CuCl was
rigorously wash by Soxhlet extraction for 24 h with CH2Cl2,
methanol and acetone, respectively, to remove any entrapped
impurities, and then dried under vacuum for 24 h at 80 oC. The
resultant CMP-IPr(CuCl) showed higher catalyst loading and
more accessible catalytic centers based on the iodo-NHC-CuCl
linkers.
BET surface area was found to be 388 m2g-1 (the Langmuir
surface area is 580 m2g-1) and the total volumes were 0.56
cm3g-1 at P/P0 = 0.99. As shown in Figure 1c, the adsorption
isotherm displayed a notable nitrogen gas uptake at low
relative pressure (P/P0<0.01) reflecting an abundant micropore
structure.[16] The TGA curve in Figure 1d reveals a stability of
the materials at least up to 270 oC.
Considering the excellent thermal stability of CMP-IPr(CuCl)
The morphology of CMP-NHC-CuCl was investigated by scan
electron microscopy (SEM) and transmittance electron
microscopy (TEM) measurements. SEM image in Figure 1a
displayed that CMP-NHC-CuCl consists of submicro spheres,
while TEM image in Figure 1b revealed the presence of
nanometer-scale pores (≈0.4 nm in diameter) on the polymer
surface. The porous properties of the networks were
investigated by nitrogen adsorption analyses at 77.3 K. The
Selectivity
Cat.
(mol%)
Time
(h)
Yield
(%)[b]
(β,β/α,β/α,α)[c]
Entry
1
2
3
4
1
2
5
5
2
2
2
6
34
50
79
92
>99:1:<1
>99:1:<1
>99:1:<1
>99:1:<1
[a] Reaction conditions: Si-B reagent (77.2 mg, 0.2 mmol), phenylacetylene (40.8
mg, 0.4 mmol), CMP-IPr(CuCl), NaOtBu (1.2 equiv. to the amount of [Cu]), MeOH
(65 μL, 1.6 mmol, 4.0 equiv.), THF (1 mL), room temperature, unless otherwise
[b]
[c]
noted.
mixture.
Yield of isolated product.
Determined by analysis of the crude
2 | J. Name., 2012, 00, 1-3
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regio- and stereoselectivity under mild conditions (room
temperature,
h).[17] CMP-IPr(CuCl) displayed excellent
2
Table2. Scope in terminal alkynes. [a]
dispersion ability in THF. To out delight, CMP-IPr(CuCl) proved
to be an effective catalyst for the hydrosilylation of
phenylacetylene with 3, and all results are shown in table 1.
The reaction could proceed smoothly in the 1 mol% CMP-
IPr(CuCl) at room temperature, affording (β,β)-(E)-4a with an
isolated yield of 34% within 2 h (entry 1). It is worth noting
that the stereoselectivity of CMP-IPr(CuCl) is comparable to
those of homogeneous catalyst and only (β,β)-(E)-4a was
produced with high regio-and site-selectivity, confirmed by the
Entry
Product
Yield (%)[b]
1
analysis of the crude mixture by H-NMR spectroscopy. When
the catalyst loading was increased 5 mol%, the yield of (β,β)-
(E)-4a reached to 79% at the same conditions (entry 3).
Moreover, the highest yield (92%) could be obtained by the
prolonged reaction time of 6 h (entry 4).
Furthermore, several types of terminal alkynes were
subjected to the catalytic reaction with boryldisiloxane 3 in
order to evaluate the scope of the present transformation, and
the results are summarized in Table 2. Functional groups such
as methyl-, bromo- and nitro- groups at the para position of
the aromatic ring were tolerated in the reaction, although
electron withdrawing substituents retarded the reaction rate
(4b-4d). Other substrates with a variety of functional groups,
such as alkyl, cyano, ether, ester, were tolerated in these
reaction (4e-4i), giving the corresponding (β,β)-(E)-
vinyldisiloxanes in good to excellent yields with no observable
byproduct formation. The reaction with propargyl alcohol did
not require the use of additional MeOH. The desired product
4j could be obtained by hydrolysis and SiO2 flash
chromatography purification.[17]
Since CMP-IPr(CuCl) is stable and insoluble in common
organic solvents, the investigation of the recycle use of CMP-
IPr(CuCl) is very convenient. After the hydrosilylation reaction
was completed, the reaction mixture was filtered to collect the
Table 3. Recycle test of CMP-IPr(CuCl) in the hydrosilylation of
phenylacetylene with boryldisiloxane 3.
vinyldisiloxanes
analysis of the crude mixture by
1H-NMR spectroscopy. [c] No additional MeOH.
and the successful incorporation of IPr(CuCl) into this network,
the catalytic behaviour of CMP-IPr(CuCl) was investigated in
detail. Firstly, the hydrosilylation of terminal alkynes with
boryldisiloxane was chosen as a model reaction to selectively
synthesize functionalized vinylsilanes. Our previous study on
NHC copper(I) catalyzed hydrosilylation had shown that
IPr(CuCl) complex was effective catalyst system to transform
terminal
alkynes
employing
1,1,3,3-Tetramethyl-1,3-
(pinacolboryl) disiloxane
3
as silicon source to (β,β)-(E)-
vinyldisiloxane 4a as the sole detectable isomer with perfect
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CMP-IPr(CuCl) also was efficient in catalyzing the
hydrosilylation of CO2 to afford the silyl formate under mild
conditions.
Experimental Section
Unless otherwise stated, all manipulations were performed
using standard Schlenk techniques under a dry nitrogen
atmosphere or an Innovative Technology glovebox under Ar.
NMR spectra were recorded on a Bruker Avance II 400M type
(1H NMR, 400 MHz; 13C NMR, 100 MHz) spectrometer. Infra-
red spectra (IR) were recorded using a Nicolet NEXUS FT-IR
spectrophotometer.THF and d6-benzene were purified by
distilling from sodium/benzophenone under a N2 atmosphere.
iodo-NHC-CuCl
1
[20] and 1,1,3,3-tetramethyl-1,3-(pinacolboryl)
were synthesized according the responding
[17]
disiloxane
3
literatures. Commerically available terminal alkynes and
triethoxysilane were used without further purification.
Synthesis of CMP-IPr(CuCl). iodo-IPr(CuCl) (368 mg, 0.5 mmol),
1,3,5-triethynylbenzene (75 mg, 0.50 mmol), tetrakis-
(triphenylphosphine) palladium (0) (30 mg, 0.025 mmol) and
CuI (20 mg, 0.10 mmol) were dissolved in a mixture of toluene
(2.5 mL) and triethylamine (1.25 mL). The reaction mixture was
heated to 80 oC and stirred for 72 h. The mixture was cooled to
room temperature, and the insoluble precipitated network
polymer was filtered and washed three times with
dichloromethane, water and methanol (30 mL×3) respectively
to remove the unreacted substrates. Further purification of
the polymer was carried out using a Soxhlet extraction with
water, CH2Cl2, methanol and acetone (1:1:1:1) for 24 h. The
product was dried under vacuum with the temperature of 80
oC for 24 h and isolated as a yellow powder (Yield: 286 mg,
86.7%). IR (KBr): 2961, 2928, 2863, 1626, 1595, 1436, 1387,
882 cm-1. Elemental combustion analysis (%) Calcd for
C41H37N2Cu (based on 100% reaction of Iodo group): C: 74.64,
H 6.11, N 4.25, Cu 9.63; Found: C 71.43, H 5.77, N 4.05. The
copper content of CMP-IPr(CuCl) was determined to be 1.4
mmol/g based on ICP analysis.
catalyst for the next round of hydrosilylation of
phenylacetylene with boryldisiloxane 3. As shown in table 3,
CMP-NHC-CuCl exhibited excellent stability, and was recycled
for four times, without obvious loss in catalytic activity.
Chemical transformation of CO2, as an inexpensive,
abundant, nontoxic and renewable C1 feedstock, always
attract extensive attention worldwide of the scientists,
especially in the areas of environment and chemistry.[18] The
NHC-copper alkoxide complex IPrCu(OtBu) have recently been
reported to catalyze the hydrosilylation of CO2 with
triethoxysilane, affording the silyl formate at room
temperature under 1 atm CO2.[5a] IPrCu(OtBu) complex is
readily prepared from the corresponding chloride through the
reaction with sodium tert-butoxide.[19] Therefore, we further
investigated the diverse activity of CMP-IPr(CuCl) to catalyze
the hydrosilylation of CO2 in the presence of catalytic amount
of NaOtBu, and the results are shown in Scheme 3. The
hydrosilylation was performed with 1.67 mol% CMP-IPr(CuCl),
although the product yield (
when IPrCu(OtBu) complex as homogeneous catalyst[9a]
However, the product yield could be significantly increased to
51.5% ( ) and 91.7% ( ), respectively, by increasing CMP-
A 26.3%) was lower than that
General procedure for CMP-IPr(CuCl) catalyzed hydrosilylation of
terminal alkynes with Si-B 3. In a glovebox, a vial was charged
with CMP-IPr(CuCl) (14.2 mg, 5 mol %), NaOtBu (2.3 mg, 6
mol%) and THF (1 mL). After 30 min stirring at room
temperature, phenylacetylene (40.8 mg, 0.4 mmol), 1,1,3,3-
.
B
C
IPrCuCl concentration to 5 mol% and 10 mol%, respectively. In
order to clarify this process, the reaction order in [CMP-IPrCuCl]
was further studied by means of in-situ FTIR (See supporting
Information, Figure S4-S9). The results showed that the
reaction is first-order in [CMP-IPrCuCl], so the rate of the silyl
formate was obviously affected by the catalyst concentration.
Conclusions
In summary, we have reported the first example of IPr(CuCl)
functionalized conjugated microporous polymer, CMP-
IPr(CuCl). CMP-IPr(CuCl) has been found to be efficient
heterogeneous catalysts for the hydrosilylation of terminal
alkynes with good substrate tolerance and could be reused at
least four times without a significant loss in catalytic efficiency.
Further investigations of the catalytic diversity showed that
tetramethyl-1,3-(pinacolboryl)disiloxane
3 (77.2 mg, 0.2 mmol)
and methanol (65 μL, 1.6 mmol, 4.0 equiv.) were sequentially
added to the solution, then continue to stir at room
temperature for 6 hours. After removal of the solvents under
reduced pressure, the crude product was purified by silica gel
column chromatography (hexane) to afford 4a as a colourless
liquid (92% isolated yield). 1H NMR (400 MHz, CDCl3): δ 7.51
(d, J = 7.4 Hz, 4 H), 7.39 (t, J = 7.4 Hz, 4 H), 7.33 (t, J = 7.4 Hz, 2
H), 7.05 (d, J = 19.2 Hz, 2 H), 6.54 (d, J = 19.2 Hz, 2 H), 0.36 (s,
12 H). 13C NMR (100 MHz, CDCl3): δ 144.66, 138.45, 128.85,
128.50, 126.88, 1.23.
4 | J. Name., 2012, 00, 1-3
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Acknowledgements
This work is supported by National Natural Science Foundation
of China (Grant No. 21402021), the Program for Changjiang
Scholars and Innovative Research Team in University
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