A step forward in solvent knitting strategies: Ruthenium and gold phosphine complex polymerization results in effective heterogenized catalysts

Article abstract of DOI:10.1039/c9cy00776h

Porous polymers based on ruthenium and gold triphenylphosphine complexes (KPhos(Ru), KPhos(Ru)Bi, KPhos(AuCl) and KPhos(AuNTf₂)) were prepared via a cost-effective solvent knitting method with [RuHClCO(PPh₃)₃] or AuXPPh₃ (X = Cl, NTf₂) as single monomers or combined with biphenyl, which represents a further approach to obtain heterogenized catalysts. The resulting materials mainly preserve the metal coordination environment of their parent complexes, are stable up to 350 °C and have reasonable surface areas (250-300 m² g^-1 for KPhos(Ru)-polymers). KPhos(Ru)s selectively catalyze the imination of alcohols in the presence of base and the results for KPhos(Au)s show they are effective for the intermolecular hydration and hydroamination of alkynes. These materials can be reused several times without significant loss of activity. This novel and simple method affords heterogenized catalysts that combine the reactivity and selectivity of their homogeneous counterparts with the stability and reusability of a heterogeneous framework.

Full text of DOI:10.1039/c9cy00776h

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DOI: 10.1039/C9CY00776H
ARTICLE
A step forward in solvent knitting strategy: ruthenium and gold
phosphine complexes polymerization results in effective
heterogenized catalysts.
Received 00th January 20xx,
Accepted 00th January 20xx
Antonio Valverde-González,a Gwendoline Marchal,a,b Eva M. Maya,a* Marta Iglesiasa*
DOI: 10.1039/x0xx00000x
Porous polymers based on ruthenium and gold triphenylphosphine complexes (KPhos(Ru), KPhos(Ru)Bi, KPhos(AuCl) and
KPhos(AuNTf2)) were prepared via cost-effective solvent knitting method of [RuHClCO(PPh3)3] or AuXPPh3 (X = Cl, NTf2) as
single monomers or combined with biphenyl, which represent an approach further to obtain heterogenized catalysts.
Resulting materials mainly preserve the metal coordination environment of their parent complexes, are stable up to 350
ºC and have reasonable surface areas (250-300 m2.g-1 KPhos(Ru)-polymers). KPhos(Ru)s selectively catalyze the imination
of alcohols in the presence of base and KPhos(Au)s result effective for the intermolecular hydration and hydroamination of
alkynes. These materials are reused several times without significant loss of activity. This novel and simple method afford
heterogenized catalysts that combine the reactivity and selectivity of their homogeneous counterparts with the stability
and reusability of a heterogeneous framework.
supports for homogeneous catalysts. This method has been
applied to prepare several series of porous polymers from
different aromatic monomers.6f, 10
Introduction
Heterogenized catalysts are usually prepared by immobilizing a
homogeneous catalyst onto a solid support and have shown
significant benefits in stability, recyclability in multiple cycles,
and separation from the reactants.1 Silica-based materials2 and
magnetic nanoparticles3 are usually used as supports but they
have the disadvantage of the lack of homogeneity of the active
sites and eventual blocking of the pores and deactivation of
the catalyst.4 In the last years porous hybrid organo-inorganic
materials (MOFs),5 and porous organic materials as porous
organic polymers (POPs)6 or covalent organic frameworks
(COFs)7 have been used as solid porous platforms to
heterogenize homogeneous catalysts. In general, POPs show a
high hydrothermal and chemical stability and could be
converted in catalysts by incorporation of catalytic sites as
building blocks by covalent bonds and can be modified by
post-synthetic methods.8
Nonetheless, the maintenance of the coordination metal
environment through this strategy has not always been
pursuit. Lai and co-workers reported the direct knitting of
palladium tetrakis(triphenylphosphine) and benzene where
the palladium atoms were spatially isolated in the framework
of the polymer.11 Alternatively, Song and co-workers knitted
1,1’-bis(diphenylphosphino)ferrocene and biphenyl affording
an effective catalyst for the reduction of 4-nitrophenol, where
the ferrocenyl units were not altered.12 Recently, during the
preparation of this manuscript, Huang group achieved a highly
effective catalyst for dehydrogenation of formic acid to
hydrogen by knitting a pincer ruthenium complex and
benzene.13
Here, we present an easy synthesis of new knitted metal-
based polymers that maintain the molecular structure of
parent Ru- and Au-complex (Scheme 1); these materials result
in effective heterogenized metal-triphenylphosphine catalysts
for the synthesis of imines, in the case of the Ru-based
polymers, and for the hydration of alkynes, in the case of the
Au-based catalyst.
Hyper-cross-linked polymers synthesized by
a knitting
polymerization method (employing AlCl3 or FeCl3 as catalyst
and dichloromethane or dimethoxymethane as cross-linker)9
are a relative new family of porous polymers with excellent
properties such as high thermal and chemical stability,
insolubility and easy post-functionalization to be used as
Results and discussion
The knitted ruthenium and gold-phosphine-polymers
(KPhos(Ru), KPhos(Ru)Bi, KPhos(AuCl), KPhos(AuNTf2)) were
synthesized in one-step hyper-crosslinking method via AlCl3-
catalyzed reaction (Scheme 1).10 In this method,
dichloromethane was employed as an external methylene
linker between the phenyl groups from the phosphine ligands
a. Instituto de Ciencia de Materiales de Madrid. CSIC. c/ Sor Juana Inés de la Cruz 3,
Cantoblanco Madrid 28049, Spain.
b. Present adress: Ecole Nationale Supérieure de Chimie de Mulhouse, 3 rue Alfred
Werner 68 093, Mullhouse, Cedex, France.
Electronic Supplementary Information (ESI) available: [details of any
supplementary information available should be included here]. See
DOI: 10.1039/x0xx00000x
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in parent ruthenium [RuHClCO(PPh3)3] or AuXPPh3 (X = Cl, NTf2) confirming that molecular structure is mainly maiVnietwaiAnrteicdle aOfntliener
DOI: 10.1039/C9CY00776H
complexes. In the case of KPhos(Ru)Bi, the polymerization the polymerization process; some others vibration bands are
occurs in presence of biphenyl which acts as a co-monomer in also present, such as (C-H) at 3100 cm-1, (C-C) at 1400 cm-1
a molar ratio of 2:1 versus the ruthenium complex.
from triphenylphosphine moieties and (P-C) at 1100 cm-1.
The resulting polymers are insoluble in water, alcohols and the KPhos(Ru)Bi spectrum also shows an extra band at 1600 cm-1
most common organic solvents. The formation of the hyper- corresponding to C=C vibration from biphenyl. FT-IR of gold-
cross-linked metal-phosphine complex network is confirmed polymers are shown in figure S5.
by FTIR, solid-state 13C-NMR, 31P-NMR, thermal analysis (TGA),
SEM and TEM microscopies. X-ray photoelectron spectroscopy
(XPS) confirms the oxidation state of ruthenium, gold and
phosphorous. The metal loading was determined by
transmission x-ray fluorescence spectroscopy (TXRF) or ICP-
OES14 resulting: 2.26 mmol/g, 22% weight (KPhos(Ru)), 0.79
mmol/g, 8% weight (KPhos(Ru)Bi), 0.72 mmol/g, 15% weight
50 230 210 190 170 150 130 110 90 70 50 30 10
ppm
250 230 210 190 170 150 130 110 90
ppm
70
50
30
10
(KPhos(AuNTf2)) and 0.97 mmol/g, 19% weight (KPhos(AuCl)).
SEM-EDX analyses confirmed that the ratio P: Ru and P: Au are
2:1 and 1:1, respectively (Figure S17). These results are in good
agreement with the inorganic residue obtained by TGA.
a
b
P
P
H
Ru
2Cl2
CH
2 Cl
Cl
CH
CO
2
P
AlCl3
AlCl
3
280 250 220 190 160 130 100 70
0
40
10
-2
260 240 220 200 180 160 140 120 100 80 60 40 20
ppm
P
Cl Ru
P
P
Cl Ru
P
ppm
P
CO
H
CO
H
(1)
CO
H
c
d
Cl Ru
P
Figure 1. 13 C-NMR spectra of a) KPhos(Ru), b) KPhos(Ru)Bi, c) KPhos(AuCl) and d)
KPhos(AuNTf2).
P
Cl Ru
P
CO
H
CO
1
P
H
Ru
P
Ru-H
Cl
KPhos(Ru)Bi
C-P
KPhos(Ru)
C-C
PPh3
C-O
CF
O
O3
Au
P
X
S
KPhos(Ru)
Cl2
CH2
CH
2
N
Au
Cl
P
O
AlCl
S
O
AlCl3
Au
P
Cl
2
CF
3
Ru-H
3
X= Cl (2)
X= NTf2 (3)
C-P
C-O
P
P
C-C
PPh3
Au
Cl
Au
O
KPhos(Ru)-Bi
F C
S
N
3
O
S
O
O
CF3
Ru-H
KPhos(AuCl)
KPhos(AuNTf
)
2
C-O
C-C
C-P
PPh3
Scheme 1. Synthesis of knitted ruthenium and gold-phosphine-polymers.
C-C
Biphenyl
1500
3000
2500
2000
1000
 (cm-1)
The 13C-CP/MAS-NMR spectra of the polymers (Figure 1)
displayed a peak at δ = 41.2 ppm corresponding to methylene
linker, from CH2Cl2, which confirms the successful C-C
coupling.15 The CO signals could not be identified because of
the low sensitivity of solid-state NMR spectroscopy. The peaks
at δ  139 (sh) and 131 ppm correspond to aromatic carbons
from triphenylphosphine ligands.16 The 31P-MAS-NMR spectra
(Figures S1-S2) show peaks at 28 and 26 ppm for both
KPhos(Ru) and KPhos(Ru)Bi polymers, at 29 ppm for
KPhos(AuCl) and at 26 ppm for KPhos(AuNTf2) which confirm
the presence of P-Ru and P-Au bonds. Further peaks at δ  60-
70 ppm are attributable to phosphorous species generated by
the polymerization process (for example Ionic phosphonium
species as (PPh3Cl)Cl).17 It is important to note that no free
phosphine (at -5 ppm) was observed.
Figure 2. FTIR spectra of parent Ru-complex and knitted Ru(PPh3)-polymers.
Figure S16 showed the XPS survey scan for the polymers. Ru
was analysed by its 3p state instead of the 3d spectra to avoid
the overlap of the C1s and Ru3d core-levels. The Ru3p region
(Figure 3a) shows a doublet peak at 464 eV and 485 eV for
Ru3p3/2 and Ru3p1/2, respectively, for the RuP species, which
confirms that ruthenium has the +2-oxidation state.18 The P2p
spectrum (Figure 3b) showed the presence of only one P-
containing species at 133.0 eV, assigned to PPh3 species. For
KPhos(AuCl), the binding energy of Au4f at 86 eV justify the
presence of gold(I) oxidation state (Figure 3c); the typical P2p
binding energy was observed at 134 eV, confirming that no
triphenylphosphine oxide was present in the sample. These
results confirm that the oxidation state of the polymer is
preserved.
FTIR spectra (Figure 2) show bands at 2058 and 1980 cm-1
corresponding to both (Ru-H) and (CO) respectively,
2 | J. Name., 2019, 00, 1-3
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calculated by N2-DFT method (Figure S13). The plot shows pore
View Article Online
DOI: 10.1039/C9CY00776H
sizes were mainly distributed around 2.4 nm, indicating
mesopores are presented in both polymers. Furthermore
KPhos(Ru)Bi also exhibits mesopores around 40 nm.
KPhos(AuNTf2) and KPhos(AuCl) polymers show low N2
adsorption (Figure S14, A and B) affording only 20 and 49 m2/g
of specific surface areas, respectively.
150
140
130
120
110
500
490
480
470
460
450
Binding Energy (eV)
Binding Energy (eV)
Table 1. Physical Properties of KPhos-polymers.
a
b
Polymer
KPhos(Ru)
KPhos(Ru)Bi
KPhosBi
KPhos(AuNTf2)
KPhos(AuCl)
SBET (m2.g-1)
VTOTAL (cm3.g-1)a
0.203
Dpore (nm)
2.2
300
250
704
20
0.107
1.45
0.12
0.07
2.2
8.3
1.7
5.9
49
a At P/P0= 0.99
120
130
140
150
80
85
90
95
100
Binding Energy (eV)
Binding Energy (eV)
c
d
280
240
200
160
120
80
Figure 3. Core-level XPS spectra Ru(3p), P(2p) (KPhos(Ru)) (up) and Au(4f), P(2p)
(KPhos(AuCl)) (down)
KPhos(Ru)Bi
KPhos(Ru)
Thermogravimetric analyses (TGA) (Figure 4) showed one-step
degradation pattern for all knitted metal-phosphine polymers.
KPhos(Ru)Bi exhibited higher thermal stability than KPhos(Ru)
with a thermal decomposition temperature of 380ºC and
300ºC respectively. Whereas knitted gold-phosphine polymers
showed similar degradation temperatures around 350ºC. As
commented previously the metal content was confirmed by
TGA. At high temperatures gold, ruthenium and phosphine
oxides are formed, Au2O3, RuO2 and P2O5; however, upon
200ºC Au2O3 decomposed in Au and O2.19 Therefore,
considering that the Ru-polymers residue is RuO2 and P2O5 and
Au and P2O5 for Au-polymers, it was possible to estimate the
gold, ruthenium and phosphorous loading by TGA analyses
which were in good agreement with those obtained by TXRF
and ICP-OES given above.
40
0
0,0
0,2
0,4
0,6
0,8
1,0
Relative Pressure (P/P )
0
Figure 5. Nitrogen adsorption/desorption isotherms of KPhos(Ru) polymers
The surface morphology was explored by the field-emission
scanning electron microscopy (SEM) and transmission electron
microscopy (TEM) (Figures 6 and S7-12) showing the typical
morphology described for this type of porous organic polymers
made by aggregates of spherical structures that remembers
the texture of a sponge. In addition, energy-dispersive X-ray
spectroscopy (SEM-EDX) and elemental mapping analysis
revealed the coherent ratio of Ru/P and Au/P (see the
Supporting Information, Figure S17).
100
80
60
40
20
0
100
80
60
40
20
0
KPhos(AuNTf
)
2
KPhos(AuCl)
100 200 300 400 500 600 700 800
100 200 300 400 500 600 700 800
Temperature (ºC)
Temperature (ºC)
KPhos(Ru)
KPhos(Ru)Bi
100
100
80
60
40
20
0
80
60
40
20
0
KPhos(Ru)Bi
KPhos(Ru)
2 µm
10 µm
100 200 300 400 500 600 700 800
100 200 300 400 500 600 700 800
Temperature (ºC)
Temperature (ºC)
Figure 4. Thermal analysis of and KPhos(AuX) (up) and KPhos(Ru) (down).
KPhos(AuCl)
KPhos(AuNTf2)
The N2 adsorption isotherms of both KPhos(Ru)Bi and
KPhos(Ru) displayed the same type II profile. The Brunauer–
Emmett–Teller (BET) surface areas are 250 m2/g and 300 m2/g
(Figure 5, Table 1) and total pore volume was found to be 0.11
and 0.20 cm3g-1, respectively. The pore distributions were
2 µm
Figure 6. SEM images of KPhos polymers
2 µm
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J. Name., 2013, 00, 1-3 | 3
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attention being the aerobic oxidative coupling ofVaielwcoArhtiocllesOanlninde
Post-funtionalization of triphenylphosphine knitted polymers
(KPhosBi(M), M: Ru, Au).
amines the most promising strategy.23
DOI: 10.1039/C9CY00776H
It is well-known, that ruthenium is a widely used and versatile
catalyst for the dehydrogenation of alcohols.24 However it is
scarcely used for the imination reaction.25 Ru-parent complex
1 is an efficient homogeneous catalyst in reactions such as
hydrogenation of aldehydes and ketones, transfer
hydrogenation or transfer hydrogenative C-C bond forming
reactions.26 Thus, these data prompted us to study possible
imination reaction from alcohols and amines with knitted Ru-
polymers as heterogeneous catalysts and the results were
compared with that obtained from homogeneous 1-complex.
Since both KPhos(Ru) and KPhos(Ru)Bi have similar
characteristics, we chose KPhos(Ru) as reference catalyst.
Reaction of 1.2 mmol of benzyl alcohol, 1.0 mmol of aniline
and 2 mol% of catalyst in toluene at 100ºC for 2 h in the
For comparative purposes, we have tried to prepare polymers
following a post-functionalization strategy (Scheme 2). Using a
similar approach to that previously reported with benzene as
co-linker.20 Triphenylphosphine was reacted with biphenyl
(molar ratio 1:1) in the presence of AlCl3 and
dimethoxymethane as external linker in dicloroethane (DCE) as
solvent yielding a polymer denoted as KPhosBi which showed
a
BET surface area of 704 m2/g (Table 1) (N2
adsorption/desorption isotherm, Figure S15), its NMR solid
state spectra are shown in Figure S3. Then, KPhosBi was
reacted with RuCl3.nH2O following a similar method to the one
used to synthesize precursor RuHClCO(PPh3)3. However, TXRF
and XPS analyses of the resulting solid revealed that the
ruthenium loading in KPhosBi(Ru) is only 0.02 mmol/g (Figure
S16). Therefore, we discarded this approach to heterogenize
the Ru-phosphine complex. Alternatively, KPhosBi was reacted
with AuCl(tht) in dichloromethane affording the corresponding
KPhosBi(Au) polymer. ICP-OES analysis revealed that the gold
loading was 1.01 mmol/g. 31P-NMR spectrum shows that P-Au
and phosphine moieties are present in the polymer (Figure S4).
XPS analysis shows a doublet corresponding to Au4f at around
85 eV. In both spectra, the phosphine characteristic peak of P
2p was observed at around 136 eV (Figure S16). In this case, it
seems that the corresponding supported Au-phosphine
complex has been formed.
presence
of
base,
afforded
quantitatively
N-
benzylidenebenzenamine (96% selectivity) (Table 2, entry 1).
Previous experiments revealed that the reaction in presence of
KOH resulted in longer reaction times (entry 4) than using
potassium tert-butoxide (entry 3), to achieve similar
conversion with the same substrate. Moreover, it was tested
that the reaction without base did not occur (entry 5). The
reaction was not efficient at room temperature and best
results were obtained in toluene at 100ºC. In absence of
catalyst, only traces of product were obtained (entry 6).
The substrate scope was examined under the optimized
conditions. Electron-rich 4-methoxyaniline, benzylamine and
1-octylamine gave excellent conversions and selectivity into
the corresponding imines (Table 2, entries 3, 7, 8), 4-
bromoaniline afforded 90% conversion after 20 h reaction
(entry 9).
P
RuCl3
AlCl3
P
KPhosBi(Ru)
P
HCOH
O
P
O
O
OH
DCE
x
KPhosBi
Table 2. Imination of benzyl alcohol with aryl amines catalyzed by KPhos(Ru)[a]
AuCl(tht)
CH2Cl2
OH
N
R
NH2
R
P
Entry Catalysts
Base
R
t
(h)
2
0.5
1.5
Conv.
(%)
100
100
100
Sel.
(%)
96
98
100
P
Cl
Au
P
1
2
3
KPhos(Ru)
RuHCl(CO)(PPh3)3
KPhos(Ru)
KOtBu Ph
KOtBu Ph
KOtBu 4-OMe-
Ph
[b]
x
KPhosBi(Au)
Scheme 2. Synthetic route for post-functionalized KPhosBi(M) polymers.
4
KOH
4-OMe-
Ph
Ph
4
97
100
KPhos(Ru)
Catalytic applications
5
6
7
8
9
KPhos(Ru)
none
KPhos(Ru)
KPhos(Ru)
KPhos(Ru)
none
20
6
2
4
20
0
-
KPhos(Ru): Imination of alcohols. This reaction from unreactive
alcohols without an oxidant, is an important non-polluting
route to provide aldehydes and related products.21 On the
other hand, imines are important compounds in modern
organic synthesis because they are key intermediates in the
synthesis of nitrogen containing heterocycles.22 Generally,
imines are formed by condensation of ketones or aldehydes
and amines, catalysed by an acid. Due to the instability of the
carbonyl group, the synthesis of imines from more stable and
low cost reactant, such as alcohols, has attracted considerable
KOtBu Ph
0.8
100
100
90
100
100
100
100
KOtBu PhCH2
KOtBu CH3(CH2)7
KOtBu 4-Br-Ph
[a]Reaction conditions: T: 100ºC, amine (1.0 mmol), benzyl alcohol (1.2 mmol),
toluene (0.5 mL), base (0.05 mol%), cat. (2.0% mmol based on Ru). [b]0.5% mol.
The possibility of recycling and reusing the catalyst, along with
the occurrence of leaching processes, were examined under
the entry 1 conditions. Recycling experiments show that the
activity of KPhos(Ru) does partially decrease after two cycles
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probably due to the some catalyst loss during the filtration and all cases, the ketone was obtained. The reactionVieewvoArltuictleioOnnlinine
DOI: 10.1039/C9CY00776H
more time is needed to achieve >90 % conversion (Figure 7). In presence of silver co-catalysts is shown in Figure S19.
order to evaluate if the structure of catalyst has changed after Therefore, the system KPhos(AuCl)/AgNTf2 was employed with
recycling we have done XPS analysis of recovered catalyst different terminal alkynes affording total conversion after 1h
(figure S21). The XPS spectrum in the region of Ru3p and P2p is reaction (entries 11-13). However, when the internal alkyne
very similar to that of fresh Ru-polymer. FT-IR after recycling methyl-phenylacetylene was employed, the reaction did not
(see figure S6) shows that (Ru-H) appears as weak signal at carried out even after 20 hours (entry 14).
2055 cm-1 and (CO) at 1982 cm-1 which indicates that the Some others silver-free co-catalysts were used such as:
coordination environment of ruthenium in the polymer is CH3CN/NH4BF4, TfOH and LiNTf2 (entries 4 - 6). Again, the best
mainly maintained. Gratifyingly, no leaching of active results were obtained in presence of lithium triflimide (entry
ruthenium species occurred. Upon removal of the catalyst by 6). However, longer reaction times were necessary to achieve
hot filtration after 30 minutes of reaction, the conversion 100% yield. Rather, when the post-functionalized
remained unaltered for 3 h (Figure S18b).
KPhosBi(AuCl)/LiNTf2 system was applied as catalyst only
traces of hydrated product were detected after 3 hours of
reaction and longer reaction times were necessary to achieve
good conversions (entry 7).
100
90
80
70
60
50
40
30
20
10
0
100
80
60
40
20
0
Table 3. Hydration of alkynes catalyzed[a]
O
MeOH / H2O
Entry
1
2
3
4
5
6
7
8
Catalyst
KPhos(AuCl)/AgNTf2
KPhos(AuCl)/AgOTf
KPhos(AuCl)/AgBF4
KPhos(AuCl)/CH3CN/NH4BF4
KPhos(AuCl)/TfOH
KPhos(AuCl)/LiNTf2
KPhosBi(AuCl)/LiNTf2
KPhos(AuCl)/-
t (h)
1
1.5
10
2
3
3
20
28
10
Yield (%)
100
60
40
25
20
100
80
1
2
3
4
5
6
7
8
Run
Figure 7. Recycling experiments with KPhos(Ru), at 2h reaction time.
KPhos(Ru) was also investigated for transfer hydrogenation of
acetophenone in i-PrOH at reflux, resulting total conversion
after 16 h of reaction. Reaction between benzyl alcohol and
acetophenone leads to a mixture of condensation products
ketone/alcohol (80/20).
2
45
40
9
10
AuCl(PPh3)/AgBF4
AuCl(PPh3)/-
30
O
MeOH / H2O
R1
R2
R1
Cat.
Based on our results and previous reports, the proposed
mechanism for the alkylation of amine with alcohol27 is that a
Ru-alkoxide intermediate was formed under basic conditions,
which catalysed the dehydrogenation of alcohol to carbonyl
compound, and subsequently, the base promotes the
condensation of carbonyl compound with amine to imine.
Entry
11
Catalyst
alkyne
t (h)
1
Yield (%)
100
O
12
13
1
1
100
100
KPhos(AuCl)/AgNTf2
14
20
traces
KPhos(AuX): Hydration of alkynes. Hydration of alkynes is
such an environmentally benign method to form carbon-
oxygen bonds. Furthermore, it has been extensively study that
the efficiency of this reaction lies on the coordination
environment of the gold centre, being far more active when it
forms a cation, although the nature of the corresponding
contranion can also affect. The hydration of phenylacetylene
was selected as model reaction to test the catalytic activity of
KPhos(AuX) (X = Cl, NTf2) polymers in presence of different co-
catalysts.
First, we carried out reactions with KPhos(AuCl) polymer in
presence of different silver-contaning cocatalysts (Table 3,
entries 1 - 3) in order to remove the halide coordinated to the
gold(I) centres and generate the catalytically suitable species
for substrate activation ([PPh3Au]+ species). It was found that
the best results were obtained in presence of silver triflimide
because the triflimide anion stabilizes the cation [PPh3Au]+, in
[a]Reaction conditions: T: 60ºC, alkyne (0.2 mmol), MeOH (0.4 mL), H2O (20 µL) cat
5mol % (based on Au), co-catalyst: 5.5 mol %.
The use of silver salts as cocatalysts significantly affected the
reusability of the catalyst, since after three cycles the catalyst
lost its efficiency. This might be a consequence of the so-called
‘silver effect’, reported by Shi and coworkers,28 which suggests
that silver cations, not only activate gold moieties but also
modified them affording different inactive complexes.
Subsequently, the possibility of recycling the catalyst, along
with the occurrence of leaching processes, was examined with
the KPhos(AuCl)/LiNTf2 system. Even though the catalyst life
has been increased, it is clearly observed how its activity
decreases in each cycle (Figure 8). Therefore, we have tried to
regenerate the catalyst by treating it with LiNTf2 in methanol
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Journal Name
overnight, and we observed that the activity slightly increased not increase after hot filtration, this experiment led to confirm
View Article Online
DOI: 10.1039/C9CY00776H
up to 70%.
that no leaching occurs during the process (see figure S20).
Finally, recycling of KPhos(AuNTf2) using 4-methoxy
phenylacetylene as substrate was performed under entry 1
condition. As can be observed in Figure 9, the catalyst
maintains its activity for ten cycles; however, the selectivity
decreases after the third run and decreases until 40% in the 6th
cycle. It is therefore necessary to regenerate the catalyst,
which is carried out by stirring it in methanol in the presence
of LiNTf2 overnight this reactivation resulted in an increase of
the selectivity to a 100% for four more cycles.
100
100
80
60
40
20
0
80
60
40
20
0
100
100
1
2
3
4
5
6
RUN
80
Figure 8. Recycling experiments with KPhos(AuCl)/LiNTf2 catalytic system.
80
60
60
With the previous results in the hand, we explore the catalytic
activity of KPhos(AuNTf2) under the standard conditions (Table
4). It was found that 4-methoxy phenylacetylene and 1-octyne
yields quantitatively the ketone after 1 h in presence of 20 µl
of water (entries 1 & 3); when reaction was performed without
water the ketone is not obtained (entries 2 & 4). When the
same conditions were applied to internal alkynes, it was found
that methyl phenylacetylene leads selectively the ketone after
3h reaction with higher water amount (entry 6); however,
diphenylacetylene only yields the enol ether (Table 3, product
A) after 22 h (entries 7, 8) and 1,4-dichlorobut-2-yne does not
react (entry 9). These findings suggest the following: (A) the
ketone is only formed after hydration of ketal, as it was
previously reported by Corma et al.29 (B) Ketal of terminal
alkyne undergoes its hydration to ketone faster than those of
internal alkynes.
40
20
0
40
20
0
1
2
3
4
5
6
RUN
7
8
9
10
Figure 9. Recycling experiments with KPhosAuNTf2 (1 h reaction time).
KPhos(AuX): Hydroamination of alkynes. The catalytic performance
of the KPhos(Au)-complexes has been also tested in the
hydroamination of phenyl acetylene with aniline as model reaction
in presence of a cocatalyst (silver salts or CH3CN/NH4BF4).30
Screening of cocatalysts was performed at 70ºC and as it can be
seen in Table 5, the performance of KPhos(AuCl) depends on the
silver salt anion. Anions as tetrafluoroborate were found to be
detrimental to the process, whereas, triflate enabled a much better
performance and triflimide stood out as the best choice, as it
happened for the hydration of alkynes. It is important to note that
when the reaction was carried out with KPhos(AuNTf2) (without
any cocatalyst) the product was obtained selectively in 2 h with high
yield (entry 1)
Table 4. Hydration of alkynes catalysed by KPhos(AuNTf2) [a]
OCH3
R2
O
C
H3CO
R1
OCH3
R2
MeOH / H2O
R2
R1
R2
R1
R1
A
B
Selec. (%)
(A/B/C)
Entry
Alkyne
H2O (µL) t (h) Conv. (%)
1
20
1
100
0/0/100
O
2
3
4
5
6
7
8
-
2
1
80
100
75
90/10/0
0/traces/99
70/30/0
15/85/0
0/0/100
100/0/0
100/0/0
Table 5. Effect of the co-catalyst in the hydroamination of phenylacetylene with aniline
promoted by KPhos(Au)-polymers [a]
20
-
1
NH2
20
40
3
100
100
30
N
3
Entry Catalyst
Co-catalyst[b]
t (h) Conv. (%) Selec. (%)
3
20
20
22
75
1
2
3
KPhos(AuNTf2)
-
2
23
2
85
98
98
94
Cl
9
22
0
-
KPhos(AuCl)
KPhos(AuCl)
AgBF4
AgOTf
100
100
Cl
[a]
Reaction conditions: T: 60ºC, alkyne (0.2 mmol), MeOH (0.4 mL), cat (10 mg,
7.2 μmol, 2.8 mol% based on Au).
4
5
KPhos(AuCl)
KPhos(AuCl)
AgNTf2
2
100
100
100
97
CH3CN/NH4BF4
1.5
In order to verify the heterogeneity of gold-catalyst a hot
filtration experiment was carried out. After 20 minutes, the
solid was separated from the reaction media and filtrate was
stirring under the same conditions. Since the conversion did
6
7
KPhos(AuCl)
AgBF4
-
-
27
24
53
28
53
45
a]Reaction conditions: T: 70ºC, amine (0.17 mmol), alkyne (0.15 mmol), toluene
[
(0.5 mL) and cat. (3.3 mg, 3.2 μmol, 2 mol% based on Au). [b]co-catalyst: 2.2mol%.
6 | J. Name., 2019, 00, 1-3
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Synthesis of KPhosBi: Triphenylphosphine (2.63Vgie,w0A.rt0ic1le Omnolinle)
and biphenyl (1.54 g, 0.01 mol)DOwI: 1a0s.103d9i/sCs9oClvYe0d0776iHn
dichloroethane (20 mL). After purging with N2 for 15 minutes,
dimethoxymethane (2.65 mL, 0.06 mol) and AlCl3 (4.0 g, 0.06
mol) were added and the mixture was heated at 80ºC for 48
hours. The same washing protocol as KPhosRu was employed.
Elemental analysis found: %C 82.2, %H 5.56. TXRF analysis: %P
1.5
Post-functionalization with RuCl3 (KPhosBi(Ru)): Previously
formed polymer KPhosBi (1.52 g) was heated at reflux in
formaldehyde and 2-metoxyethanol (1:4) with RuCl3.nH2O (160
mg, 0.77 mmol)32 for 48 h. The resulting polymer was washed
two times with each solvent in the following order: methanol,
water, acetone and tetrahydrofurane. Elemental analysis
found: %C 85.4, %H 5.66. TXRF analysis: %Ru 0.02, %P 1.5.
Post-functionalization with AuCl(tht) (KPhosBi(Au)): KPhosBi
(100 mg) was heated under reflux in ethanol (20 mL) with
AuCl(tht) (107 mg, 0.530mmol)32 overnight. The resulting solid
was washed with dichloromethane, methanol, acetone and
tetrahydrofurane. Elemental analysis found: %C 52.9, %H 3.44.
TXRF analysis: %Au 2.0, %P 1.5.
Conclusions
This manuscript presents four new heterogenized catalysts
formed by polymerization of phosphine metal complexes via
solvent knitting method. In this way, polymerization of
RuH(CO)Cl(PPh3)3 resulted in a single-site robust material
which maintained its catalytic activity after six cycles in the
synthesis of imines. On the other hand the highly active
homogeneous catalyst Au(PPh3)NTf2 has been polymerized by
the same procedure leading to a heterogeneous framework
that, also, maintained its catalytic activity even after 10 cycles
in the hydration of alkynes and proved to be active in the
hydroamination of alkynes.
In conclusion, we have extend the knitting polymerization
strategy to the field of transition metal complexes affording a
straightforward route to obtain metal containing polymers and
open the possibility to heterogenize many other soluble
catalysts.
Experimental
Materials
RuHClCO(PPh3)3 and AuX(PPh3) (X = Cl, NTf2) complexes were
prepared according to literature.31 Triphenylphosphine,
biphenyl, iron trichloride, aluminium trichloride, ruthenium
trichloride, chloro(tetrahydrothiophene)gold(I) and potassium
tetrachloroaurate(III) were obtained from commercial sources.
Catalytic activity
Typical procedure for the synthesis of imines: In a 5 mL
SUPELCO reactor: 0.1 mmol of amine, 0.12 mmol of benzyl
alcohol and 2.0 mg of KPhosRu in 0.5 mL of toluene are mixed
and heated at 100ºC for the corresponding time (Table 2). The
conversion was analyzed by GC-MS chromatography.
Typical procedure for the hydration of alkynes: a) without co-
catalyst: alkyne (0.2 mmol), 10 mg (7.2 µmol) of
KPhos(AuNTf2), 0.4 mL of methanol and 20 µL of H2O were
introduced in a 5 mL SUPELCO reactor and the mixture heated
under stirring at 60ºC for the corresponding time (Table 4); b)
in presence of co-catalyst: In a 5 mL SUPELCO reactor: alkyne
(0.2 mmol), KPhos(AuCl) (10 mg, 9.7 µmol) and co-catalyst
(10.7 µmol) are mixed in 0.4 mL of methanol and 20 µL of H2O
at 60ºC for the corresponding time (Table 3).
Preparation of polymers
Synthesis of KPhos(Ru): In a sealed tube, using a procedure
similar to that previously reported for knitted polymers,10
[RuHClCO(PPh3)3] (118 mg, 0.134 mmol) in dichloromethane
(10 mL) was flushed with N2. After 15 minutes AlCl3 (1.58 g,
12.03 mmol) was added and the mixture heated at 40ºC for 72
hours. Then, the solid was washed with dicloromethane, HCl
(aq) 4% (vol), tetrahydrofuran and acetone and the brown
resulting solid dried at 70ºC overnight. Yield 90%. Elemental
analysis found: %C 47.9, %H 3.9. TXRF analysis: %Ru 22.0, %P
14.1.
Synthesis of KPhos(Ru)Bi: Following the above method,
biphenyl (32.4 mg, 0.210 mmol) was added to the solution of
[RuHClCO(PPh3)3] (100 mg, 0.105 mmol) in dichloromethane
(12 mL). After flushing N2 for 15 minutes, AlCl3 (1.40 g, 10.5
mmol) was added and the mixture heated at 40ºC for 72
hours. The same work-up was employed. Yield: 97%. Elemental
analysis found: %C 64.3, %H 4.12. TXRF analysis: %Ru 8.0, %P
4.9.
Typical procedure for the hydroamination of alkynes: In a 5
mL SUPELCO reactor: aniline (0.17 mmol), alkyne (0.15 mmol),
KPhos(AuX) (3.3 mg, 3.2 μmol) and co-catalyst (3.52 µmol) are
mixed in dry toluene (0.5 mL) at 70ºC. Conversion was
analysed by GC-MS (Table 5).
Some representative examples of the chromatograms
obtained are recorded in Figures S21-S25
Conflicts of interest
Synthesis of KPhos(AuCl): Following the above method, (PPh3)
AuCl(PPh3) (401.4 mg, 0.813 mmol), AlCl3 (1.08 g, 8.13 mmol)
was refluxed in dichloromethane (63 mL) for 48 h. The same
work-up was employed. Yield 96%. Elemental analysis found:
%C 42.5, %H 3.37. ICP analysis: %Au 19.0, %P 15.0.
Synthesis of KPhos(AuNTf2): Following the above method
(PPh3)Au(NTf2) (500 mg, 0.676 mmol), AlCl3 (0.90 g, 6.76 mmol)
was heated at 40ºC in dichloromethane (65 mL) for 48 h. Yield
98% The same work-up was employed. Elemental analysis found:
%C 82.2, %H 5.56. ICP analysis: %Au 14.9, %P 13.3.
“There are no conflicts to declare”.
Acknowledgements
Authors acknowledge to MINEICO of Spain MAT2017-82288-
C2-2-P project for financial support. AVG thanks Ministerio de
Educación y Formación Profesional for FPU17/03463.
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The knitting strategy have been applied to obtain metal-phosphine porouDsOoI: r10g.1a0n39ic/C9CY00776H
polymers (Kphos(M)) that result effective heterogenized catalysts towards different
reactions.
X
Au
P
P
CO
H
Ru
Ru
Cl
P
P
P
P
Au
Au
X
CO
H
Ru
Ru
Cl
X
P
P
Au
: CH2,
X