Alkene hydrosilylation catalyzed by easily assembled Ni(ii)-carboxylate MOFs

Article abstract of DOI:10.1039/c9sc00126c

We report the first Ni MOF catalysts for anti-Markovnikov hydrosilylation of alkenes. These catalysts are bench-stable and easily-assembled from simple Ni salts and carboxylic acids. The best catalyst gives turnover numbers up to 9500 and is robust even a

Full text of DOI:10.1039/c9sc00126c

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Alkene Hydrosilylation Catalyzed by Easily Assembled Ni(II)-
Carboxylate MOFs
Zhikun Zhang,a Lichen Baia and Xile Hu*a
Received 00th January 20xx,
Accepted 00th January 20xx
DOI: 10.1039/x0xx00000x
www.rsc.org/
We report the first Ni MOF catalysts for anti-Markovnikov catalyst, the Fe-containing 2D Hf-MOF, had been developed for
43
hydrosilylation of alkenes. These catalysts are bench-stable and alkene hydrosilylation,
and it was applied for the
easily-assembled from simple Ni salts and carboxylic acids. The best hydrosilylation of only four simple alkenes. This Fe MOF catalyst
catalyst gives turnover numbers up to 9500 and is robust even after was prepared by post-synthetic metalation strategy.
a
10 recycling runs. The catalyst can be applied for the hydrosilylation However, the synthesis of ligands containing two types of
of a wide range of alkenes, achieving good synthetic utility and orthogonal coordination groups, necessary for this strategy, can
functional group tolerance.
be challenging. An analogous strategy was adapted for the
development of Co-coordination polymer catalysts for alkyne
hydrosilylation and alkene hydroborylation.44, 45
Catalytic hydrosilylation of alkenes1-7 is one of the most
important methods to synthesize organosilanes, which are
precursors to silicon-based polymers and intermediates in
organic synthesis8-13. Pt-based catalysts14-16 are most efficient
Here we report an alternative MOF system that is easy to
prepare, stable, and exhibits broad substrate scope for alkene
hydrosilylation. Our catalysts are based on Ni carboxylate
MOFs46-48, which can be prepared by mixing simple Ni salts with
di- or polycarboxylate ligands.49 The Ni centers at the nodes of
these MOFs can be accessible reaction centers.50 Some Ni
carboxylate MOFs are reported to catalyze organic reactions51-
54 as well as electrochemical oxygen evolution55. However, none
is known to catalyze alkene hydrosilylation prior to this work. In
fact, these Ni MOFs are the first Ni-based heterogeneous
catalysts for alkene hydrosilylation.
We started with a Ni MOF of the benzenedicarboxylic acid
ligand (BDC, L1), which was characterized previously.55 This
MOF is made of ultrathin 2-dimensional nanosheets, in which
the hydroxyl-coordinated nickel center could act as the active
site for hydrosilylation. In initial exploration, we also screened
analogous compounds assembled from three other commonly
for hydrosilylation. However, the low abundance and high cost
18
of Pt17,
have motivated the development of base metal
catalysts. A growing number of Fe, Co, Ni, Cu and Mn complexes
are reported as efficient homogeneous catalysts in alkene
hydrosilylation4-7, 19-33. Through rational ligand development, it
is possible to turn the reactivity, 20 regioselectivity,4, 31 and even
enantioselectivity6 of base metal catalysts. Despite this
progress, significant improvement of base metal catalysts is still
required for practical applications. The designer ligands and
complexes require multi-step synthesis and can be expensive.
Many of reported catalysts are air and moisture sensitive,
making them difficult to handle. More importantly, the
separation of homogeneous catalysts from reaction mixture can
be problematic and costly.
Heterogenized catalysts based on metal-organic
frameworks (MOFs) exhibit both the tunability of homogeneous
catalysts and the stability and practicality of heterogeneous
catalysts.34-41 In pioneering work, Lin and co-workers
incorporated active metal complexes into MOFs for alkene
hydrosilylation.42, 43 Nevertheless, only one base metal MOF
used di- and tri-carboxylate ligands
Hydrosilylation of n-decene (1a) by Ph2SiH2 (
(L2- , Table 1).
L4
2
) was used as a
test reaction. A robustness test consisting of three consecutive
runs was employed to identify the most robust catalysts (Table
1). It was noted that with the same nickel salt and ligands,
different synthetic procedures gave catalysts with different
activities (see section 3.1 and 3.2 in the supporting
information). For each metal ligand combination, results from
the best catalysts are shown in Table 1. To our satisfaction, all
a.Laboratory of Inorganic Synthesis and Catalysis, Institute of Chemical Sciences
and Engineering, École Polytechnique Fédérale de Lausanne (EPFL), ISIC-LSCI,
Lausanne 1015, Switzerland. E-mail: xile.hu@epfl.ch
four ligands (L1
and robustness (Table 1, entries 1-4). Biphenyl-4,4'-dicarboxylic
acid (L4) was slightly better than the other three ligands (L1 L3
-L4) gave Ni-MOFs with high catalytic efficiency
Electronic Supplementary Information (ESI) available: [details of any supplementary
information available should be included here]. See DOI: 10.1039/x0xx00000x
-
)
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(Table 1, entry 4). With a simple nickel salt without a ligand, a catalyst (Fig. 1b), similar to the previously reported Ni-L1-1 55
.
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DOI: 10.1039/C9SC00126C
moderate yield was obtained in the first run (Table 1, entry 5). Transmission electron microscope (TEM) indicated the thin
However, numerous black particles were formed during the nature of the catalyst (Fig. 1c). Element mapping showed that
reaction, which were presumably nickel nanoparticles. Very low Ni and O were uniformly distributed throughout the sample
to negligible yields were obtained in 2nd and 3rd runs. We also (Fig. S1, Supporting Information), and X-ray photoelectron
tested some other reported nickel MOFs, 51, 54, 56-58 such as [Ni2- spectroscopy (XPS) indicated Ni was coordinated to carboxylate
(BDC)2-DABCO]
,
Ni-HKUST-1
,
Ni-MOF-74
,
[Ni3(2,6- ligands (Fig. S2, Supporting Information). According to N2
NDC)3(bipy)1.5 and [Ni(C8H4O4)(C5H5NO)] (Table 1, entry 6-10). adsorption experiment (Fig. S3, Supporting Information), the
]
These Ni MOFs all catalyzed the hydrosilylation in good to surface area was about 120 m2/g, and the pore size distribution
excellent yields in the first run; however, they were less robust was narrow and uniform. All pores were between 3.0 nm and
and the yields dropped significantly in the 2nd and 3rd runs. 4.0 nm. Thermogravimetry Analysis (TGA) suggested that the
Recently many cobalt, iron and manganese complexes were catalyst was thermal stable until 400 oC (Fig. S4, Supporting
developed for homogeneous hydrosilylation of alkenes4-7, 59
.
Information). Infra-red (IR) spectrum suggested the existence of
We attempted to prepare Co, Fe, and Mn-MOFs by combining Ni-OH moieties (Fig. S5, Supporting Information).
of a Co, Fe, or Mn salt with L1 under conditions similar to those
for the synthesis of Ni-L1 MOF. However, these compounds
were poor catalysts even in the first run (entries 11-13, Table 1).
Overall the results in Table 1 indicated that Ni carboxylate MOFs
were the most efficient and robust catalysts for alkene
hydrosilylation.
Table 1. Screening of robust MOF catalysts for hydrosilylation of n-decene[a]
Figure 1. (a) PXRD pattern of Ni-L4-1. (b) SEM image of Ni-L4-1; (c) TEM image of Ni-L4-
1
The robustness of Ni-L4-1 was further tested in 10-recycling
catalytic runs. The catalyst maintained a similar level of
efficiency during 8 runs, and afterwards slightly lower yields
were obtained (Figure 2). Even after 10 runs, the yield was still
higher than 60%. The post-catalytic characterization of the
catalyst suggested the catalyst remained in its initial state after
multiple catalytic runs (Section 4.2, Supporting Information).
These results suggest the catalyst is robust.
Although the results from the recycling experiments were
consistent with the catalyst being heterogeneous, they were
not proofs. To further probe whether the catalysis was
homogeneous or heterogeneous in nature, we conducted a
filtration experiment (Scheme 1 and section 5, Supporting
Information). After 20 minutes of catalytic hydrosilylation, the
yield was 60%. If the reaction was continued for 1.5 h, the final
yield was 87%. If the reaction medium was centrifuged to
separate the solution and solid phase, and the solution phase
was allowed to react for another 1.5 h, no further
hydrosilylation beyond the initial 60% was observed. The
possibility that a homogeneous catalyst species was deactivated
by centrifugation could be ruled out because the solid phase
was still active. This result gives further support that Ni-L4-1 is
a heterogeneous catalyst.
Entry
1
catalysts
Ni-L1-1
Ni-L2-1
Ni-L3-1
Ni-L4-1
1st
85
85
88
87
79
90
67
71
62
82
<1
14
2
2nd
82
85
71
82
10
84
14
52
86
15
nd
nd
nd
3rd
78
88
80
92
3
2
3
4
.
5
NiCl2 6H2O
6
[Ni2-(BDC)2-DABCO]
Ni-HKUST-1
77
6
7
8
Ni-MOF-74
17
15
8
9
[Ni3(2,6-NDC)3(bipy)1.5
[Ni(C8H4O4)(C5H5NO)]
Co-L1-1
]
10
11[b]
12[b]
13[b]
nd
nd
nd
Fe-L1-1
Mn-L1-1
[a] Conditions: 0.2 mmol 1a, 0.21 mmol diphenylsilane 2, 2.5 mol% catalyst and
10 mol% NaOMe, 2 mL tetrahydrofuran, 40 oC reaction temperature. The yields
were obtained through GC with dodecane as the internal standard, the results
are the average values of two parallel experiments. [b] Thes scale was 0.1
mmol. nd = not determined.
As Ni-L4-1 was the optimized catalyst, it was subjected to
further characterization (Fig. 1a-1c and section 4.1, Supporting
Information). According to powder X-ray diffraction (PXRD)
pattern (Fig. 1a), the catalyst is crystalline. Scanning Electron
Microscope (SEM) showed sheet-like morphology of the
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sufficient to furnish the reaction in 95% yield after 40 hours,
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DOI: 10.1039/C9SC00126C
corresponding to a turnover number (TON) of 9500. Silanols are
key intermediates for the synthesis of silicon-based polymeric
material.61-63 A catalytic amount of sodium hydroxide could be
used to transfer the silane product (3b) into a silanol (4) in a
one-pot procedure (Scheme 2b). The latter step does not
require nickel catalysis (Section 3.5, Supporting Information)64.
Several experiments were conducted to obtain preliminary
insights in the mechanism of the reaction. When a deuterated
silane, Ph2SiD2 (D-2) was used for the hydrosilylation of 1d
,
deuterium scrambling was observed in -carbon positions
, , 
of D-3d (Scheme 3a). In homogeneous Ni-catalyzed
hydrosilylation of alkenes, nickel hydride (Ni-H)65 species are
commonly proposed as the key intermediate.30, 66-69 The result
in Scheme 3a suggests that an analogous Ni-H species in the Ni-
MOF catalyst is an intermediate. When the final reaction
mixture after hydrosilylation was quenched with water,
hydrogen evolution was observed (Scheme 3b). An analogous
quenching of the reaction mixture without the alkene substrate
yielded copious H2. These results suggest the Ni-H species as
the resting state of the catalyst. Although the crystal structure
of Ni-L4-1 is inaccessible due to poor crystallinity, we suspect
the local structure of Ni centers to be similar to the Ni centers
in Ni-L1-1, which is supported by their similar IR and UV-vis
spectra (Fig. S5 and S6, Supporting Information). The active site,
thus, is a Ni center with an exchangeable ligand such as
hydroxyl. Upon silane addition, this Ni-OH group is converted to
the Ni-H intermediate. There are two possible roles for NaOMe:
to activate silane by forming a 5-coordinate silicon intermediate
prone to hydride transfer,32 or to form a Ni-OMe species that
reacts with silane to form the Ni-H.30 Finally, to probe whether
the reaction occurred exclusive on a defect site rather than a
node site, a defect poison, NaSCH3, was used as an additive in
the hydrosilylation. (Scheme 3c). In the presence of NaSCH3, the
hydrosilylation still proceeded smoothly to give a yield of 89%.
This result suggest the defect sites are not the major reaction
sites.
Figure 2. Testing the robustness of Ni-L4-1 in ten recycling experiments with 1a and 2 as
substrates
Scheme 1. Probing the heterogeneous nature of Ni-L4-1
The scope of this heterogeneous hydrosilylation was then
explored using Ni
Makovnikov selectivity was observed. Unhindered alkyl alkenes
were hydrosilylated in high yields (1a 1e). The internal alkenyl
-L4-1 as catalyst (Table 2). Generally, anti-
-
carbon could be substituted by a secondary (1f) or tertiary alkyl
group (1g). When the substrate contained both an internal
(cyclic) and a terminal C-C double bond (1h), hydrosilylation was
selective on the terminal position. Functional groups such as
chloro (1i), trifluoromethyl (1j), cyanide (1k), and silyl (1l
groups were readily tolerated. Hydroxyl and carbonyl groups
needed to be protected (1o 1p). Ester group (1q 1r) was
compatible. Although nickel-catalyzed ring-opening of epoxide
was reported,60 epoxide was tolerated by this method (1s
1t).
Allylic ether (1u) and allylic amine (1v 1w) were also suitable
-1n)
,
,
,
,
Table 2. Substrates scope [a, b]
substrates. Styrene (1x) was hydrosilylated at both α and β
positions, due to stabilization of benzyl intermediates. Anti-
Makovnikov selectivity was again obtained for α-substituted
styrenes (1y, 1z). For an acyclic internal alkene, 2-octene, the
substrate was first isomerized to a terminal alkene before
hydrosilylation to give the terminal silane (3b'). Similar results
were previously reported in homogeneous and nanoparticle
catalysis.25 Normal hydrosilylation occurred on cyclic alkenes
such as norbornene
(1ac) and cyclopentene (1ad) as
isomerization was either impossible or indistinguishable. When
1-allylpyrene (1aa), a rather big molecule, was used as the
substrate, nearly no product (3aa) was obtained. Comparing the
results using 1e and 1aa as substrates suggests catalysis is
sensitive to the size of the substrate, which indicates that the
reaction occurs mostly inside the mesopores.
To show the potential of the current method in practical
applications, a 150-mmol scale synthesis was carried out using
1b and
2 as substrates (Scheme 2a). 0.01 mol% of catalyst was
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Scheme 3. Mechanism study: (a) Isotope labelling experiment; (b) Quenching by water;
the quench was after full conversion of silane in the hydrosilylation reaction. (c) Catalyst
poison test.
Conclusions
In summary, we have developed efficient and robust MOF
catalysts for hydrosilylation of alkenes. The catalysts are based
on Ni carboxylate MOFs, which can be easily assembled from
readily available Ni salts and carboxylic acids. The best catalyst,
Ni-L4-1, shows high activity even after 10 recycling
experiments. Up to 9500 TONs are achieved, the highest for a
base metal heterogeneous catalyst. This catalyst can be applied
for hydrosilylation of a large number of alkenes, with good
functional group tolerance. This work demonstrates the
synthetic utility of base metal MOF catalysts for alkene
hydrosilylation.
Conflicts of interest
[a] Conditions: 0.5 mmol (1.0 eq.) alkenes and 0.525 mmol (1.05 eq.)
diphenylsilane, 2.5 mol% Ni-L4-1, 10 mol% NaOMe, 2.0-5.0 mL
tetrahydrofuran (THF), reaction temperature: 40-80 oC, reaction
time: 2-84 hours. [b] The yields are isolated yields through column
chromatography or preparation thin-layer chromatography with
silica gel.
The authors declare no conflict of interest
Acknowledgements
This work is supported by the Swiss National Science
Foundation and the European Research Council (no.681292).
We thank the following individuals at EPFL for experimental
assistance and discussion: Dr. Jun Gu, Weiyan Ni, Laurent
Liardet, Ilia Kochetygov, Prof. Dr. Wendy L. Queen, and Dr.
Pascal A. Schouwink.
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Chemical Science
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DOI: 10.1039/C9SC00126C
Easily-assembled Ni MOFs are efficient and robust catalysts for alkene hydrosilylation.