Incorporation of PdCl2P2 Complexes in Ni-MOF for Catalyzing Heck Arylation of Functionalized Olefins

Article abstract of DOI:10.1002/ejic.201900618

Two palladium complexes of a PdCl₂P₂ type with P = tri(1-piperidinyl)phosphine (Pd-1) and triphenylphosphine (Pd-2) were successfully immobilized on [Ni₈(OH)₄(OH₂)₂(L)₆]_n (Ni-MOF) material [L=4,4′-(benzene-1,4-diyldiethyne-2,1-diyl)bis(1-H-pyrazole)] to form Pd@Ni-MOF composites. The presence of big octahedral cavities in the Ni-MOF structure (2.4 nm) enabled incorporation of PdCl₂P₂ molecules inside the Ni-MOF, as confirmed by physicochemical measurements and computer simulation. The Pd@Ni-MOF composites catalyzed arylation of estragole by iodobenzene with an efficiency higher than that for the corresponding PdCl₂P₂ compounds without MOF. Arylation of eugenol by PhB(OH)₂ unexpectedly resulted in the formation of ether as the main product. This was explained by the dominating activity of the Cu@MOF catalyst, formed in situ under the reaction conditions.

Full text of DOI:10.1002/ejic.201900618

A Journal of
Accepted Article
Title: Incorporation of PdCl2P2 complexes in Ni-MOF as catalysts for
Heck arylation of functionalised olefins
Authors: Stanislawa Tarnowicz-Ligus, Adam Augustyniak, and Anna
Trzeciak
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To be cited as: Eur. J. Inorg. Chem. 10.1002/ejic.201900618
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10.1002/ejic.201900618
European Journal of Inorganic Chemistry
Incorporation of PdCl2P2 complexes in Ni-MOF as catalysts for Heck arylation
of functionalised olefins.
Stanisława Tarnowicz-Ligus, MSc; Dr. Adam Augustyniak; Prof. Dr. Anna M. Trzeciak*
Faculty of Chemistry University of Wrocław, 14 F. Joliot-Curie, 50-383 Wrocław, Poland
*corresponding author: anna.trzeciak@chem.uni.wroc.pl
Abstract
Two palladium complexes of a PdCl2P2 type with P=tri(1-piperidinyl)phosphine (Pd-1) and
triphenylphosphine (Pd-2) were successfully immobilised on [Ni8(OH)4(OH2)2(L)6]n (Ni-MOF)
material (L=4,4'-(benzene-1,4-diyldiethyne-2,1-diyl)bis(1-H-pyrazole)) to form Pd@Ni-MOF
composites. The presence of big octahedral cavities in the Ni-MOF structure (2.4 nm) enabled
incorporation of PdCl2P2 molecules inside the Ni-MOF, as confirmed by physicochemical
measurements and computer simulation. The Pd@Ni-MOF composites catalysed arylation of
estragole by iodobenzene with efficiency higher than corresponding PdCl2P2 compounds
without MOF. Arylation of eugenol by PhB(OH)2 unexpectedly resulted in formation of ether
as the main product. This was explained by the dominating activity of the Cu@MOF catalyst,
formed in situ in reaction conditions.
.
Introduction
Palladium complexes are recognised as highly active catalysts of various C-C bond forming
reactions leading to arylated products.[1-9] In this area, the arylation of olefins already bearing
one phenyl ring, occuppies a special place as a method enabling preparation of differently
substituted stilbenes for the pharmaceutical industry. [10-13] Arylation of olefinic substrates
can be performed according to the Heck procedure, using aryl halide as a source of the aryl
group.[14-16] Alternatively, in the Heck-type reaction, phenylboronic acid donates a phenyl
group to the substrate and addition of the oxidant is necessary to reoxidise the palladium.[17-
20] Both methods work very efficiently, although the first one, Heck coupling is more universal.
However, the problem which is often addressed in a homogeneous system is good separation
of the catalyst from the reaction mixture to guarantee metal-free products.[1] The recommended
solution is immobilisation of the catalyst using inorganic or organic support. [21-26] In the past,
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10.1002/ejic.201900618
European Journal of Inorganic Chemistry
metal-organic frameworks (MOFs) have been studied as potential carriers for metal
catalysts.[27-30]
Metal-organic frameworks (MOFs) present an attractive class of materials due to their highly
porous nature and their chemical and structural diversity. The special nature of these
compounds is evidenced by a wide range of applications in numerous areas, such as sensing,
medicine, gas separation and catalysis.[31-34] Due to the permanent porosity and accessibility
of voids, MOFs are perfectly suited to host other molecules and, as a result, to create composites
with new properties. In most cases, the incorporation primarily concerned gases, organic
compounds and metal nanoparticles as guest molecules.[35-37] In contrast, encapsulation of
metal complexes in MOFs are scarce, probably due to pore size limitations and the stability of
MOFs. To date, only a few examples have been reported on the successful incorporation and
release of ruthenium non-conventional anticancer drugs such as [Ru(p-cymene)Cl2(pta)]
(RAPTA-C) to the CPO-27-Ni and [Ni8(μ4-OH)4(μ4-OH2)2(μ4-4,4′-(buta-1,3-diyne-1,4-
diyl)bispyrazolato)6]n MOFs. [38-39]
It is worth mentioning the remarkable approach reported by Grela et al. in which ruthenium
alkylidene complexes were successfully supported inside (Al)MIL-101-NH2·HCl MOF and
used as catalysts an olefin metathesis in a flow system. [40] A typical photocatalyst, a
[Ru(bpy)3]2+ complex, was incorporated into numerous MOFs such as ZJU-100, PCN-99, UiO-
66, MIL-125-NH2.[41-44] Che and coworkers introduced pincer platinum(II) complexes into a
series of MOFs materials as efficient catalysts for photoinduced dehydrogenation reactions.[45]
Wang et al. reported luminescent organogold (III) photocatalyst immobilised in MOF1 and
ZJU-28 materials.[46] The original synthetic strategy, based on a direct incorporation of
Pd(H2bpydc)Cl2 (H2bpydc = 2,2′-bipyridine-5,5′-dicarboxylic acid) in the UiO-67 type MOF,
has been applied to obtain a single-site catalyst for C-Cl bond activation [47].
Phosphine ligands play an important role in the creation of highly active metal catalysts,
creating an optimal environment for substrates activation through electronic and steric
influence.[48] In palladium catalytic systems, phosphines stabilise metal complexes and
promote a homogeneous reaction pathway. Immobilisation of such a catalyst on the solid carrier
can facilitate a heterogeneous mechanism and solve separation problems. However, the
incorporation of the phosphine complexes into a MOF material has never been examined yet.
The previously reported Pd-phosphine-MOF composites were formed by the direct
coordination of Pd to the ligand used as a linker. [49]
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Herein, we report the successful encapsulation of two palladium phosphine complexes
of a PdCl2P2 type in the cavity of a pyrazolate Ni-MOF. The Ni-MOF was chosen as the support,
based on the following considerations: (i) the strength of the Ni–azolate bonds conferring high
stability of the Ni-MOF material, (ii) the large-pores of Ni-MOF with two types of nanocages,
octahedral and tetrahedral voids of about 2.4 nm and 1.1 nm inner size, respectively.[50] The
Pd@Ni-MOF composites were used as catalysts in the model Heck and Heck-type arylation of
estragole and eugenol.
Results and discussion
Synthesis and characterisation of Pd@Ni-MOF
The highly porous and robust MOF material [Ni8(OH)4(OH2)2(L)6]n (Ni-MOF) where L=4,4'-
(benzene-1,4-diyldiethyne-2,1-diyl)bis(1-H-pyrazole) [50] was chosen as a platform for the
incorporation of two phosphine palladium complexes of PdCl2P2 type containing tri(1-
piperidinyl)phosphine (Pd-1) and triphenylphosphine (Pd-2) as the P-ligands. The Ni-MOF
shows remarkable thermal and chemical stability, high porosity and robustness. It was expected
therefore, that its structure would be preserved in catalytic reaction conditions. Additionally,
octahedral voids of about 2.4 nm are big enough for the encapsulation of the phosphine
palladium complexes (Figure 1). According to the computer simulation (grand canonical Monte
Carlo) two molecules of Pd-1 and three molecules of Pd-2 could be accommodated in the Ni-
MOF structure (see supplementary material).
Figure 1. View of the octahedral voids in (a) the structure of Ni-MOF and (b) the structure of the Pd-
1 (above) and Pd-2 (below) complexes.
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The Pd-1 and Pd-2 complexes were immobilised by suspending the activated Ni-MOF in
toluene or dichloromethane solutions of the palladium complexes.
The BET surface area of the Ni-MOF was estimated at 3020 m2g−1 which was higher
than that reported by Navarro et al. (2215 m2 g−1). [50] The difference was most likely caused
by the lower content of DMF in the studied Ni-MOF. Figure 2 a-b shows the N2 adsorption-
desorption isotherm for Pd-1@Ni-MOF and Pd-2@Ni-MOF. The surface area decreased to
1967 m2g−1 for Pd-1@Ni-MOF and to 2225 m2 g−1 for Pd-2@Ni-MOF as a result of
incorporation of palladium complexes inside the Ni-MOF (Table 1).
Figure 2. a) and b) N2 (77 K) adsorption isotherms for Ni-MOF (red), a) Pd1@Ni-MOF and b) Pd2@Ni-
MOF (blue). Empty symbols denote desorption.
Table 1. BET surface area and total pore volume for Ni-MOF, Pd-1@Ni-MOF and Pd-2@Ni-MOF.
BET Surface Area (m²/g) Total pore volume (cm³/g)
Ni-MOF
3020(24)
1967(11)
2225(46)
1.48
0.98
1.09
Pd-1@NiMOF
Pd-2@NiMOF
The XRPD method evidenced that after bonding of the Pd complexes, the Ni-MOF material
maintained its crystallinity (Figure 3).
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10.1002/ejic.201900618
European Journal of Inorganic Chemistry
Figure 3. XRPD patterns of Ni-MOF as synthesised, Pd-1@Ni-MOF, Pd-2@Ni-MOF.
The XPS spectra revealed two peaks at 337.1 and 342.2 eV for Pd-1@Ni-MOF and at 337.6
and 342.9 eV for Pd-2@Ni-MOF assigned to the 3d5/2 and 3d3/2 core levels of divalent
palladium (Table 2). Additionally, the P2p binding energy equal to 132.3 eV for Pd-1@Ni-
MOF and 131.6 eV for Pd-2@Ni-MOF were close to the values determined in Pd(II) complexes
with phosphine ligands. [51-52]
Table 2. XPS data (BE, eV) for Pd-1@Ni-MOF and Pd-2@Ni-MOF
Pd-1@Ni-MOF
132.3
Pd-2@Ni-MOF
131.6
P2p
Pd 3d3/2
Pd 3d5/2
337.1
337.6
342.3
342.9
In contrast, analysis of the IR spectrum was not informative about the presence of Pd-1 and
Pd-2 complexes in the porous Ni-MOF matrix. The positions of (C=C), (C=N) and (C-N)
bands of the pyrazole ring of the ligand in the Pd-1@Ni-MOF and Pd-2@Ni-MOF spectra were
almost identical compared to pristine Ni-MOF. A small difference was observed only for the
(P–C) band situated at ca. 1090 cm-1 in the Ni-MOF and Pd-2@Ni-MOF spectra.
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Catalytic activity of Pd@MOF in Heck and Heck-type reactions.
The obtained Pd@Ni-MOF catalysts were employed in Heck and Heck-type couplings
of eugenol and estragole. It was expected that both substrates would be transformed to
corresponding stilbenes, 1 or 2 by arylation with iodobenzene (Heck coupling) or with
phenylboronic acid (Heck-type coupling) (Figure 4). Formation of some amounts of products
1b and 2b was also expected on the basis of our earlier experience with the Pd(OAc)2 catalyst
[53].
Figure 4. Heck and Heck-type reactions of eugenole and estragol catalysed by Pd@Ni-MOF.
The first tests, carried out using a low amount of Pd@Ni-MOF, 0.1 mol%, showed that in Heck
conditions only Pd-1@Ni-MOF was active and it converted 33% of estragole to the desired
products (Table 3). However, this catalyst did not form any product from eugenol. In the same
conditions the second catalyst, Pd-2@Ni-MOF, was not active in the Heck coupling of either ,
eugenol and estragole substrate. Better results were obtained in a Heck-type coupling with
phenylboronic acid as the source of the phenyl group. Conversion of estragole was relatively
low for both catalysts and Pd-2@Ni-MOF provided better results, with 25% of product 2 as a
mixture of E and Z isomers. Unexpectedly, arylation of eugenol resulted in formation of a new
product, ether 1c, as the main one for both catalysts. Ether 1c was not observed in our earlier
studies carried out using Pd(OAc)2 under similar conditions. On the other hand, formation of
ethers in copper-mediated reactions of phenylboronic acid and phenol derivatives is known as
the Chan-Lam process.[54-56] In order to explain the presence of 1c in our reactions, additional
experiments were performed in the absence of the Pd@Ni-MOF catalyst. Elimination of
Pd@Ni-MOF from the reaction mixture resulted in formation of 35% of 1c as the only product
(Table 4). A similar result, 30% of 1c, was achieved in the presence of pure Ni-MOF without
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10.1002/ejic.201900618
European Journal of Inorganic Chemistry
palladium (Table 4). These results indicated that ether 1c was formed in the Chen-Lan process
by the contribution of the Cu(OAc)2 used in our system as an oxidant of palladium. Domination
of the Cu(OAc)2 activity over that of palladium led to the formation of product mixture,
composed of 2 and 1c.
Table 3. Results of the arylation of eugenol and estragole with iodobenzene and phenylboronic
acid catalysed by Pd@Ni-MOFcatalysts.
Conversion
of PhI or
olefin
(%)
1 (E/Z) or
2 (E/Z) (%)
1c
(%)
Entry
Catalyst
Base
ArX
PhI
Olefin
1
2
3
4
5
6
7
8
Pd-1@Ni-MOF
Pd-2@Ni-MOF
Pd-1@Ni-MOF
Pd-2@Ni-MOF
Pd-1@Ni-MOF
Pd-2@Ni-MOF
Pd-1@Ni-MOF
Pd-2@Ni-MOF
-
-
-
-
-
-
eugenol
estragole
eugenol
estragole
K2CO3
33
-
22/12
-
-
-
40
42
8
6/3
13/9
6/2
15/9
31
20
-
-
PhB(OH)2
25
1
Reaction conditions: PhI (1 mmol) or PhB(OH)2 (1.5 mmol), olefin (1 mmol), K2CO3 or Cu(OAc)2 (2 mmol), [Pd]
(1×10-6 mol), DMF (5 mL), 110oC, 6h. Yield based on GC-MS.
Catalytic activity of Pd-1@MOF
Further studies on the activity of Pd@Ni-MOF catalysts were undertaken using a higher
amount of palladium: 1 mol% for the Heck coupling of substrates with iodobenzene and 0.5
mol% for the coupling with phenylboronic acid (Table 4). First, Pd-1@Ni-MOF was tested and
the Pd-1 complex without MOF was also used as a reference. Interestingly, Heck arylation of
estragole gave better results (76% conversion) with immobilised Pd-1@MOF than with the Pd-
1 complex only (67%). Both catalysts selectively formed the expected stilbene and two
stereoisomers, 1E and 1Z, were identified with the main one being 1E. Attempts to recycle Pd-
1@Ni-MOF gave positive results and the reaction was repeated three times with the same
catalyst sample. However, conversion of iodobenzene decreased from 76% to 53% indicating
some loss of catalytic efficiency. A possible reason for this could be decomposition of the
catalyst and leaching of palladium. In fact, ICP analyses of the Pd-1@Ni-MOF catalyst
recovered after the third run evidenced a decrease of palladium content to 0.042%.
The second series of arylation reactions with Pd-1@Ni-MOF was carried out using eugenol as
the substrate. The reference reaction with the Pd-1 catalyst resulted in 100% conversion of
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10.1002/ejic.201900618
European Journal of Inorganic Chemistry
eugenol to the corresponding stilbene, present in two isomeric forms, E and Z, in comparable
amounts. The reactivity of Pd-1@Ni-MOF appeared quite different as besides the expected
stilbene, product 1c was also formed with a 20% yield. In this reaction, conversion of eugenol
was 50% and it decreased to 33% for the recovered catalyst. Moreover, in five subsequent runs
the selectivity changed and 1c became the main product. It could therefore be assumed that the
palladium immobilised in the MOF was active only in the first run and formed product 2. In
the next runs, the yield of product 2 decreased significantly and formation of ether 1c should
be assigned to the activity of Cu(OAc)2 only.
Table 4. Results of the arylation of eugenol and estragole catalysed by Pd-1 and Pd-1@Ni-
MOF.
Conversion
of PhI or
olefin
(%)
54
1 (E/Z) or
2 (E/Z) (%)
Entry
Catalyst
Run
ArX
PhI
Olefin
1c (%)
1
2
3
4
5
Pd-1a
Pd-1
-
-
-
-
-
-
-
32/18
36/22
48/22
50/15
53/0
67
76
1
2
3
estragole
Pd-1@Ni-MOF
65
53
6
7
8
Without catalyst
Ni-MOF
-
-
-
35
30
100
50
33
34
28
48
36
-
-
35
30
-
Pd-1
53/42
15/13
8/8
6/6
3/3
3/3
2/2
9
1
2
3
4
5
6
20
17
20
18
36
28
10
11
12
13
14
eugenol
PhB(OH)2
Pd-1@Ni-MOF
Heck reaction conditions: PhI (1 mmol), olefin (1 mmol), K2CO3 (2 mmol), [Pd] (1×10-5 mol), [Pd] (0.5×10-5
a
mol) DMF (5 mL)
Heck-type reaction conditions: PhB(OH)2 (1.5 mmol), eugenol (1 mmol), Cu(OAc)2 (2 mmol), [Pd] (0.5×10-5 mol),
DMF (5 mL). Yield based on GC-MS.
Pd-1 - Dichlorobis[tri(1-piperidinyl)phosphine]-palladium(II)
Catalytic activity of Pd-2@Ni-MOF
Results obtained with the application of Pd-2@Ni-MOF catalyst are presented in Table 5. The
positive effect of Ni-MOF on the substrates conversion is seen clearly when the productivities
of Pd-2 and Pd-2@Ni-MOF were compared. Thus, the Pd-2 complex provided 54% of stilbene
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10.1002/ejic.201900618
European Journal of Inorganic Chemistry
while Pd-2@Ni-MOF formed 68% of product 1. Recycling of Pd-2@Ni-MOF was performed
five times with satisfactory results. The yield of products decreased to 58% but it was still
comparable with results obtained in a homogeneous system with a Pd-2 complex. The
composition of the products was stable within the series of reuse experiments and the desired
stilbene was mainly formed. The amount of side product 1b remained at the level of ca. 6%.
In the next step of the studies, the Pd-2 catalyst was employed as a pure complex and in an
immobilised form, Pd-2@Ni-MOF, to the arylation of eugenol with phenylboronic acid. In this
case, the Pd-2 complex was more active than Pd-2@Ni-MOF with conversion of 86% versus
58%. Similarly, as in the reaction with Pd-1@Ni-MOF, product 1c was also formed in this
system. The yield of 1c increased in subsequent catalytic runs from 11% in the first reaction to
23% in the fourth one. At the same time, the amount of stilbene decreased from 43% to 8%.
The trend of the changes was analogous to that observed for Pd-1@Ni-MOF. It is seen that the
activity of Pd-2@Ni-MOF catalyst decreased fast in the Heck-type conditions, namely in the
presence of an excess of Cu(OAc)2. In order to explain the reason for this phenomenon,
SEM/EDX studies of the recovered catalyst were undertaken. In the sample of the isolated Pd-
2@Ni-MOF, only a small amount of palladium was found, ca. 0.1 weight%. In contrast, a high
amount of copper was present, ca. 50 weight%. Most probably, the copper covered completely
the catalyst surface and blocked access of the substrates to the active palladium centres.
Moreover, partial exchange of nickel centres by copper centers should be considered. It has
been recently shown that such process occurred effectively in mild conditions [57].
It was therefore interesting to check whether such a catalyst would be useful in the catalytic
process. The answer was positive because the reaction of eugenol with phenylboronic acid
performed in the presence of the recovered catalyst produced 23% of ether 1c.
Table 5. Results of the arylation of eugenol and estragole catalysed by Pd-2 and Pd-2@Ni-
MOF.
Olefin
conversion
(%)
1 (E/Z) or
2 (E/Z)
(%)
26/12
36/16
44/25
35/27
29/28
28/23
1b or
2b
(%)
5
5
6
6
6
6
1c
(%)
Entry
Catalyst
Run
ArX
Olefin
1
2
3
4
5
6
Pd-2a
Pd-2
46
57
75
68
63
57
-
-
-
-
-
-
-
-
1
2
3
4
PhI
estragole
Pd-2@Ni-MOF
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European Journal of Inorganic Chemistry
7
8
5
58
58
26/26
27/25
6
6
-
-
6
9
Pd-2
Pd-2b
-
-
86
84
58
43
38
38
48/35
49/31
23/20
12/7
5/5
3
4
3
-
-
10
11
12
13
14
-
1
2
3
4
11
17
21
23
PhB(OH)2
eugenol
Pd-2@Ni-MOF
1
4/4
1
Heck reaction conditions: PhI (1 mmol), olefin (1 mmol), K2CO3 (2 mmol), [Pd] (1×10-5 mol), [Pd] (0.5×10-5
mol) DMF (5 mL)
Heck-type reaction conditions: PhB(OH)2 (1.5 mmol), eugenol (1 mmol), Cu(OAc)2 (2 mmol), [Pd] (0.5×10-5 mol),
b [Pd] (1×10-5 mol), DMF (5 mL). Yield based on GC-MS.
a
Pd-2 Dichlorobis[tripnenylphosphine]-palladium(II)
Unfortunately, we did not succeed in the conversion of eugenol to the coupling product in the
Heck reaction with iodobenzene. No product was obtained at low (Table 3) or higher catalyst
concentrations (1 mol%). It can be assumed that the presence of the OH group in the eugenol
molecule hindered access to active palladium centers in the MOF structure and blocked the
reaction.
Conclusions
In summary, we presented the first example of the immobilisation of two palladium complexes
of PdCl2P2 type on [Ni8(OH)4(OH2)2(L)6]n (Ni-MOF). The efficiency of the synthetic strategy,
based on simple impregnation from the organic solution, was confirmed by different analyses,
such as SEM/EDX, ICP, XRPD and BET surface area measurements. In addition, the computer
similation indicated the possible incorporation of PdCl2P2 compounds in the octahedral cavities
of the Ni-MOF. The immobilisation of PdCl2P2 complexes on the Ni-MOF resulted in an
increase of the catalytic activity in the arylation of estragole by iodobenzene. This positive
effect can be explained by the improvement of the contact between the catalyst and the reactants
in the porous Ni-MOF matrix. The heterogenised Pd@Ni-MOF catalyst was successfully
separated and used in the next catalytic runs, however, some decrease in its productivity was
noted, probably because of some decomposition. In the arylation of eugenol carried out with
PhB(OH)2 in the presence of the Cu(OAc)2 co-catalyst, instead of the desired stilbene, an ether
was formed. It was found, that copper covered the surface of the Ni-MOF support completely
and blocked the activity of the palladium. Consequently, copper activated the OH group of
eugenol and facilitated etherification. Interestingly, the in situ formed Cu@MOF catalyst was
also active in the formation of an ether. In this case, the ability of the Ni-MOF to form a
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10.1002/ejic.201900618
European Journal of Inorganic Chemistry
composite with transition metals changed the reaction selectivity from palladium-catalysed to
a copper-catalysed one.
Experimental Section
All reagents and solvents were purchased from commercial sources. Copper(I) iodide, dichloro-
bis(triphenylphosphine) palladium(II), dichlorobis[tri(1-piperidinyl)phosphine] palladium(II),
nickel(II) acetate tetrahydrate, 1-Boc-4-iodopyrazole and 1,4-diethynylbenzene were purchased
from Sigma-Aldrich and used without purification.
XRPD data were collected on a Bruker D2-PHASER diffractometer using CuKα radiation (λ =
1.5418 Å). The compounds were manually grounded in an agate mortar, then deposited in the
hollow of a zero background silicon sample holder. N2 adsorption isotherms were measured at
77 K on a Micrometrics 3Flex surface characterization analyzer. Prior to measurement, the
DMF molecules present in the powdered samples were exchanged with CH2Cl2 for 12 h. Next,
the samples were heated at 130 °C for 7 h and outgassed at 10-5 bar. IR-ATR absorption bands
were measured by spectrophotometer Bruker Tensor 27. Inductively Coupled Plasma Mass
spectrometry (ICP-OES) measurements were recorded on a iCAP 7400 DUO (Thermo Fisher
Scientific) spectrometer.
X-ray photoelectron spectra (XPS) were conducted on a Kratos Axis Ultra-DLD X-ray
photoelectron spectrometer equipped with Al Kα radiation (1486.6 eV). Elemental (C, H, N)
analyses were obtained in a THERMO SCIENTIFIC Flash 2000 instrument.
The organic products of the catalytic experiments were analyzed with a GC (HP 5890II) and
MS (HP 5971a).
Synthesis of the MOF
[Ni8(OH)4(H2O)2(L)6]n·solv (Ni-MOF) was prepared according to a reported procedure [50].
Pd-1@Ni-MOF
150 mg of the activated MOF and 67 mg of Pd-1 were placed in 20 mL of dichloromethane.
The content of the vial was stirred at RT for 24 h. The solid was collected by centrifugation and
washed with dichloromethane (2 x 10 mL). Green solid was dried overnight at RT.
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10.1002/ejic.201900618
European Journal of Inorganic Chemistry
IR (ATR, cm−1): 1498 (m) [ν(C=C+C=N)], 1369 (w), 1251 (vw), 1161(w) [ν(C−N)], 1058 (m),
1020 (w), 835 (s) [(C−HAR )] 642 (m).
Pd (ICP) 2.45 wt%; Pd (EDX) 1.14 wt%; P (EDX) 1.10 wt%
Pd-2@Ni-MOF
150 mg of the activated MOF and 78 mg of Pd-2 were placed in 20 mL of toluene. The content
of the vial was stirred at RT for 24 h. The solid was collected by centrifugation and washed
with toluene (2 x 10 mL) and acetone (1 x 10 mL). Green solid was dried overnight at RT.
IR (ATR, cm−1): 1497 (m) [ν(C=C+C=N)], 1367 (m), 1224 (m) [ν(C−N)], 1098(vw) [ν(P–C)],
1060 (w), 1018 (w), 837 (m) [(C−HAR )], 642 (m), 532 (w)
Pd (ICP) 1.22 weight%; Pd (EDX) 1.18 weight%; P (EDX) 0.53 weight%
Heck reaction
The reaction was carried out in a 50 mL Schlenk tube. The solid substrates, K2CO3 (2 mmol),
and the Pd catalyst (1×10-6˗1×10-5 mol) were weighed and placed in the Schlenk tube under an
N2 atmosphere. Next, olefin (1 mmol), iodobenzene (1 mmol), and 5 mL of the DMF were
added with a pipette. The Schlenk tube was closed with a rubber plug, and the reaction mixture
was stirred at 110 °C in oil bath. After the given reaction time, the Schlenk tube was cooled
down, and the organic products were separated by extraction with diethyl ether (three times
with 5, 4, and 2 mL). For better phase separation, 5 mL of water was added, and the products
were GC-MS analyzed with mesitylene (0.1 mL) as the internal standard.
Heck-type reaction
The reaction was carried out in a 50 mL Schlenk tube. The solid substrates, copper (II) acetate
(2 mmol), phenylboronic acid (1.5 mmol), and the Pd catalyst (1×10-6˗1×10-5) were weighed
and placed in the Schlenk tube under an N2 atmosphere. Next, olefin (1 mmol) and 5 mL of the
solvent (DMF) were added with a pipette. The Schlenk tube was closed with a rubber plug, and
the reaction mixture was stirred at 110 °C in oil bath. After the given reaction time, the Schlenk
tube was cooled down, and the organic products were separated by extraction with diethyl ether
(three times with 5, 4, and 2 mL). For better phase separation, 5 mL of water was added, and
the products were GC-MS analyzed with mesitylene (0.1 mL) as the internal standard.
Acknowledgements
This article is protected by copyright. All rights reserved.

10.1002/ejic.201900618
European Journal of Inorganic Chemistry
Financial support of the National Science Center (NCN, Poland) with grant
2017/25/B/ST5/00394 is gratefully acknowledged.
We thank Prof. Jorge Navarro from Departamento de Química Inorganica, Universidad
de Granada, for providing software of Materials Studio 2018.
We are grateful to Mr Marek Hojniak (Faculty of Chemistry, University of Wroclaw) for
GC and GC-MS analyses.
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