Carbon-sulphur cross coupling reactions catalyzed by nickel-based coordination polymers based on metalloligands

Article abstract of DOI:10.1039/c7dt02064c

This work illustrates two Ni²⁺ based coordination polymers (CPs, 1-Ni and 2-Ni) synthesized using two related Co³⁺ based metalloligands offering appended arylcarboxylate groups. The crystal structure of 1-Ni displays a porous 3D network having well-defined major and minor pores whereas 2-Ni exhibits a somewhat densely packed structure. Both CPs supported the exchange of coordinated water molecules and the inclusion of iodine within their porous structure whereas binding studies illustrated that the Ni(ii) ion in these CPs can bind thiophenol, a reagent used in the C-S cross coupling reactions. The two CPs functioned as the reusable heterogeneous catalysts for the C-S cross coupling reactions between substituted aromatic halides and thiophenol as well as cyclohexanethiol and ethanethiol.

Full text of DOI:10.1039/c7dt02064c

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DOI: 10.1039/C7DT02064C
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Carbon-sulphur cross coupling reactions catalyzed by nickel-based
coordination polymers based on metalloligands
Gulshan Kumar,a Firasat Hussaina and Rajeev Guptaa,*
Received 00th January 20xx,
Accepted 00th January 20xx
This work illustrates two Ni2+ based coordination polymers (CPs, 1-Ni and 2-Ni) synthesized using two related Co3+ based
metalloligands offering appended arylcarboxylate groups. Crystal structure of 1-Ni displays a porous 3D network having well-
defined major and minor pores whereas 2-Ni exhibits a somewhat densely packed structure. Both CPs supported exchange
of coordinated water molecules and inclusion of iodine within their porous structure whereas binding studies illustrated
that the Ni(II) ion in these CPs can bind thiophenol, a reagent used in the C-S cross coupling reactions. The two CPs functioned
as the reusable heterogeneous catalysts for the C-S cross coupling reactions between substituted aromatic halides to that
of thiophenol as well as cyclohexanethiol and ethanethiol.
DOI: 10.1039/x0xx00000x
www.rsc.org/
Coordination polymers (CPs) have emerged as the notable class
of materials for significant applications in many fields, particularly in
heterogeneous catalysis.10 The later feature has become possible
Introduction
Carbon–heteroatom (C–X; where X = N, O, S, etc.) bond forming
reactions have emerged as one of the important classes of synthetic
tools due to their extensive chemical scope and diversity.1 C–S cross
coupling reactions are of perennial focus due to the proliferation of
such linkages in natural products, pharmaceutically as well as
industrially important molecules.2 Since the first report by Migita and
co-workers3 involving cross coupling between aryl halides and thiols
using Pd(PPh3)4 as the catalyst, a large number of catalytic systems
based on various transition metals have been investigated.4 Recent
advances in C–S cross coupling reactions have shown that the
catalysts with electron-rich ligands are effective and usually function
in anhydrous organic solvents under inert atmosphere.5 Although,
significant attention has been given to develop Pd-based catalysts;
their large scale use has been limited due to the high cost of Pd metal
and the disadvantages associated with air and moisture sensitivity of
several Pd-catalysts.6 For non-precious transition metal-based
catalysts, reactions often require either higher temperature or high
catalyst loading.7 Furthermore, many catalysts are only effective with
aryl iodides but display negligible activity with cheap and readily
available aryl bromides and chlorides.8 Similarly, catalytic
effectiveness significantly drops if aliphatic thiols are being employed
in place of aromatic thiols. It is therefore clear that despite notable
progress in C-S cross coupling reactions;9 there are several unfulfilled
challenges: (i) developing efficient catalysts based on non-precious
metals; (ii) carrying out C–S cross coupling reactions using both
aromatic and aliphatic thiols; and (iii) performing C-S cross coupling
reactions heterogeneously. Therefore, development of effective
catalysts to overcome these difficulties remains a fruitful yet a
challenging task.
mostly due to the highly crystalline nature, stable framework
structure and inherent porosity of CPs. All these features collectively
contribute to produce noteworthy heterogeneous catalytic
systems.10 Intriguingly, most of the CPs have been developed using
non-transition metals (such as Zn2+ and Cd2+) and therefore
significantly limiting their potential as the heterogeneous catalysts
for challenging organic transformations.11 We anticipated that the
introduction of an appropriate transition metal in CPs would enable
them to be used for challenging organic transformations including C–
S cross coupling reactions.12 In addition, development of non-
precious metals based infinite-dimensional CPs will not only assure
cheaper and readily available catalysts but also reusable
heterogeneous catalysts.13 In this work, we report nickel-based
stable CPs with well-defined pores and channels that efficiently and
heterogeneously perform C-S cross coupling reactions between
various aryl halides to that of aromatic as well as aliphatic thiols.
Results and Discussion
Synthesis and characterization of CPs 1-Ni and 2-Ni
Green-coloured crystalline 1-Ni and 2-Ni were respectively
synthesized by the reaction of metalloligands 1 and 2 with Ni(OAc)2
followed by crystallization from water-acetone (Scheme 1). Both CPs
show broad νO-H stretches in the range of 3360-3410 cm-1 due to the
presence of coordinated as well as lattice water molecules (Fig. S1
and S2, ESI).14 Strong bands in the region of 1545-1565 cm-1
correspond to both arylcarboxylate νCOO and amidic νc=o stretches.14
For two CPs, TGA supports the presence of both coordinated as well
as lattice water molecules by displaying weight changes in the
temprature range of 50-160 °C (Fig. S3 and S4, ESI). For 1-Ni, an
observed weight loss of 20.46% fits nicely wih the calculated value of
20.85% corresponding to eight coordinated and six latttice water
molecules. An almost similar pattern, with identical number of water
molecules, was observed for 2-Ni with 20.98% weight loss (calcd.
a. Department of Chemistry, University of Delhi, Delhi 110007, India.
E-mail: rgupta@chemistry.du.ac.in; Web: http://people.du.ac.in/~rgupta/;
Fax: +91-11-2766-6605; Tel: +91-11-2766-6646
Electronic Supplementary Information (ESI) available: [Figures for FTIR, UV/Vis, and
NMR spectra, PXRD patterns, SEM, TGA, DSC plots; and an X-ray table]. CCDC
1552248. See DOI: 10.1039/x0xx00000x
This journal is © The Royal Society of Chemistry 20xx
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20.58%). For both CPs, DSC plots exhibit a broad exothermic feature bond distance is longer than the Co−Npyridine distance V(1ie.w86Ar9ti(c5le)OÅn)li.n1e9
DOI: 10.1039/C7DT02064C
The Ni(II) ion is six-coordinated where two coordinations come from
two Ocarboxylate from two different metalloligands whereas the
remaining four sites are satisfied by the water molecules (Fig. 1c).
The Ni-Ocarboxylate (2.053(3) Å) bond distances are shorter than that of
Ni-Owater ones (avg. 2.079 Å).
in the region of 60-160 °C for the loss of water molecules, thus
further supporting the TGA results. Notably, TGA studies suggest that
both CPs are thermally stable up to ca. 400 °C. The diffuse-
reflectance absorption spectra of 1-Ni and 2-Ni display broad
spectral features at ca. 460 and ca. 620 nm (Fig. S5 and S6, ESI). The
band at ca. 620 nm corresponds to Co3+-based metalloligand as
A metalloligand offers four arylcarboxylate groups and all four
noted before.15 X-ray powder diffraction (XRPD) patterns were coordinate four different Ni(II) ions in various directions. As a result,
a three-dimensional (3D) star-shaped architecture is formed if
viewed along the c axis (Fig. 1d and 1e). Importantly, 1-Ni exhibits
the presence of well-defined minor and major pores in the resultant
network. While the minor pores are triangular in shape constituted
by three metalloligands coordinated to three nickel ions; hexagonal
major pores are formed by the assembly of six metalloligands and six
nickel ions. The minor and major pores offer dimensions of 8.84 x
9.75 Å2 and 25.98 x 27.47 Å2, respectively. Both minor and major
pores are arranged into channels throughout the network (Fig 1e).
Interestingly, whiles minor pores are filled by the lattice water
molecules; major pores are largely vacant. Such unique structural
features are expected to enhance substrate accessibility during the
catalytic applications. Topology of 1-Ni was examined using the
TOPOS network simplification approach.20 A network with 4-fold
interpenetrated, four-connected three-dimensional qtz topology
with {64.82} point symbol was noted where Co3+-based
metalloligands acted as the four-connected nodes linked through the
secondary nickel atoms (Fig. 1f). It is suggested that the presence of
large void in the crystal space has facilitated high-fold
interpenetration.21 Notably, 4-fold interpenetrated qtz topology is
quite rare and only a few examples have been reported in the
literature.22
measured to ascertain the crystalline homogeneity and purity of the
bulk product. A close resemblence between the experimental XRPD
patterns to that of simulated ones from the single crystal diffraction
data indicates that a single crystalline phase has resulted during the
synthesis (Fig. S7 and S8, ESI). In addition, experimental XRPD pattern
for 2-Ni was subjected to Le Bail refinement16 with lattice parameters
generated from the single crystal X-ray diffraction data and such an
exercise provides satisfactory match (Fig. S8b, ESI). The experimental
XRPD patterns for two CPs display notable differences, a fact that
was confirmed by their different crystal structures (vide infra).
O
O
O
O
OH2
O
O
O
H
H
2O
OH2
H
H
2O
O
O
H
Ni
Ni
2
H
2O
O
H
2O
O
O
O
OH2
OH2
O
O
H
H
2O
H
2O
Ni
Ni
Ni
OH2
O
2O
Ni
H
2O
O
OH2
O
H
2O
H
O
O
O
H
2O
O
O
H
2
2O
O
O
O
O
O
O
H
O
2
N
C
N
N
N
N
o
N
N
o
C
N
N
N
2-Ni
N
O
N
O
2O
O
O
O
H
OH2
H
2O
H
2O
H
2O
O
O
OH2
O
OH2
H
2O
O
Ni
Ni
O
Ni
H
2O
O
H
Ni
O
2
O
O
O
H
2O
O
OH2
H
O
2O
H
2O
OH2
OH2
OH2
OH2
H
2O
O
Ni
O
H
Ni
1-Ni
O
O
O
H
H
2O
O
O
O
O
Scheme 1. Chemical drawings of CPs 1-Ni and 2-Ni based on the crystal
structures. A [Ni(H2O)6]2+ cluster in 2-Ni has been omitted for clarity. In both
CPs, only partial fragments of arylcaroxylate groups from metalloligands are
shown for clarity.
We also attempted to characterize 2-Ni crystallographically but
low data quality and poor structure convergence only allowed partial
structure.23 The partial structure displays that two Ni(II) ions are
bridged by a hydroxide group while coordinating to Ocarboxylate groups
from different metalloligands (see Scheme 1). Every nickel atom is
additionally coordinated by three water molecules. The coordination
of Co3+-based metalloligands to that of {Ni2(µ-OH)(H2O)6}-based
SBUs resulted in the generation of a 3D structure. The crystal
structure of 2-Ni also displayed the presence of a [Ni(H2O)6] cluster,
which remained largely uncoordinated but balances the overall
anionic charge of the resultant network. We have observed similar
[M(H2O)6] clusters with our earlier CPs where they primarily balance
the charge on the CPs.14b There are notable structural differences
between the two CPs. In 1-Ni, every nickel atom is coordinated to
two Ocarboxylate groups in trans fashion while further ligated to four
water molecules. In contrast, every nickel atom in 2-Ni is coordinated
by two monodentate Ocarboxylate groups while ligated to three water
molecules in addition to a bridging µ-OH group and a bridging
Crystal Structures
Single-crystal X-ray diffraction analysis reveals that 1-Ni crystallizes
in enantiomorphic space group P6222 in hexagonal lattice system
(Table S1, ESI). The asymmetric unit of 1-Ni is consists of 1/4th of a
metalloligand, one nickel atom, three coordinated water molecules,
and a lattice water molecule (Fig. 1a). A highly disordered lattice
water molecule, with site occupancy factor of 0.25, present at a
special position of a 2-fold axis was squeezed.17 Another lattice water
molecule (O1W), present at the general position in the asymmetric
unit, grows up to a total of four lattice water molecules in the unit
cell. The Co3+ ion (with point symmetry 222), Ni2+ ion and two
coordinated water molecules (O4 and O6) are on a 2-fold axis.
Similarly, another 2-fold axis passes through the pyridine ring
bisecting it (Fig 1a). Every metalloligand provides one negative
charge whereas four arylcarboxylate groups add four negative Ocarboxylate group. Therefore, involvement of two nickel atoms and
charges; therefore, two Ni2+ ions and a proton balance the overall 5−
charge with the network composition of (H+)[(1)Ni2(H2O)8]n.18 In a
metalloligand, two deprotonated tridentate ligands are arranged
meridionally around a Co3+ ion maintaining a compressed octahedral
geometry (Fig. 1b).17 The Co3+ ion is coordinated by four anionic
Namide atoms in a distorted equatorial basal plane whereas two
Npyridine atoms occupy the axial positions.19 The Co−Namide (1.957(3) Å)
three Ocarboxylate groups from different metalloligands generates a
much more densely packed 3D material in 2-Ni when compared to 1-
Ni. We anticipate that such a stark difference between two CPs may
result in considerable difference in their catalytic performance (vide
infra).
Exchange, binding and inclusion studies
2 | J. Name., 2012, 00, 1-3
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As both 1-Ni and 2-Ni display coordination of a large number of water 1-Ni (Fig. S9, ESI).15a The exchange was also attempted with
View Article Online
DOI: 10.1039/C7DT02064C
molecules to the Ni(II) center; solvent-exchange studies were carried methanol vapours where methanol was noted to replace most of the
out to evaluate possible replacement of the labile water molecules coordinated as well as lattice water molecules. Importantly, νO-C
with potential substrate and/or reagents.24 For such studies, 1-Ni stretch for the exchanged CH3OH was clearly observed at 1020 cm-1
was selected as a prototype example. 1-Ni was heated up to 80 °C as a sharp feature (Fig. S10, ESI).15a
under vacuum for 6 h to remove coordinated and lattice water
molecules. Subsequently, de-solvated 1-Ni was allowed to re-solvate
with the vapours of D2O. Such an experiment caused neat exchange
of H2O by D2O that is evident by the observation of νO−D stretches at
ca. 2500 cm−1 with a shift of ca. 900 cm-1 when compared to pristine
C1
C2
(a)
(b)
(c)
Ni1
Ni1
O5
O6
C3
O1
N1
O2
C4
N2
O3
C11
C6
Co1
C7
C8
C5
C10
N2
O3
O2
C11
C11
O4
C9
O5
O4
N2
O2
O3
Ni1
Ni1
Ni1
O5
O6
(d)
(e)
(f)
27.47x
25.98 Å
9.75 x 8.84 Å
Figure 1. (a) Asymmetric unit of 1-Ni, hydrogen atoms and two lattice water molecules are omitted for clarity. Selected bond distances (Å): Co1-N(1), 1.869(5);
Co1-N(2), 1.957(3); Ni1-O(3), 2.053(3); Ni1-O(4), 2.093(6); Ni1-O(5), 2.038(3); Ni1-O(6), 2.106(6). Selected bond angles (°): N(1)-Co1-N(2), 81.95(11); O(3)-Ni1-
O(5), 91.81(13); O(3)-Ni1-O(4), 87.91(12); O(3)-Ni1-O(6), 92.09(12); O(4)-Ni1-O(6), 180.0; O(5)-Ni1-O(6), 89.06(12); O(5)-Ni1-O(4), 90.91(12). (b) Partial crystal
structure of 1-Ni illustrating the coordination of arylcarboxylate fragments to the secondary Ni(II) atoms. (c) Coordination environment around a Ni(II) ion and
its bonding to Ocarboxylate groups from two different metalloligands. (d) 3D network structure displaying the presence of minor and major pores in a view along
the c axis. (e) An off-set view along the c axis displaying the presence of channels in the crystal structure; lattice water molecules are omitted for clarity. (f) a
4-fold interpenetrated qtz topological representation of 1-Ni.
To investigate possible inclusion, a batch of 25 mg of 1-Ni was de- was further confirmed by the Job’s plot as well as linear regression
solvated under vacuum and allowed to equilibrate with iodine fitting for a 1:1 stoichiometry between 1-Ni and thiophenol (Fig. 2b).
vapours. Importantly, nearly 3 mg of iodine was adsorbed within the The absorption spectral titration provided Kb value of 7.44 x 10-2 M-1.
pores and channels of 1-Ni which correspond to ca. 10.4% weight Such an experiment strongly supported the binding of a potential
change. Notably, adsorption of iodine vapours led to distinct colour substrate and/or reagent to the Ni(II) center in CPs.
change of 1-Ni from green to dark brown (Fig. S11, ESI).25 More
importantly, iodine adsorption process was reversible as the green
coloured 1-Ni was regenerated after evacuating the dark brown
solid, suggesting the stable nature of network in accommodating and
releasing molecular iodine.
1.5
1.4
1.3
1.2
1.1
1.0
0.9
0.8
0.7
0.6
0.5
0.4
0.3
0.2
0.1
0.0
0.11
0.10
0.09
0.08
0.07
0.06
0.05
500
400
300
200
100
0
0.000
0.005
0.010
0.015
0.020
1/ [Thiophenol]
1-Ni 1-Ni + Thiophenol
We also attempted to understand the potential binding of
thiophenol to the Ni(II) center in CPs. Thiophenol was selected as it
was utilized as a nucleophile in the C-S cross coupling reactions using
two CPs (vide infra). For such a purpose, when 1-Ni was titrated with
thiophenol in water,26 a yellow solution of 1-Ni was changed to
orange after the addition of one equiv. of thiophenol (see inset, Fig.
(a)
(b)
400
450
500
550
600
650
700
750
800
0.00
0.25
0.50
0.75
1.00
λ(nm)
Equivalents of Thiophenol
Figure 2. (a) UV-Vis spectral titration of 1-Ni with thiophenol in water; inset
shows color change of 1-Ni after the addition of thiophenol. (b) Change in the
2a). Such a titration neatly illustrated spectral changes wherein peaks absorption intensity (at 604 nm) of 1-Ni as a function of equivalents of
thiophenol; inset displays linear regression fitting curve for 1:1 binding
between 1-Ni and thiophenol.
at 600 and 450 nm respectively increased and decreased as a
function of thiophenol equivalents (Fig. 2a). The 1:1 stoichiometry
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C-S cross-coupling catalytic reactions
iodobenzene (entries 1-3, Table 2). Although, lower yields were
View Article Online
noted both with chlorobenzene (38-40%) aDnOdI:b1r0o.m10o39b/eCn7zDeTn0e20(6604C-
65%) when compared to iodobenzene (90 - 98%); both 1-Ni and 2-Ni
are able to activate significantly stable C-Cl and C-Br bonds.28
Interestingly, activation and therefore reactivity of C-Br bond can
always be enhanced by placing an electron-withdrawing –NO2 group
at the para position of bromobenzene (entry 4). Subsequently,
catalysis scope was explored with various substituted iodobenzene.
For example, 4-iodotoluene (entry 5) and 4-iodoanisole (entry 6)
resulted in excellent yield of the cross-coupled product. However, in
case of 2-iodotoluene (entry 7) and 2-iodoanisole (entry 8); the
product formation was somewhat lower. This is most probably due
to the steric hindrance caused by the methyl or methoxy group
located ortho to the iodide group and thus restricting the accessibility
of the nucleophile. Indeed, moving such groups to meta position
immediately improved the product yields (entries 9 and 10). Aryl
iodides bearing alkyl chains were equally effective in promoting the
C-S cross coupling reactions (entries 11-13). We also attempted to
use a few aliphatic thiols as the nucleophiles in order to evaluate the
effectiveness of the present heterogeneous catalysts. Satisfyingly,
both 1-Ni and 2-Ni promoted coupling of cyclohexanethiol as well as
ethanethiol with a few aromatic iodides producing C-S cross coupled
products in excellent yields (entries 14-18). It can be unambiguously
noticed that 1-Ni is a better catalyst than 2-Ni producing higher
product with nearly all tested aryl halides. This is most probably due
to an open structure offered by 1-Ni as a result of well-defined pores
and channels throughout the 3D material when compared to
somewhat densely packed 2-Ni (cf. crystal structures).
Mechanistically, we propose that the Ni-ligated water molecule is
first replaced by a R-thiolate ion forming a [Ni-SR] species. The in-situ
formed [Ni-SR] species then directs the coordinated SR− to attack the
aryl halide to produce the cross-coupling product, Aryl-SR, while
regenerating the catalyst.
The exchange studies suggested the potential of the present CPs in
supporting possible replacement of the coordinated water molecules
by suitable substrates and/or reagents. On the other hand,
thiophenol binding has asserted binding of at least one equiv. of a
substrate to the Ni(II) center. Moreover, I2 adsorption infers the
presence of sufficient porosity for the facile diffusion of substrates
and/or reagents, a fact clearly noticeable from the occurrence of
triangular and hexangular pores in the crystal structure of 1-Ni.
Collectively, these studies ascertain that both CPs are suitable
candidates for catalysis whereas 3D infinite nature of CPs further
suggests possible heterogeneous nature of the catalysis. We selected
cross-coupling reaction of aryl halides with thiophenol and
alkanethiols as the possible platform to test the present CPs.
Initially, reaction conditions were optimised using 1-Ni as the
prototype catalyst, iodobenzene as the model substrate and
thiophenol as the choice of nucleophile. In a typical reaction,
iodobenzene was reacted with thiophenol varying the catalyst, base,
solvent, temperature, and stirring time (Table 1). Use of Ni(OAc)2 or
NiCl2 as the catalyst in THF did not result in any product (entries 1
and 2) although NiCl2 in DMF with KOH resulted in 10% product
formation (entry 3). Similarly, either Co(OAc)2 or CoCl2 as the catalyst
or metalloligands 1 or 2 as the catalyst did not drive the C-S coupling
(entries 4 and 5). Likewise, 1-Ni as a catalyst in DMF; however,
without a base, did not produce any product (entry 6). Screening of
several bases (NaOH, KOH, KOtBu and K3PO4) as well as solvents (THF,
toluene, MeOH, benzene, DMSO, DMF) suggested that the best C-S
coupling results were obtained in KOH/DMSO (76%, entry 13) and
NaOH/DMF systems (98%, entry 14) when compared to other
combinations (entries 7-14). Similarly, additional control and
optimisation experiments advocated the requirement of 80 °C as the
most suited temperature and 6 h stirring duration for the maximum
product yield (data not shown). These experiments allowed us to
utilize such reaction conditions to illustrate the scope as well as
versatility of the present CPs as the catalysts for the assorted C-S
cross coupling reactions (Table 2).27
Table 2. C-S cross coupling reactions using CPs 1-Ni and 2-Ni as the catalysts.
Yield (%)
S.
N
1-Ni
Ni
2-
Ar-X
Product
Table 1. Control and optimization experiments for the C-S cross coupling
reactions. The yield was calculated using the GC.
S
1
l
C
I
H
S
S
40
65
98
99
97
96
38
60
90
91
88
90
-
mo
2
l
%
a a
s
t
t
C
y
l
+
,
ase o ven
B
t
S
l
-
80 oC 6 8
,
S
h
r
B
2
3
4
5
6
S. No.
1
2
3
4
5
6
7
8
Catalyst
Base
Solvent
Yield (%)
S
S
S
Ni(OAc)2, NiCl2
Ni(OAc)2, NiCl2
Ni(OAc)2, NiCl2
Co(OAc)2, CoCl2
1,2
NaOH
KOH
KOH
KOH
KOH
-
THF
THF
DMF
DMF
DMF
DMF
DMF
DMF
THF
0,0
0,0
0, 10
0,0
0,0
0
0
0
0
0
I
r
N
B
O2
O2N
1-Ni
1-Ni
1-Ni
1-Ni
1-Ni
1-Ni
1-Ni
1-Ni
K3PO4
KOtBu
e
M
I
e
M
9
NaOH, KOH
NaOH, KOH
NaOH, KOH
NaOH, KOH
KOH
10
11
12
13
14
Toluene
MeOH
Benzene
DMSO
DMF
S
0
e
O
M
I
5, 14
76
98
e
M O
1-Ni
NaOH
S
I
7
87
80
e
M
e
M
In order to evaluate the activation and reactivity of various aryl
halides by CPs 1-Ni and 2-Ni; a comparative reaction of thiophenol
was examined with chlorobenzene, bromobenzene, as well as
4 | J. Name., 2012, 00, 1-3
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DOI: 10.1039/C7DT02064C
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Figure 3. (a) C-S cross coupling reaction between iodobenzene and thiophenol
in presence of 1-Ni. (b) Disappearance of iodobenzene with the progress of
the reaction. (c) Catalyst 1-Ni was filtered after 4 h leading to termination of
reaction. (d) Catalyst 1-Ni was re-added after 2 h causing commencement of
the reaction and leading to completeness.
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Taking advantage of heterogeneous nature of catalysis, 1-Ni can
be recovered in nearly quantitative yield and reused several times
without conspicuous loss of activity (Fig. 4). Further, FTIR spectrum
of the recovered 1-Ni after 5th catalytic cycle exhibits superimposable
resonances to that of as-synthesized 1-Ni (Fig. S12, ESI).
Furthermore, a comparison between the powder XRD patterns of
pristine 1-Ni to that of recovered 1-Ni after every catalytic cycle
revealed that the crystallinity as well as structural integrity is
preserved during the catalytic cycles (Fig. S13, ESI). Finally, SEM
images of pristine 1-Ni were nearly identical when compared to the
ones of recovered sample (Fig. S14, ESI). In fact, there is no
appreciable change in the morphology of the material before and
after the fifth catalytic run. Collectively, these experiments
convincingly point toward the stable and reusable nature of the
present CPs in carrying out the C-S cross coupling reactions.
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Reaction condition: catalyst 2-mol%; nucleophile: NaSR; solvent: DMF;
temperature: 80 °C; Reaction Time: 6 h. The product yield was calculated
using GC wherein yields are average of two independent sets.
Reusability and recyclability studies
Both reusability and recyclability are considered as the significant
parameters in heterogeneous catalysis.29 The importance of a
catalyst increases manifold if it can be recovered and reused. Thus,
few experiments were performed to prove the true heterogeneous
nature of catalysis and to illustrate the recyclability of CPs. For such
studies, 1-Ni was selected as a model catalyst in a coupling reaction
between iodobenzene and thiophenol. The first experiment was to
ascertain the true heterogeneous nature of 1-Ni and to confirm that
no catalytically-active species has been leached out during the
catalysis. Therefore, ‘hot filtration test’ was performed in which 1-Ni
was filtered during the course of catalysis. As illustrated in Fig. 3, the
C-S cross coupling reaction completely stops when 1-Ni was removed
by filtration at 4 h whereas its re-addition at 6 h resumes the
catalysis. This figure also displays the disappearance of iodobenzene
as a function of time (red dots) that correlates nicely with the product
formation. This simple experiment unambiguously infers that 1-Ni is
stable and actually carries out the C-S cross coupling reaction.
100
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Figure 4. Reusability of 1-Ni as a catalyst for the C-S cross coupling reaction
between 4-iodotoluene and thiophenol.
Experimental section
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Journal Name
Materials and Reagents
oil. The data collection, cell refinement and reductionVwiewerAertidcloenOenlibnye
All chemicals and reagents of analytical grades were used without CrysAlisPro, ver. 1.171.33.49b.32 The structure was solved by direct
further purification. The standard literature methods were used to methods using SIR-200433 and refined by using SHELXL34 program in
purify the solvents.30 Metalloligands Et4N[Co(L-4COOH)2] (1) and an enantiomorphic space group P6222 in hexagonal lattice system.
Et4N[Co(L-3COOH)2] (2) were synthesized according to our earlier All non-hydrogen atoms were refined anisotropically. The Co(III) ion
DOI: 10.1039/C7DT02064C
report.31
(with point symmetry 222), Ni(II) ion and two coordinated water
molecules with O4 and O6 atoms were on a 2-fold axis. Similarly
another such axis passes through N and para C atoms of the pyridine
ring bisecting it. All hydrogen atoms were fixed geometrically (riding
on their respective C atoms with Uiso 1.2 times of the C atom), except
for the hydrogen atoms attached to the coordinated and
uncoordinated water molecules. The latter were located from the
difference Fourier and were refined with restraints over their bond
distance 0.82(2) Å with Uiso 1.2 times their oxygen atoms. Their bond
angles were also restrained near ideal values using DANG. The
refinement also showed large solvent accessible voids of total
potential solvent area volume of 3410 Å3 (50.5%) with the total
volume per unit cell of 6745 Å3. For 1-Ni structure 50.5% (3410 Å3) of
the unit cell amounts to solvent accessible voids which can host
remaining water molecules. The solvent accessible voids were
located at three positions -0(x) -0(y) -0.011(z) of 2870 Å3, 0.333(x)
0.667(y) 0.665(z) and 0.667(x) 0.333(y) 0.013(z) each of 270 Å3
respectively. As there was a large amount of diffused electron
density (all less than 1.0 e Å3, however) the model was SQUEEZED to
remove any diffused solvent by using the programme PLATON
SQUEEZE.17 The latter significantly improved R = 0.0543 for 3255
(observed) and R = 0.0712 for 4121 reflections with 173 number of
parameters and 12 restraints. The fact that the residual electron
density was less than 1 eÅ3; signifies that this large amount of
diffused electron density may be due to the large number of water
molecules present only in the voids. The final model being submitted
here is the SQUEEZED one. Details of the crystallographic data
collection and structural solution parameter are provided in Table S1
(ESI).
Synthesis of (H+)[(1)Ni2(H2O)8]n.5H2O (1-Ni). The metalloligand 1
(100 mg, 0.1004 mmol) was dissolved in 10 mL methanol. A
methanolic solution (5 mL) of Ni(OAc)2 (62.5 mg, 0.2510 mmol) was
added drop-wise to it at room temperature. An instant precipitation
was noticed; however, reaction was allowed to stir for 2 h to ensure
complete precipitation. The product was filtered and re-dissolved in
water. The vapour diffusion of acetone to the aforementioned
aqueous solution produced a green coloured crystalline material,
suitable for X-ray diffraction, within 4-5 d. This product was filtered
and dried under vacuum. Yield: 103 mg (84 %). C42H49CoNi2N6O25.H2O
(1-Ni.H2O: 1232.23): calcd. C 40.94, H 4.17, N 6.82; found C 40.46, H
4.11, N 7.15. FTIR spectrum (Zn-Se ATR, selected peaks): (ν/cm–1) =
3387 (OH), 1573, 1565 (C=O). Diffuse reflectance UV/Vis spectrum; λ
= 460, 620 nm.
Synthesis of [(2)Ni2(µ-OH)(H2O)6{Ni(H2O)6}].2H2O (2-Ni). This
compound was also synthesized in an identical method with an
identical scale as mentioned for 1-Ni. Yield: 108 mg (83 %);
C42H51CoNi3N6O27 (1306.90): calcd. C 38.60, H 3.93, N 6.43; found C
39.05, H 3.88, N 6.90; FTIR spectrum (Zn-Se ATR, selected peaks):
(ν/cm–1) = 3395 (OH), 1563, 1562 (C=O). Diffuse reflectance UV/Vis
spectrum; λ = 458, 622 nm.
Physical measurements
The elemental analysis data were obtained with an Elementar
Analysen Systeme GmbH Vario EL-III instrument. The FTIR spectra
were recorded with a Perkin-Elmer Spectrum-Two spectrometer
having Zn-Se ATR. The NMR spectroscopic measurements were
carried out with a Jeol 400 MHz spectrometer. Perkin Elmer Clarus-
580 and Shimadzu QP-2010 instruments were respectively used for
the gas chromatography (GC) and GC-MS studies having RTX-5SIL-MS
column. Thermal gravimetric analysis (TGA) and differential scanning
calorimetry (DSC) were performed with Shimadzu DTG 60 and TA-
DSC Q200 instruments, respectively, under nitrogen atmosphere.
The X-ray powder diffraction studies were performed either with an
X’Pert Pro from PANalytical or a Bruker AXS D8 Discover instrument
(Cu-Kα radiation, λ = 1.54184 Å). The samples were ground and
subjected to the range of θ = 5–35° at a slow scan rate at room
temperature. The experimental X-ray powder diffraction pattern for
2-Ni was subjected to Le Bail Refinement using TOPAS3 software
with lattice parameters generated from the single crystal X-ray
diffraction data.16
Typical procedure for C-S coupling reaction
In a typical reaction, a mixture of aryl halide and sodium salt of a thiol
in DMF were allowed to react in 1:1.5 ratio at 80 °C for 6-8 h under
nitrogen atmosphere in presence of 2 mol% of 1-Ni or 2-Ni. Thin layer
chromatography (TLC) and/or gas chromatography (GC) techniques
were used to monitor the progress of the reaction. After completion,
the reaction was quenched by the addition of 2 ml of ethyl acetate
which instantly caused precipitation of the catalyst which was then
filtered and dried under vacuum. The recovered catalyst was
characterized by the FTIR spectra and powder X-ray diffraction
studies. The ethyl acetate layer was washed with water (2-3 times)
and dried over anhyd. Na2SO4. The solvent was evaporated under
vacuum to isolate the organic product. The crude organic product
was purified by the flash column chromatography on silica gel using
5% EtOAc-hexanes as the eluent. The organic product(s) were
analyzed by the GC/GC-MS techniques as well as proton NMR
spectra. The characterization data for a few representative products
X-Ray Diffraction Studies
Single crystal X-ray diffraction data collection for 1-Ni was done on
an Oxford Xcalibur CCD diffractometer at 173 K. The crystals used
were highly sensitive to air and were studied in the crystallographic
6 | J. Name., 2012, 00, 1-3
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ARTICLE
are provided below whereas their 1H NMR and 13C NMR spectra are groups. Crystal structure of 1-Ni displayed a 3D neVtiwewoArrktichleaOvnilninge
two types of pores whereas 2-Ni exhibite
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C
included in the ESI (Figures S15-S32, ESI).
packed network. Both CPs supported exchange of coordinated
water molecules and inclusion of iodine within the porous
structure. Binding studies established that the Ni(II) ion in these
CPs bind one equiv. of thiophenol. Both CPs functioned as the
reusable heterogeneous catalysts for the C-S cross coupling
reactions between substituted aromatic halides to that of
Characterization data for a few representative products:
Phenyl(4-tolyl)sulfane. Isolated yield: 87 mg (87 %). 1H NMR
spectrum (400 MHz, CDCl3): δ 7.29 (d, J= 8.4Hz, 2H), 7.25 (d, J= 4.6Hz,
4H), 7.18 (t, J= 4.6Hz, 1H), 7.12 (d, J= 8.4Hz, 2H). 13C NMR spectrum
(100 MHz, CDCl3): δ 137.5, 137.0, 132.2, 131.2, 130.0, 129.7, 129.0, thiophenol as well as cyclohexanethiol and ethanethiol. The
importance of the present CPs increases manifold as they use
earth-abundant nickel as the catalytic metal and are able to
utilize both aromatic as well as aliphatic S-based nucleophiles
while carrying out the reactions heterogeneously.
126.3, 21.1.
1
4-Methoxyphenyl(phenyl)sulfane. Isolated yield: 90 mg (83 %). H
NMR spectrum (400 MHz, CDCl3): δ 7.42 (d, J= 9.16Hz, 2H), 7.23 (d,
J= 8.3Hz, 2H), 7.16 (m, 3H), 6.90 (d, J= 9.9Hz, 2H), 3.81 (s, 3H). 13C
NMR spectrum (100 MHz, CDCl3): δ 159.7, 138.5, 135.3, 128.8, 128.1,
125.6, 124.1, 114.9, 55.2.
Acknowledgements
RG acknowledges the financial support from the Science and
Engineering Research Board (EMR/2016/000888), New Delhi
and the University of Delhi. Authors thank Prof. G. Hundal
(GNDU) and an anonymous reviewer for crystallographic
assistance, Mr. Sunil Yadav for catalysis assistance, Dr. Dyanne
Cruickshank (Rigaku Diffraction) for data collection of 2-Ni, CIF-
USIC at this university for the instrumental facilities and AIRF–
JNU (New Delhi) for the GC–MS facility.
Phenyl(2-tolyl)sulfane. Isolated yield: 83 mg (83 %). 1H NMR
spectrum (400 MHz, CDCl3): δ 7.82 (m, 4H), 7.71 (m, 5H), 2.39 (s, 3H).
13C NMR spectrum (100 MHz, CDCl3): δ 159.9, 137.1, 135.2, 131.3,
129.8, 129.2, 127.2, 115.8, 112.7, 55.2.
4-Nitrophenyl(phenyl)sulfane. Isolated yield: 110 mg (95 %). 1H
NMR spectrum (400 MHz, CDCl3): δ 8.04 (d, J = 9.1, 2H), 7.52 (m, 2H),
7.4 (m, 3H), 7.15 (d, J= 8.3Hz, 2H). 13C NMR spectrum (100 MHz,
CDCl3): δ 148.5, 145.3, 134.7, 130.3, 130.0, 129.6, 126.6, 124.0.
Cyclohexyl(4-methoxyphenl)sulfane. Isolated yield: 86 mg (78 %). 1H
NMR spectrum (400 MHz, CDCl3): δ 7.36 (d, J= 8.3Hz, 2H), 6.81 (d, J =
8.3Hz, 2H), 3.78 (s, 3H), 2.86 (m, 1H), 1.90 (m, 2H), 1.73 (m, 2H), 1.24
(m, 5H). ). 13C NMR spectrum (100 MHz, CDCl3): δ 159.2, 135.5, 124.9,
114.2, 55.3, 47.9, 33.4, 26.2, 25.7.
Notes and references
1
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Cyclohexyl(2-tolyl)sulfane. Isolated yield: 91 mg (88 %). 1H NMR
spectrum (400 MHz, CDCl3): δ 7.34 (m, 1H), 7.13 (m, 2H), 3.07 (m,
1H), 2.38 (s, 3H), 1.96 (m, 1H), 1.76 (m, 2H), 1.31 (m, 5H). 13C NMR
spectrum (100 MHz, CDCl3): δ 139.2, 134.5, 131.1, 130.1, 126.3,
126.1, 45.8, 33.3, 26.1, 25.8, 20.8.
3
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T. Migita, T. Shimizu, Y. Asami, J. Shiobara, Y. Kato, M. Kosugi,
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NMR spectrum (400 MHz, CDCl3): δ 7.49 (d, J= 7.6Hz, 4H), 7.26 (m,
3H), 7.13 (d, J= 8.4Hz, 2H), 2.57 (t, J= 7.2, 2H), 1.63 (m, J= 8.4Hz, 2H),
0.93 (t, J= 7.6Hz, 3H). 13C NMR spectrum (100 MHz, CDCl3): δ 136.9,
132.0, 129.8, 129.4, 129.0, 127.4, 127.1, 126.4, 37.6, 24.4, 13.7.
1
4-Isopropylphenyl(phenyl)sulfane. Isolated yield: 98 mg (86 %). H
5
NMR spectrum (400 MHz, CDCl3): δ 7.49 (m, 1H), 7.30 (m, 3H), 7.24
(m, 3H), 7.19 (m, 2H), 2.87 (m, J= 6.8Hz, 1H), 1.24 (d, J=6.8Hz, 6H).
13C NMR spectrum (100 MHz, CDCl3): δ 148.3, 131.9, 129.9, 129.0,
127.4, 127.1, 126.4, 32.7, 23.8.
2002,
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6
, 5005; (d) M. A. Fernandez-
,
4-Butylphenyl(phenyl)sulfane. Isolated yield: 102 mg (84 %). 1H
NMR spectrum (400 MHz, CDCl3): δ 7.30 (d, J= 7.6Hz, 4H), 7.27 (m,
2H), 7.19 (m, 1H), 7.13 (d, J= 8.4Hz, 2H), 2.59 (t, J= 7.6Hz, 2H), 1.58
(q, J= 6.8Hz, 2H), 1.35 (m, J= 7.6Hz, 2H), 0.92 (t, J= 7.6Hz, 3H). 13C
NMR spectrum (100 MHz, CDCl3): δ 142.6, 136.8, 132.0, 129.8, 129.3,
129.0, 126.3, 35.2, 33.4, 22.4, 13.9.
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In this work, we showed the synthesis and characterization of
two Ni(II) based coordination polymers using two Co(III) based
metalloligands decorated with appended arylcarboxylate
This journal is © The Royal Society of Chemistry 20xx
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6
2
10 (a) L. Q. Ma, C. Abney, W. Lin, Chem. Soc. Rev., 2009, 38, 1248; 26 1-Ni was soluble in water therefore enabling us to study its
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(e) M. Zhao, S. Ou, C. D. Wu, Acc. Chem. Res., 2014, 47, 1199.
in the catalytic performance in presence of air, presence of
water considerably reduces the C-S product formation. We
suggest that the presence of additional water molecules
suppresses the dissociation of coordination water molecules
and such a situation disfavours the coordination of thiol to the
nickel center. Further increasing the concentration of water
resulted in partial dissolution of 1-Ni and 2-Ni and therefore a
drop in the catalytic performance.
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,
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18 The charge on 1-Ni has been balanced by assuming a proton
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23 CP 2-Ni always produced poorly-diffracting thin needle-like
crystals and one such effort resulted in data collection and
incomplete partial structure solution. Crystal data: cell =
triclinic; space group = P-1; a = 15.7805(6) Å, b = 26.8694(14)
Å, c = 27.4877(17) Å;
α = 96.129(5)°, β = 97.123(4)°, γ =
92.315(4) ; V = 11482.1; Z = 8.
°
8 | J. Name., 2012, 00, 1-3
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