Synthesis of heterogeneous Ru(ii)-1,2,3-triazole catalyst supported over SBA-15: Application to the hydrogen transfer reaction and unusual highly selective 1,4-disubstituted triazole formation: Via multicomponent click reaction

Article abstract of DOI:10.1039/c7cy02619f

In the present study, we demonstrate a simple and efficient method for ligand formation and covalent anchoring to a heterogeneous support via click reaction. The complex tris(triphenylphosphine)ruthenium(ii) dichloride [RuCl₂(PPh₃)₃] anchored over the click modified ligand of SBA-15 forms a new highly efficient heterogeneous SBA-15-Tz-Ru(ii)TPP catalyst. Solid state ¹³C, ²⁹Si, and ³¹P CP-MAS NMR spectra provide evidence for the formation of the heterogeneous catalyst. SBA-15-Tz-Ru(ii)TPP catalyst was screened for the multicomponent click cycloaddition reaction in water medium as a green solvent and it exhibited unusual and excellent selectivity for the formation of 1,4-disubstituted triazole product under mild reaction condition. In addition, SBA-15-Tz-Ru(ii)TPP catalyst also catalyzed the hydrogen transfer reaction of various carbonyl compounds with excellent catalytic activity to give the corresponding alcohols. The heterogeneous catalyst can be recycled and reused several times (five) without a loss in reactivity.

Full text of DOI:10.1039/c7cy02619f

View Article Online
View Journal
Catalysis
Science &
Technology
Accepted Manuscript
This article can be cited before page numbers have been issued, to do this please use: Y. Sasson, J.
Rathod, P. Sharma, A. P. Singh and P. -. Kumar, Catal. Sci. Technol., 2018, DOI: 10.1039/C7CY02619F.
This is an Accepted Manuscript, which has been through the
Volume 6 Number 1 7 January 2016 Pages 1–308
Royal Society of Chemistry peer review process and has been
accepted for publication.
Catalysis
Science &
Technology
Accepted Manuscripts are published online shortly after
www.rsc.org/catalysis
acceptance, before technical editing, formatting and proof reading.
Using this free service, authors can make their results available
to the community, in citable form, before we publish the edited
article. We will replace this Accepted Manuscript with the edited
and formatted Advance Article as soon as it is available.
You can find more information about Accepted Manuscripts in the
author guidelines.
Please note that technical editing may introduce minor changes
to the text and/or graphics, which may alter content. The journal’s
ISSN 2044-4753
standard Terms & Conditions and the ethical guidelines, outlined
in our author and reviewer resource centre, still apply. In no
event shall the Royal Society of Chemistry be held responsible
PAPER
Qingzhu Zhang et al.
Catalytic mechanism of C–F bond cleavage: insights from QM/MM
analysis of fluoroacetate dehalogenase
for any errors or omissions in this Accepted Manuscript or any
consequences arising from the use of any information it contains.
rsc.li/catalysis

Please do not adjust margins
Catalysis Science & Technology
Page 1 of 16
View Article Online
DOI: 10.1039/C7CY02619F
Catalysis Science & Technology
ARTICLE
Synthesis of Heterogeneous Ru(II)-1,2,3-Triazole catalyst
supported over SBA-15: Application to the Transfer Hydrogen
reaction and unusual highly selective 1,4-disbustituted traizole
formation via Multicomponent Click Reaction
Ok Received 00th January 20xx,
Accepted 00th January 20xx
DOI: 10.1039/x0xx00000x
Priti Sharma#[a], Jayant Rathod#[c], A.P. Singh*[b], Pradeep Kumar*[c] and Yoel Sasson*[a]
www.rsc.org/
In the present study we demonstrate a simple and efficient method for ligand formation and covalent anchoring to
heterogeneous support via click reaction. The complex tris(triphenylphosphine)ruthenium(II) dichloride [RuCl2(PPh3)3]
anchored over the click modified ligand of SBA-15, forms a new highly efficient heterogeneous SBA-15-Tz-Ru(II)TPP
catalyst. Solid state 13C, 29Si, & 31P CP-MAS NMR spectra provide evidence for the formation of the heterogeneous catalyst.
SBA-15-Tz-Ru(II)TPP catalyst was screened for the multi component click cycloaddition reaction in water medium as green
solvent exhibited unusual and excellent selectivity for the formation of 1,4-disubstituted triazole product under mild
reaction condition. In addition, SBA-15-Tz-Ru(II)TPP catalyst also catalyzed the hydrogen transfer reaction of various
carbonyl compounds with excellent catalytic activity to give the corresponding alcohols. The heterogeneous catalyst can
be recycled and reused several times (five) without the loss in reactivity.
spin crossover complexes.[6] Crowley et, al. documented a
book chapter is the extension of the appricable light of Click-
Triazole in coordination chemistry.[7] With the fact, that 1,2,3-
Introduction
In recent years, the “click chemistry” reaction is growing
exceptionally with enhanced attention of the world wide
researcher due to its applications in various fields such as
medicine[1], material and polymer[2]. The click chemistry is
associated with several advantage, such as simple and mild
reaction procedure, atom efficient, compatibility with broad
range of functional groups.[3] Apart from extensive application
of click chemistry in various fields, novel ligand design and
modification via 1,2,3-triazole has added a new dimention in
the area of coordiantion chemistry. In click chemistry high
level of selectivity has been demonstrated exclusively either
1,4 or 1,5-substituted 1,2,3-triazole with excellent yields, with
its further application as coordination ligands with a various
metal complexes.[4] In a remarkable work, S. Hecht et al.
utilized the click chemistry and its chelating ability for
transition metal complex via coordination [Clickates based on
2,6-bis(1,2,3-triazol-4-yl)pyridines].[5] In addition, Sarkar and
his co-workers designed and synthesised novel ligands via click
reaction (1,2,3-triazole) for metal complexes coordination and
triazole shows good capability with metal complexes in
coordination chemistry due to its homogeneous nature, it
suffers the drawback of recyclability. In our recent work we
have shown that the substituted 1,2,3-triazole can replace the
traditional ligand and coordinate with metal complex via
nitrogen-donor ligands in an efficient way.[8] In same context,
we tried to design a new ligand with a covalent attachment to
the heterogeneous support in a single step via 1,2,3-traizole
formation (click reaction) (Scheme 1,2). Further, in the field of
heterogeneous catalysis,[9] precisely, mesoporous materials
like SBA-15 are preferred candidates for functionalization due
to their high hydrothermal stability, large pore size and thick
walls, which can be easily functionalized using free hydroxyl
group of mesoporous SBA-15 (scheme 2).[10]
In literature, copper catalyzed click reaction generally
proceeds with two component reaction system using organic
azide.[11] However the key component of click reaction, organic
azides are prone to explode and highly hazardous in process of
purification and isolation.[12] Some reports are available by
following in-situ azides synthesis, but faces drawback of
tedious procedure coupled with high temperature and long
reaction time, which might lead to the side product formation
(homo coupling) and 1,5-disubstituted 1,2,3-triazole.[13]
This journal is © The Royal Society of Chemistry 20xx
J. Name., 2013, 00, 1-3 | 1
Please do not adjust margins

Please do not adjust margins
Catalysis Science & Technology
Page 2 of 16
View Article Online
DOI: 10.1039/C7CY02619F
ARTICLE
Journal Name
Liu and co-workers reported the catalyst
dependent regioselective click reaction with
the homogeneous cyclopentadienyl free
ligands Ru-catalyst, for the selective
formation of 1,4-disubstituted 1,2,3-
triazole.[17] In the same context the present
protocol here, multi-component, and
selective 1,4-disubstituted 1,2,3-triazole
regioselective product is achieved by using
SBA-15-Tz-Ru(II)TPP heterogeneous catalyst.
However the reaction sequence follows first
the Ru-catalyzed cycloaddition of azide and
alkyne to give the intermediate 4-phenyl-1H-
1,2,3-triazole followed by sequential in-situ
substitution reaction with benzyl bromide to
give the 1,4-disubstituted 1,2,3-triazole
compounds by homogenous RuCl2(PPh3)3
complex and heterogeneous SBA-15-Tz-
Ru(II)TPP catalyst (Scheme 3, 5.a, b, c).
Catalytic hydrogen transfer (CTH) reactions
were developed as an alternative to the
traditional catalytic hydrogenation processes
and to avoid the processes, where hydrogen
gas is used under pressure.[18] [19]
The
,
hydrogen transfer reaction has been performed employing
catalyst such as homogenous catalyst[20], metal alloys[21], metal
oxides[22] and organometallic complexes[23] on various solid
supports[24] etc. But, ruthenium complex catalyzed reaction are
Scheme 1. Schematic diagram of; (A) 3-azidopropyltrimethoxysilane
synthesis, (B) Azide-organo-functionalization over SBA-15, (C) SBA-
15 ligand fabrication via 2-proprgylamine, and (D) [RuCl2(PPh3)3] most fundamental and favored with a broad coverage in
25]
hydrogen transfer reactions.[18d,
Although, reported
complex anchoring over SBA-15-Tz
.
processes generally progress in harsh reaction conditions and
[26]
most of them are not recyclable.
For the best usage of
homogeneous catalyst is to heterogenization over solid
support.
Scheme 3. Multi component click cycloaddition model
reaction.
Scheme 2: Schematic representation of Click chemistry usage
in ligand formation and covalent anchoring in an elementary
step.
Scheme 4. Schematic diagram hydrogen transfer model
reaction using carbonyl functional (>C=O) group and
isopropanol.
Recently apart from copper, many other metal[14] like
ruthenium[15] complexes are reported, to catalyze the
cycloaddition of terminal acetylenes and azides selectively to
give 1,5 or 1,4-disubstituted triazole.[16] In a remarkable work;
Herein, we report a new heterogeneous catalyst, complexes
[RuCl2(PPh3)3], over 1,4-substituted 1,2,3-triazole liganded
SBA-15 (click modified) and screened its catalytic properties in
2 | J. Name., 2012, 00, 1-3
This journal is © The Royal Society of Chemistry 20xx
Please do not adjust margins

Please do not adjust margins
Catalysis Science & Technology
Page 3 of 16
View Article Online
DOI: 10.1039/C7CY02619F
Journal Name
ARTICLE
multi component click cycloaddition and hydrogen transfer presented in figure 1. The observed X-ray diffraction pattern
reaction.
demonstrates characteristic highly ordered hexagonal
mesoporous silica framework of the synthesized click modified
materials (Fig.1).[27] The characteristic hexagonal phase
(p6mm) of SBA-15 shows three reflection planes, intense peak
at (100), peaks with low intensity (110) and (200) are visible in
all modified SBA-15 materials at 2y = 0.949°, 1.565° and
1.799°, respectively. The observed results support high degree
of orderedness of the two dimensional (2D) hexagonal phase
(Fig.1a).[28] The peak intensities of reflections (100) in SBA-15-
N3, SBA-15-Tz and SBA-15-Tz-Ru(II)TPP are in decreasing order
from calcined SBA-15 to modified SBA-15 material moderatly
in figure 1 (a-d), due to surface modification and anchored
organometallic complex, respectively, by using free clickable
surface of SBA-15 (Fig. 1a-d).[29]
Results and discussion
The synthesis strategy employed to fabricate SBA-15-Tz-
Ru(II)TPP heterogeneous catalysts is shown in scheme 1. As
per scheme 1, free hydroxyl group of mesoporous SBA-15
heterogeneous support, is first covalently anchored by azido
linker group (3-Az-PTMS), and then modified to triazole ligand
via click reaction by propargylamine. Further, procedure
involves stirring and refluxing a mixture of click functionalized
SBA-15-Tz, with solution of [RuCl2(PPh3)3] in DMF for 12 h
under argon atmosphere. (Scheme 1).
FTIR spectra witnesses the presence of surface silanols,
hydroxyl group, anchored complex, RuCl2(PPh3)3 in (a) Calcined
SBA-15, (b) SBA-15-N3, (c) SBA-15-Tz, (d) SBA-15-Tz Ru(II)TPP,
(e) RuCl2(PPh3)3, (f) 3-Az-PTMS, materials in figure 2. The
strong visible bands in the range of 807–770 cm-1 and 1038-
1090 cm-1 are accountable for symmetric and asymmetric
stretching vibrations of the Si–O–Si bonds SBA-15, and
a
b
27, 29]
modified SBA-15 materials respectively (Fig.2 a-d).[8,
Further, a strong band is observed in the mid-infrared region
at 906 cm−1, attributed to the Si-OH vibrations (Fig.2 a-d). The
FT-IR spectra of SBA-15-N3, SBA-15-Tz and SBA-15-Tz-Ru(II)TPP
materials, exhibit two bands at 2990 cm-1 and 2891 cm-1, are
asymmetric and symmetric vibrations of the -CH2 groups of the
linker propyl chain (3-azidopropyltrimethoxy silane) (Fig.2 b-d)
c
d
1
2
3
4
5
2 Theta (°)
respectively. Furthermore, SBA-15-N3 shows
a
sharp
Figure 1. Small angle XRD patterns of; (a) SBA-15, (b) SBA-15-
absorbance at 2104 cm-1, characteristic stretching vibration of
organic azide (-N3). The presence of similar absorption band
N3, (c) SBA-15-Tz, (d) SBA-15-Tz-Ru(II)TPP.
visible
in
the
pure
homogeneous
3-
azidopropyltrimehtoxysilane linkers (2104 cm-1), proves
successful anchoring of the linker to calcined SBA-15 (Fig.2
b,f).[30] Further, the complete consumption of above
mentioned (-N3, 2104 cm-1) characteristic peak in SBA-15-Tz
material, demonstrates that 3-azidopropyl tethering agent
successfully reacted with propargylamine via click reaction
(Fig. 2c). A strong characteristic vibration of PPh3 (aromatic
region) complex in FT-IR evidenced at 683, 700, 1076, 1437,
1481 and 3050 cm−1 in homogeneous catalyst, whereas with
less intensity same vibration are visible in heterogeneous
catalyst SBA-15-Tz-Ru(II)TPP, supports the fact that, PPh3
group may leave the complex after anchoring (due to trans
effect) (Fig. 2e and 2d).[31] The spectra of heterogenized
complex SBA-15-Tz-Ru(II)TPP catalyst witnesses characteristic
peaks of the neat catalyst, indicating the structural retention
of [RuCl2(PPh3)3] complex after immobilization.
f
1076
906
1156
1481
e
d
3050
c
1437
683
b
a
2891
2990
2104
559
807
1038
4000 3500 3000 2500 2000 1500 1000 500
-1
Wavenumber (cm )
The 13C solid state CP MAS NMR spectra of (A) SBA-15-N3, (B)
SBA-15-Tz-Ru(II)TPP are depicted in figure 3. The presence of
peaks at 10, 23 and 54 ppm are assigned to the carbon atoms
of the linker propyl chain in azido (SBA-15-N3) group, indicates
covalent azido functionalization of SBA-15 (Fig. 3a). The
appearance of additional intense peaks precisely in aromatic
region of PPh3 group from 117 to 138 ppm (consisting 127,
143, 144, 146) clearly demonstrate the functionalization of the
Figure 2. FT-IR spectra of; (a) Calcined SBA-15, (b) SBA-15-N3,
(c) SBA-15-Tz, (d) SBA-15-Tz-Ru(II)TPP, (e) RuCl2(PPh3)3, (f) 3-
Az-PTMS.
The synthesized catalysts were characterized by different
physicochemical characterization techniques and the results
are discussed here in detail. The XRD pattern of SBA-15 (a),
SBA-15-N3 (b), SBA-15-Tz (c) and SBA-15-Tz-Ru(II)TPP (d) are
This journal is © The Royal Society of Chemistry 20xx
J. Name., 2018, 00, 1-3 | 3
Please do not adjust margins

Please do not adjust margins
Catalysis Science & Technology
Page 4 of 16
View Article Online
DOI: 10.1039/C7CY02619F
ARTICLE
Journal Name
The spectrum exhibited in figure 4A broad resonance peaks
from -90 to -120 ppm, is indicative for a range of Si–O–Si bond.
While the bands centered at -93 ppm, -102 ppm and -111 ppm
are assigned to Q2 [(SiO)2Si(OH)2], Q3 [(SiO)3Si(OH)] and Q4
[(SiO)4Si] sites of the framework of SBA-15, respectively (Fig. 4
B). In general, the Q3 sites are considered to be loaded with Si–
OH groups. The Q2 sites are frequently attainable for possible
anchoring with organic complexes. 29Si CP MAS NMR spectrum
of SBA-15-Tz-Ru(II)TPP show two peaks at -67 ppm and at -60
ppm which are designated to T3 [SiR(OSi)3] and T2
[Si(OH)R(OSi)2], respectively (Fig. 4B).[27a, 29-30] The presence of
sharp T3 peak indicates the covalent anchoring of 3-
azidopropyltrimethoxy silane over clickable mesoporous SBA-
15 surface for further anchoring of complex (Fig. 4B) (SI, Fig.
S7).
2
3
1
4,5,7
a
6
7
b
200 180 160 140 120 100 80 60 40 20
ppm
0 -20
31P CP MAS NMR spectrum of heterogeneous catalyst SBA-
Figure 3. 13C CP-MAS NMR of; (a) SBA-15-N3, (b) SBA-15-Tz- 15-Tz-Ru(II)TPP exhibits two 31P signals at d = 34, 50 ppm (Fig.
Ru(II)TPP.
S1). After interacting to click modified SBA-15 triazole ligand
one equatorial PPh3 group leaves from the RuCl2(PPh3)3
homogeneous complexes system (due to strong trans effect of
another PPh3 group, two non-equivalent phosphorus
environment).[31, 33] The spectrum represents two signals (d =
34, 50 ppm) of merging in one peak intensity, indicating the
presence of two non-equivalent phosphorus atoms in the
synthesized catalyst SBA-15-Tz-Ru(II)TPP (Fig. S1).
3
Q
A
2
4
Q
Q
14
800
700
600
500
400
300
200
100
0
a(32.7Å)
a
12
10
8
6
4
2
0
-2
(25.6Å)
b
-160 -140 -120 -100 -80 -60 -40
ppm
10 20 30 40 50 60 70 80 90100
Pore radius Å
b
B
3
T
3
Q
4
2
Q
T
0.0
0.2
0.4
0.6
0.8
1.0
Relative Pressure p/p
0
2
Figure 5. N2 adsorption-desorption isotherm & Pore size
distribution (inset) of: (a) calcined SBA-15, (b) catalyst SBA-15-
Tz-Ru(II)TPP.
Q
-140 -120 -100 -80 -60 -40 -20
ppm
Table 1. Textural properties of SBA-15 & catalyst SBA-15-Tz-
Ru(II)TPP.
Figure 4. 29Si CP-MAS NMR of: (A) calcined SBA-15, (B) SBA-15-
BET
Average
Pore vo3lume
Tz-Ru(II)TPP.
surface
pore radius) (Vp, cm /g)
(Å)
area
Ru(II)TPP complex over clickable SBA-15 support (Fig. 3b).[8, 30a,
32]
These NMR results demonstrate the successful
2
(m /g)
SBA-15
830.7
m²/g
314.6
m²/g
32.7 Å
1.13 cc/g
immobilization of [RuCl2(PPh3)3] complex on the clickable
surface of SBA-15 support.
SBA-15-Tz-
Ru(II)TPP
25.696 Å
0.425 cc/g
The functionalization of free hydroxyl groups of SBA-15 with
organic moiety could be accessed by 29Si CP MAS NMR
spectroscopy. Figure 4 (A,B) exhibit the 29Si CP MAS NMR
spectra of calcined SBA-15 and SBA-15-Tz-Ru(II)TPP catalyst.
4 | J. Name., 2012, 00, 1-3
This journal is © The Royal Society of Chemistry 20xx
Please do not adjust margins

Please do not adjust margins
Catalysis Science & Technology
Page 5 of 16
View Article Online
DOI: 10.1039/C7CY02619F
Journal Name
ARTICLE
The observed nitrogen adsorption desorption results of SBA- The XPS spectrum of SBA-15-Tz-Ru(II)TPP is displayed in figure
15, SBA-15-Tz-Ru(II)TPP with corresponding pore size 6. The accuracy of the observed binding energy (B.E.) is ±0.3
distribution curves are plotted in figure
5 and details eV. The Ru3d core level XPS spectrum shows two binding
summarized in table 1. The surface area, average pore energy (B.E.) peaks centered at 282 eV and 286 eV,
diameter and pore volume observed for SBA-15 and SBA-15- respectively. The first peak (282 eV) is well resolved and can be
Tz-Ru(II)TPP catalyst are summarized in the table 1. Both assigned to the BE of Ru3d5/2. As the second peak (286 eV) is
synthesized materials SBA-15 and SBA-15-Tz-Ru(II)TPP exhibit associated with the contribution Ru3d3/2, the peak at 286 eV is
type IV adsorption isotherms with a hysteresis characteristic deconvoluted and can be assigned to the existence of Ru in the
for mesoporous materials with uniformly size, completely +2 oxidation state in catalyst SBA-15-Tz-Ru(II)TPP (Fig. 6).[34]
P
reversible nature, with a capillary condensation step at XPS analysis value for the 2p3/2 and 2p1/2 core level are
P/Po=0.3–0.4 (As per IUPAC classification). The total surface distinguished at 131.3 and 132.1 respectively (Fig. S5). The
area, average pore radius and pore volume observed for SBA- value for phosphorous (P) XPS in SBA-15-Tz-Ru(II)TPP is in good
15 and SBA-15-Tz-Ru(II)TPP, were observed 830 m2g-1, 32.7Å, agreement with the literature value and confirms the
1.13 cm3g-1 and 314 m2g-1, 25.7 Å, 0.425 cm3g-1, respectively. [RuCl2(PPh3)3] complex retained when anchored over the
The noticeable change (decrease) in total mesoporous surface organomodified support SBA-15 (Fig. S6).[31a]. For the clear
area (62%), pore radius (21%) and pore volume (53%) after aspects of Ru, P, Cl elements presence in SBA-15-Tz-Ru(II)TPP
tris(triphenylphosphine)ruthenium(II) dichloride [RuCl2(PPh3)3] is confirmed by HR-XPS with complete spectrum (SI, Fig. S8).
immobilization over click modified SBA-15 is indicative of the
The thermal behavior of all the synthesized materials (A)
successful immobilization of complex over the mesoporous SBA-15, (B) SBA-15-N3, (C) SBA-15-Tz, (D) SBA-15-Tz-Ru(II)TPP
SBA-15 (Table 1) and consistent with the XRD and XPS results was studied by thermo gravimetric analysis (TGA), in air
(Figure 1, 5, 6).
atmosphere, from temperature up to 1000°C with an
increment of 10°C min−1 (Figure 7). The TGA plots of all click
modified SBA-15 samples show nearly 6% weight loss below
120°C, due to the desorption of absorbed water molecules
(Fig. 7,a-d). In the shown TGA plot, almost no weight loss was
observed for the calcined SBA-15 material between 120°C and
200°C, indicates the complete discharge of surfactant from
SBA-15 (Fig. 7a). The TGA results of the SBA-15-N3 material
show weight loss in two steps. In the first step, a weight loss
between 70°C and 140°C corresponds to the loss of water
2000
1800
1600
1400
1200
1000
800
Ru3d
3/2
286.2
Ru3d
5/2
282
600
400
200
291
288
285
282
279
276
Binding energy (eV.)
Figure 6. Ru XPS spectrum of SBA-15-Tz-Ru(II)TPP.
100
Figure 8. SEM images of (A) calcined SBA-15 and (B) SBA-15-Tz-
90
80
70
60
50
a
b
Ru(II)TPP.
c
d
0
200
400
600
800
1000
o
Temperature
( C)
Figure 7. TGA analysis of: (a) Calcined SBA-15, (b) SBA-15-N3,
(c) SBA-15-Tz, (d) SBA-15-Tz-Ru(II)TPP.
Figure 9. TEM images of SBA-15-Tz-Ru(II)TPP at different
magnification at; (A) 100 nm , (B) 20 nm.
This journal is © The Royal Society of Chemistry 20xx
J. Name., 2018, 00, 1-3 | 5
Please do not adjust margins

Please do not adjust margins
Catalysis Science & Technology
Page 6 of 16
View Article Online
DOI: 10.1039/C7CY02619F
ARTICLE
Journal Name
(adsorbed moisture). In the second step, a weight loss was acetylene, sodium azide and benzyl bromide using
observed in the range of 255°C–365°C; temperature regions homogeneous Ru Catalyst with respect to solvent and ligands
(255–365°C) attributed to 3-Az-PTMS (Fig. 7b). The TGA plot of and compare the results with our synthesised heterogeneous
SBA-15-N3 quantitatively shows the ~11.25% weight loss, Ru catalyst on the regioselectivity of the triazole formation (
which is greater than the calcined SBA-15, strongly supports Table 2). As per literature precedence the click reaction using
the on track anchoring of the 3-Az-PTMS over SBA-15 (Fig. Ru as catalyst gives the 1,5-disubstituted triazole heterocycles.
7a,b). In the case of click modified triazole complex SBA-15–Tz, When the Cu salt is used as catalyst, it shows different
one extra step weight loss in range of 250°C to 350°C was selectivity and provides the 1,4-disubstituted triazols. There
observed along with existing weight losses shown in the SBA- are only two reports for the Ru catalysed click reaction which
15-N3 (Fig.7.b,c). A categorical comparison of heterogenized show the contradicting result than the usual outcome for
SBA-15-Tz-Ru(II)TPP, and functionalized SBA-15-Tz in terms of reaction with certain limitations. So considering this we
weight loss shows an ~2 weight % loading of the complex hypothesized the multi componant click reaction of alkyne,
material, results are in good agreement with XPS and ICP-OES sodium azide and benzyl bromide.
results (Fig. 7a-d, Fig.S5, S9).
In order to optimize the reaction condition phenyl acetylene,
The SEM images of (A) SBA-15 and (B) SBA-15-Tz-Ru(II)TPP sodium azide and benzyl bromide were slected as model
are shown in figure 8. The morphology of SBA-15-Tz-Ru(II)TPP substrate and screened with various Ru catalyst for the click
was owned with the host mesoporous material SBA-15 after reaction, We began with RuCl3 as catalyst and PPh3 as ligand
the anchoring of [RuCl2(PPh3)3] complex on azido using DMF as solvent at 90 °C the reaction ended up with the
functionalized SBA-15.[27a,
30a]
The calcined SBA-15 shows very poor yields and reverse selectivity (i.e. 1, 4 substituted
cylindrical rod-like structure with wormlike morphology in the triazole) (Table 2 entry 1). Further to optimize reaction
SEM images. Further, the SBA-15-Tz-Ru(II)TPP demonstrated to conditions various solvents like DMSO, dioxane, toluene were
be alike molecular based material, the large molecular system tested but unfortunately there was little improvement with
changes into closely compacted together with respect to the maximum yield up to 26 % (Table 2, entry 2-4). To our delight,
SBA-15 after the [RuCl2(PPh3)3] complex is immobilized over when reaction was performed using water as solvent, the yield
the clickable mesoporous surface (Fig. 8 A,B). Moreover, the was increased up to 48% with reverse selectivity. To optimize
EDX pattern of SBA-15 and SBA-15-Tz-Ru(II)TPP indicates the the yield, the reaction was performed with different ligands
presence of ruthenium in the synthesized heterogeneous such as DMAP and 2-amino-6-picoline but it ended up with
catalyst SBA-15-Tz-Ru(II)TPP (Fig. S2).
lowering in the yield of product (Table 2. entry 6, 7). When the
The TEM images of the SBA-15 and SBA-15-Tz-Ru(II)TPP Ru catalyst was changed to [Ru(p-cym)Cl]2 the improvement in
provide structural evidence that the material is organized into the yield was not observed, We then considered the reaction
ordered arrays of two dimensional hexagonal mesopores and in homogeneous conditions switching over to heterogeneous
parallel channel structure with thick walls of the mesoporous condition from the homogeneous. Accordingly when the
materials clearly visualized with the different magnifications reaction performed with organosilica supported Ru catalyst
(Fig. 9 A,B, SI: S3). However, after the anchoring of the SBA-15-Tz-Ru(II)TPP , in water as solvent, and the reaction
[RuCl2(PPh3)3] complex over the clickable mesoporous proceeded very smoothly with the excellent yield of desired
channels of SBA-15 the image show darker contrast meso product and with reverse selectivity (88%) (Table 2, entry 9).
parallel channels, in comparison to the SBA-15 surface, We further proceeded to optimize the reaction condition with
corresponds to the proper anchoring of [RuCl2(PPh3)3] complex heterogeneous catalyst to establish a protocol in, water as a
over the clickable surface of the SBA-15 (Fig. 9 A,B).[27] EDX green solvent. Few of catalytic systems are active in aqueous
obtained from TEM analysis evidently confirms the presence of solution, such as CuSO4/copper ion complex[37] but, with high
elemental ruthenium, phosphorous in the heterogeneous concentration of copper complex. At our hand, we optimised
catalyst SBA-15-Tz-Ru(II)TPP (Fig. S4).
the multi component click reaction with respect to solvent,
and temperature and the results are summarized in table 3 &
4.
Catalytic Activity
Multicomponent Click Reaction
After thorough characterization, we proceeded further in
screening of multi component click cycloaddition of alkyne,
azide and alkyl halide (Scheme 3). This represents a powerful
method for the 1,4-disubstituted 1,2,3-triazole formation
compared to traditional click two component reaction. Scheme 5a. Intermediate 4-phenyl-1H-1,2,3-triazole formation
Extensive research have been done in multicomponent
reaction, but only few of them are recyclable and need
additives for enforced recycling viz; supported copper
catalyst.[35] However, these catalytic system suffers from
drawbacks, like use of additive, sodium ascorbate, and organic
solvents like dioxane, acetonitrile for reactions.[36]. We began Scheme 5b. Intermediate 4-phenyl-1H-1,2,3-triazole formation
with optimising the multicomponant click reaction of phenyl via homogeneous Catalyst
6 | J. Name., 2012, 00, 1-3
This journal is © The Royal Society of Chemistry 20xx
Please do not adjust margins

Please do not adjust margins
Catalysis Science & Technology
Page 7 of 16
View Article Online
DOI: 10.1039/C7CY02619F
Journal Name
ARTICLE
follows; water (88%) > DMF (63%) > EtOH (50%) > DMSO (46%)
> t-BuOH (35%) > THF (20%), respectively.
Lower temperature does not favor the formation of the
product (1,4-disubstituted 1,2,3-triazole), however the yield of
the triazole increased sharply up to 88% with an increase in
the reaction temperature at 90°C for 12 h under optimized
Scheme 5c. Intermediate 4-phenyl-1H-1,2,3-triazole reacts reaction conditions. It is noteworthy that the optimum
with BnBr
reaction temperature with respect to conversion towards the
triazole product, under the present reaction conditions, was
A variety of solvents, such as, DMSO, DMF, EtOH, t-BuOH, THF found to be 90°C. To establish the proficiency in catalytic
and water were screened, in the presence of SBA-15-Tz- activity of synthesized heterogeneous SBA-15-Tz-Ru(II)TPP
Ru(II)TPP catalyst at 90 °C, in a model reaction of the multi catalyst under optimized reaction conditions, a wide series of
component click cycloaddition between phenyl acetylene (1 nonsubstituted and substituted phenyl acetylenes were
mmol), benzyl bromide (1.2 mmol) and sodium azide (1.2 allowed to react with benzyl halides and sodium azide to
mmol) (Table 3). Solvents like DMSO, DMF, EtOH, t-BuOH THF produce the corresponding triazole, in good to excellent yields
were not able to give a significant yield (20-63%) even after 24 (Table 4). The mono-substituted phenyl acetylenes afforded
h reaction time period (Table 3, entries 1, 2, 3, 4, 5 and 8). In the product triazole in 88% yield (Table 4, entry 1). It is
addition, the reaction was also carried out at room evident that the electron withdrawing or electron donating
temperature using SBA-15-Tz-Ru(II)TPP catalyst in the
groups (EWG and EDG) attached to the phenyl acetylenes do
not affect much the rate of reaction (Table 4
entries 2-10). In case of methyl (-CH3) nitro (-
NO2) and –CN and -COMe substituted phenyl
acetylene reacted smooothly and obtaind
excellent yield of respective triazoles (Table 4
entries 2, 5, 3, 6). Similarly, the reaction with
alkoxy substituted phenyl acetylene also
furnished the corresponding product in good
to excellent yield of product (Table 4 entries
4, 7, 8, 9). Interestingly, the bulky aromatic
acetylenes also afforded the corresponding
product in excellent yield (~89%) (Table 4,
entry 10) (SI, S10, S11).
Though, the exact mechanism is not clearly
understood at this point but to support the
regioselective formation of 1,4-disubstituted
1,2,3-triazole product,
a few controlled
experiments were performed. In the present
study,
Ru-catalyzed
gives the
1,4-disubstituted
multi-component
reaction
exclusively
the
regioselective
compounds.[38] As our proposed method is
triazole
multi-component,
the
opposite
regioselectivity can be achieved; if the
reaction sequence follows first the Ru-
catalyzed cycloaddition of azide and alkyne to
give the intermediate 4-phenyl-1H-1,2,3-
triazole followed by sequential in situ
Figure 10. Plausible mechanism for the Multicomponant click substitution reaction with benzyl bromide to give the reported
reaction.
1,4-disubstituted 1,2,3-triazole compounds (scheme 5a). To
prove our hypothesis, first the reaction was carried out
presence of water and DMSO solvent under similar reaction without benzyl bromide, which was completed within six hours
conditions. But no progress of reaction was observed even furnishing the 4-phenyl-1H-1,2,3-triazole in excellent yield (83
after 24 h reaction period (Table 3, entries 1 and 7). The green %) under the optimized reaction conditions (NMR data are in
solvent water was found to be the most suitable under the good agreement with the literature report) (Scheme 5b) (See
optimized reaction conditions (Table 3, entry 9). From the SI for NMR detail, S11). The isolated intermediate when
obtained results of the solvent optimization for the conversion subjected to substitution reaction with benzyl bromide under
of phenylacetylene, the reactivity order of solvents emerged as the similar reaction condition, it afforded expected 1,4-
This journal is © The Royal Society of Chemistry 20xx
J. Name., 2018, 00, 1-3 | 7
Please do not adjust margins

Please do not adjust margins
Catalysis Science & Technology
Page 8 of 16
View Article Online
DOI: 10.1039/C7CY02619F
ARTICLE
Journal Name
disubstituted 1,2,3-triazole product (Scheme 5c). The same
To study the heterogeneous nature and stability of
product was obtained even employing the homogeneous synthesized SBA-15-Tz-Ru(II)TPP catalyst, Sheldon's hot
catalyst tris(triphenylphosphine)ruthenium(II) dichloride filtration test was carried out showing that there is nearly no
[RuCl2(PPh3)3]. The plausible mechanism for the regio ruthenium leaching into the reaction solution during course of
selectivity formation of 1,4-disubstituted triazole is given in the reaction. To perform the Sheldon's hot filtration test for
figure 10.
optimized reaction condition, catalyst SBA-15-Tz-Ru(II)TPP was
filtered out from the reaction mixture after 1 h during the
reaction, and the filtrate was again transfered into the RBF for
Hydrogen Transfer Reaction
Generally, classical hydrogen transfer reaction needs dry further continuation of the reaction without catalyst. The GC
organic solvent, inert atmosphere, prolonged reaction time analysis of filtrate was confirmed that conversation was up to
period and homogeneous catalysts.[11a, 39]. Backvall et al. 41% of corresponding product. As confirmed by GC analysis
reported appreciable activity of various homogeneous there was no improvement in the yield of hydrogen
ruthenium catalyzed hydrogen transfer reaction of different transferred product even prolongation of hot filtrate reaction
ketones.[40] In addition, few groups demonstrated potential of for addtional 10 h. Similarly the hot filtration test of
other metal complexes in homogeneous system for hydrogen multicomponent click cycloaddition was also performed under
transfer reactions. However, these catalytic systems face the optimized condition, SBA-15-Tz-Ru(II)TPP catalyst was filtered
drawbacks viz; tedious synthesis procedure, low TON, no off from the reaction mixture after 2 h and the reaction
recycling of expensive catalysts.[41] whereas the present continued uninterrupted in the absence of heterogeneous
developed protocol comprises benefits with minimal amount catalyst up to next 12 h. GC analysis showed that 20%
of catalyst, reuse and recycling of catalyst with high TON under conversion to the corresponding product after 2 h and the
ambient catalytic reaction conditions.
further conversion of multi component click cycloaddition
The synthesized heterogeneous SBA-15-Tz-Ru(II)TPP catalyst remained constant up to 12 h. In both reactions, results show
was investigated for hydrogen transfer reaction using product formation more than 80% (ICP result, SI, S9).
cyclohexanone as a model substrate. Under the optimized
reaction conditions the heterogeneous catalyst SBA-15-Tz-
(A)
(B)
100
Ru(II)TPP (30 mg), isopropanol (10 mL), 2-cyclohexanone (2
mmol) and NaOH (0.5 mmol) was stirred at 80°C (Scheme 4).
The progress of the reaction was monitored by GC. After the
80
completion of reaction the usual workup gave the expected
product in excellent yields.
To demonstrate the catalytic strength of SBA-15-Tz-Ru(II)TPP,
60
a blank reaction was carried out without SBA-15-Tz-Ru(II)TPP
catalyst and no product was detected in GC even after 24 h
using isopropanol and cyclohexanone as a standard substrate
40
under the optimised reaction conditions.
In order to further optimise the reaction conditions, various
bases such as NEt3, NaHCO3, KOH, NaOH and K2CO3 were
20
screened for the model reaction [Substrate isopropanol (10
mL) and cyclohexanone (2 mmol)]. The order of reactivity for
the transfer hydrogenation reaction of the cyclohexanone in
0
Fresh
I cycle
II cycle III cycle IV cycle V cycle
the presence of various bases could be arranged in following
order NaOH (100%) > KOH (98%) > K2CO3 (50%) > NaHCO3
Cycle
(40%) ≫ NEt3 (10%). NaOH was found to be the most suitable
base for the reaction (Table 5).
Figure 11. Recycle study of (A) hydrogen transfer reaction, (B)
A variety of carbonyl compounds were hydrogenated under
transfer hydrogenation reaction conditions using different
alcohols as hydrogen doner using SBA-15-Tz-Ru(II)TPP catalyst
results are summerised in Table 6. Carbonyl compounds such
as benzaldehyde, cyclohexanone, acetophenone, were
hydrogenated smoothly using isopropanol to give the excellent
yield of corresponding alcohols (Table 6, entries 1, 2, 3, 4).
Further, the aldehyde with electron withdowing group such as
4-chloro and 4-nitrobenzaldehyde reacted at much faster rate
irrespective of the hydrogen donor alcohols (primary,
secondary, tertiary) furnishing the corresponding product in
excellent yields and with high TON (Table 6, entries 5-10).
Multi component click cycloaddition.
Further, for the stability and recyclability study of the
developed heterogeneous catalyst, SBA-15-Tz-Ru(II)TPP was
recycled five times (fresh + four cycles) in both one pot multi
component click cycloaddition, and in the hydrogen transfer
reaction. After each cycle, the heterogeneous SBA-15-Tz-
Ru(II)TPP catalyst was removed by simple centrifugation,
washed several times with a suitable solvent dichloromethane
or ethanol (10 mL at 80°C) and dried under oven overnight
(Fig. 11). In every cycle, no considerable change was observed
in the conversion and selectivity of the corresponding reaction
product. Finally, after the last cycle, the ICP-OES analysis of the
8 | J. Name., 2012, 00, 1-3
This journal is © The Royal Society of Chemistry 20xx
Please do not adjust margins

Please do not adjust margins
Catalysis Science & Technology
Page 9 of 16
View Article Online
DOI: 10.1039/C7CY02619F
Journal Name
ARTICLE
used catalyst showed nearly stable ruthenium metal content SBA-15 was modified with 3-azidopropyltrimethoxysilane (Az-
with respect to the fresh catalyst (SI, S9). Conducted PTMS) via post grafting method.[8, 30a] In 1 g SBA-15 mixture
experiments confirm the heterogeneous nature of SBA-15-Tz- with 50 mL toluene, 3.5 mL 3-azidopropyl trimethoxysilane
Ru(II)TPP and stability which could be retained up to the (Az-PTMS) was added. The resulting mixture was stirred for 12
several cycle of the reactions.
h at 90ºC in inert atmosphere. After completion of reaction,
the solid was filtered and washed with toluene to remove
unreacted 3-Az-PTMS, further dried at 60°C for 12 h in oven to
get SBA-15-N3. Yield: 1.20 g (solid) and preserved under inert
atmosphere (Scheme 1B).
Conclusions
In summary, we demonstrated an efficient method for ligand
synthesis and covalent tethering to solid support, in a single
Ligand formation by using SBA-15-N3 and propargylamine (Via
click)
step using "click chemistry".
heterogeneous SBA-15-Tz-Ru(II)TPP catalyst is developed by
immobilizing [RuCl2(PPh3)3] complex over triazole
A new highly efficient,
Triazole ligand formation over clickable SBA-15 surface was
accomplished by following a method described in an earlier
report from our group.[8] In a 25 mL round bottom flask with a
magnetic stir bar, copper(I) iodide (0.5 mg) and vacuum
distilled N,N-diisopropylethylamine (DIPEA) (1 mL) were
charged with anhydrous, nitrogen-purged dimethylformamide
(DMF) (3 mL). The reaction mixture was stirred (till the solution
turned green) and in further step, transferred to
tetrahydrofuran (THF) reaction mixture (7.5 mL) containing 3-
azidopropyltrimethoxysilane (Az-PTMS) modified mesoporous
SBA-15 (SBA-15-N3) (0.5 g). Further, the propargylamine (10
mmol) were added and stirred at 50°C for 12 h. The modified
material was ultrasonicated for 20 min, washed with THF, and
dried under inert atmosphere. The material was kept in
desiccators in absence of light for further characterization and
modification (Scheme 1C). The obtained material is
abbreviated as SBA-15-Tz (yield 0.75 g).
functionalized SBA-15. The catalytic efficiency of SBA-15-Tz-
Ru(II)TPP was established for multicomponent click
cycloaddition and hydrogen transfer reaction. Surprisingly,
multi-component cycloaddition reaction exhibit remarkable
reactivity in water medium for the regioselective synthesis of
1,4-disubstituted 1,2,3-triazole in excellent yields in contrast to
the literature report of 1,5-disubstituted 1,2,3-triazole
formation. Additionally, in hydrogen transfer reactions,
screened carbonyl compounds, shows up to 100% conversion
to give hydrogen transferred products. The salient features of
the heterogeneous catalyst SBA-15-Tz-Ru(II)TPP are its stability
in water as reaction medium, heterogeneous nature and
recyclability without loss of activity.
B Synthetic procedures, Materials and methods, Crystallography.
Experimental
The materials used, such as Pluronic 123 (P123, average
SBA-15-Tz anchoring by tris(triphenylphosphine)ruthenium(II)
dichloride [RuCl2(PPh3)3] complex
Mol.Wt.
=
5800), tetraethylorthosilicate (TEOS), 3-
(3-APTMS), [RuCl2(PPh3)3],
aminopropyltrimethoxysilane
Modified SBA-15 material (SBA-15-Tz) (1 g) was added to the
solution of [RuCl2(PPh3)3] (0.15 mmol) in DMF (50 mL) and
refluxed under argon for 12 h. Later, the product was allowed
to cool and filtered. The obtained gray color solid was washed
with THF (25 mL) and acetone (25 mL). Further, product was
soxhlet extracted with dichloromethane (CH2Cl2) for 24 h to
remove unreacted [RuCl2(PPh3)3] and organic impurities
(Scheme 1D). The resulting product was dried with the help of
vacuum at 75°C to furnish 1.4 g of the SBA-15-Tz-Ru(II)TPP.
sodium azide (NaN3), N, N-diisopropylethylamine (DIPEA),
copper iodide (CuI), propargylamine, aldehyde, alcohols were
purchased from Aldrich. Furthermore, solvents like
dichloromethane (DCM), tetrahydrofuran (THF), acetonitrile
(CH3CN) and toluene were purchased from Merck.
Synthesis of heterogeneous catalyst SBA-15-Tz-Ru(II)TPP:
The synthesis of SBA-15 was carried out by following the well
[27a, 28a, 29]
established modified literature procedure
with the
following initial molar compositions, (180.043) TEOS: 4.4 g P123
Mavg = 5800 [EO20–PO70–EO20]: (8.33) H2O: (0.24) HCl, Pluronic
123 called as P123 (4.4 g), a triblock co-polymer (surfactant),
was dispersed in 30 g distilled water and stirred for 1.5 h. 120
g of 2M HCl added into the solution with constant stirring and
continued for further 2 h. At the same time, 9 g of TEOS
(precursor) was added drop wise and resulting solution was
maintained at 35°C for next 24 h with stirring. The mixture was
kept for hydrothermal treatment at 100°C for 48 h under static
conditions. The obtained material was filtered, washed with
distilled water and dried in oven at 70°C for 12 h, and later
calcined at 540°C for 8 h in air to get calcined SBA-15 (11.5 g).
Multi Component Click reaction
In the 50 mL round bottom flask, alkyne (1 mmol), sodium
azide (1.2 mmol), benzyl bromide (1.2 mmol) and SBA-15-Tz-
Ru(II)TPP catalyst 15 mg were taken followed by addition of 3
ml of water as solvent. The mixture was stirred at 90°C in the
preheated oil bath for given time. Progress of the reaction was
monitored by TLC (2:8 ethyl acetate: pet ether). After the
completion of reaction, 10 mL of ethyl acetate added to the
reaction mixture and filtered to recover the SBA-15-Tz-
Ru(II)TPP catalyst. Residue was washed with ethyl acetate (5
mL x 3 times). Combined organic layer was dried with
anhydrous sodium sulphate and concentrated under the
reduced pressure. The crude product was purified by the
Surface modification over SBA-15 via azide group
This journal is © The Royal Society of Chemistry 20xx
J. Name., 2018, 00, 1-3 | 9
Please do not adjust margins

Please do not adjust margins
Catalysis Science & Technology
Page 10 of 16
View Article Online
DOI: 10.1039/C7CY02619F
ARTICLE
Journal Name
column chromatography to get the product 4 a-n (Scheme 3). The APS acknowledges CSIR, New Delhi for the financial
The product was characterized by GCMS and 1H & 13C NMR support in the form of an Emeritus Scientist project (P81103).
analysis (SI, S10, S11).
PK is grateful to INSA, New Delhi for financial support under
senior scientist program. Jayant Rathod thanks the Council of
Scientific and Industrial Research (CSIR), New Delhi for a Senior
Research Fellowship. P. Sharma gratefully acknowledges the
project (Grant No. 207/12 Israel grant) for financial support.
Hydrogen Transfer Reaction
In a 25 mL two neck round bottom flask, carbonyl compounds
(2 mmol), NaOH (0.5 mmol), alcohol (isopropanol) (10 mL), and
SBA-15-Tz-Ru(II)TPP catalyst (30 mg) were stirred under argon
at 80°C. The reaction mixture was analyzed by GC at measured
time intervals (Scheme 4).
Notes and references
1
a)H. C. Kolb, K. B. Sharpless, Drug Discov. Today 2003,
8, 1128-1137; b)D. Dheer, V. Singh, R. Shankar,
Bioorganic Chemistry 2017, 71, 30-54.
J.-F. Lutz, Z. Zarafshani, Adv. Drug Deliv. Rev. 2008, 60,
958-970.
Results and Discussion
Characterization
2
3
Powder X-ray diffraction (XRD) patterns were measured on a
PAN analytical X’pert Pro dual goniometer diffractometer using
Ni-filtered CuKa radiation (l = 1.5404 Å) over the range 0.5–51
(SAXRD). N2 adsorption–desorption isotherms, pore size
distributions as well as the textural properties of the hybrid
a)R. Huisgen, G. Szeimies, L. Möbius, Chem. Ber. 1967
,
100, 2494-2507; b)M. S. Singh, S. Chowdhury, S. Koley,
Tetrahedron 2016, 72, 5257-5283.
4
a)H. Struthers, T. L. Mindt, R. Schibli, Dalton Trans.
2010, 39, 675-696; b)T. Romero, R. A. Orenes, A.
Espinosa, A. Tárraga, P. Molina, Inorg. Chem. 2011, 50,
8214-8224; c)J. P. Byrne, J. A. Kitchen, T. Gunnlaugsson,
Chem. Soc. Rev. 2014, 43, 5302-5325.
materials were determined by using
a Autosorb 1C
Quantachrome USA. The program consisting of both an
adsorption and desorption branch typically ran at -196°C after
samples were degassed at 150°C for 4 h. The BET method was
applied to calculate the total surface area at relative pressures
of P/P0 = 0.65–0.45 and the BJH model was applied to the
adsorption branch of the isotherm to determine the total pore
volume and average pore diameter at a relative pressure of
P/P0 = 0.99. Pore size distribution curves were obtained via the
NLDFT model assuming cylindrical pore geometry. Magic angle
spinning (MAS) NMR spectra of 29Si, 31P and 13C nuclei were
recorded on a BRUKER DSX300 spectrometer at 7.05 T
(resonance frequencies 59.595 MHz, rotor speed 10 000 Hz
and 75.43 MHz, rotor speed 10 000 Hz). XPS analysis was
conducted using XPS Kratos AXIs Ultra (Kratos Analytical Ltd.,
UK) high resolution photoelectron spectroscopy instrument.
FTIR spectra were recorded on a Bruker Alpha-T. Sample
morphology was observed by extra High-Resolution Scanning
Electron Microscopy (MagellanTM 400 L). Thermal analysis
(TGA) of the samples was conducted using a Pyris Diamond
TGA analyzer with a heating rate of 100ºC min−1 under air
atmosphere. GC analyses were performed using Focus GC from
Thermo Electron Corporation, equipped with low polarity ZB-5
column. GC analyses were performed using Trace 1300 Gas
Chromatograph model from Thermo Scientific, equipped with
the Rxi-1ms (crossbond 100% dimethyl polysiloxane) column.
Conversion based on GC area. The ruthenium (Ru) content of
product was determined by an Inductively Coupled Plasma
Mass Spectrometry (ICPMS) spectrometer (Agilent 7500 cx).
5
6
R. M. Meudtner, M. Ostermeier, R. Goddard, C.
Limberg, S. Hecht, Chem. – Eur. J. 2007, 13, 9834-9840.
a)D. Schweinfurth, R. Pattacini, S. Strobel, B. Sarkar,
Dalton Trans. 2009, 9291-9297; b)D. Schweinfurth, C.-
Y. Su, S.-C. Wei, P. Braunstein, B. Sarkar, Dalton Trans.
2012, 41, 12984-12990.
7
J. D. Crowley, D. A. McMorran, in Click Triazoles (Ed.: J.
Košmrlj), Springer Berlin Heidelberg, Berlin, Heidelberg,
2012, pp. 31-83.
8
9
P. Sharma, A. P. Singh, RSC Adv. 2014, 4, 43070-43079.
S.-H. Cho, T. Gadzikwa, M. Afshari, S. T. Nguyen, J. T.
Hupp, Eur. J. Inorg. Chem. 2007, 2007, 4863-4867.
a)C. T. Kresge, M. E. Leonowicz, W. J. Roth, J. C. Vartuli,
J. S. Beck, Nature 1992, 359, 710-712; b)J. S. Beck, J. C.
Vartuli, W. J. Roth, M. E. Leonowicz, C. T. Kresge, K. D.
Schmitt, C. T. W. Chu, D. H. Olson, E. W. Sheppard, S. B.
McCullen, J. B. Higgins, J. L. Schlenker, J. Am. Chem.
Soc. 1992, 114, 10834-10843.
10
11
a)R. D. Patil, Y. Sasson, Asian J. Org. Chem. 2015, 4,
1258-1261; b)S.-Q. Bai, L. Jiang, J.-L. Zuo, T. S. A. Hor,
Dalton Trans. 2013, 42, 11319-11326; c)Z. Gonda, Z.
Novak, Dalton Trans. 2010, 39, 726-729; d)D. Wang, M.
Zhao, X. Liu, Y. Chen, N. Li, B. Chen, Org. Biomol. Chem.
2012, 10, 229-231; e)F. Wang, H. Fu, Y. Jiang, Y. Zhao,
Green Chem. 2008, 10, 452-456.
12
13
a)L. Jiang, Z. Wang, S.-Q. Bai, T. S. A. Hor, Dalton Trans.
2013, 42, 9437-9443; b)F. Nador, M. A. Volpe, F.
Alonso, A. Feldhoff, A. Kirschning, G. Radivoy, Appl.
Catal. A. 2013, 455, 39-45.
Conflicts of interest
“There are no conflicts to declare”.
a)M. Singla, P. Mathur, M. Gupta, M. S. Hundal,
Transition Met. Chem. 2008, 33, 175-182; b)K. R.
Gruenwald, A. M. Kirillov, M. Haukka, J. Sanchiz, A. J. L.
Pombeiro, Dalton Trans. 2009, 12, 2109-2120.
Acknowledgements
10 | J. Name., 2012, 00, 1-3
This journal is © The Royal Society of Chemistry 20xx
Please do not adjust margins

Please do not adjust margins
Catalysis Science & Technology
Page 11 of 16
View Article Online
DOI: 10.1039/C7CY02619F
Journal Name
ARTICLE
14
a)C. Wang, D. Ikhlef, S. Kahlal, J.-Y. Saillard, D. Astruc, 30
a)M. Kar, B. Malvi, A. Das, S. Panneri, S. S. Gupta, J.
Mater. Chem. 2011, 21, 6690-6697; b)B. Malvi, B. R.
Sarkar, D. Pati, R. Mathew, T. G. Ajithkumar, S. Sen
Gupta, J. Mater. Chem. 2009, 19, 1409-1416; c)J. Gao,
X. Zhang, S. Xu, J. Liu, F. Tan, X. Li, Z. Qu, Y. Zhang, X.
Quan, Chem. Asian J. 2014, 9, 908-914.
Coordination Chemistry Reviews 2016, 316, 1-20; b)A.
Tăbăcaru, B. Furdui, I. O. Ghinea, G. Cârâc, R. M. Dinică,
Inorganica Chimica Acta 2017, 455, 329-349.
15
16
J. R. Johansson, T. Beke-Somfai, A. Said Stålsmeden, N.
Kann, Chemical Reviews 2016, 116, 14726-14768.
a)B. C. Boren, S. Narayan, L. K. Rasmussen, L. Zhang, H. 31
a)A. Ghosh, R. Kumar, Micropor. Mesopor. Mat. 2005
,
Zhao, Z. Lin, G. Jia, V. V. Fokin, J. Am. Chem. Soc. 2008
,
87, 33-44; b)T. Joseph, S. S. Deshpande, S. B. Halligudi,
A. Vinu, S. Ernst, M. Hartmann, J. Mol. Catal. A: Chem.
2003, 206, 13-21.
130, 8923-8930; b)S. Oppilliart, G. Mousseau, L. Zhang,
G. Jia, P. Thuéry, B. Rousseau, J.-C. Cintrat, Tetrahedron
2007, 63, 8094-8098; c)M. M. Majireck, S. M. Weinreb, 32
J. Org. Chem. 2006, 71, 8680-8683; d)Y.-H. Lo, T.-H.
Wang, C.-Y. Lee, Y.-H. Feng, Organometallics 2012, 31, 33
6887-6899; e)D.-R. Hou, T.-C. Kuan, Y.-K. Li, R. Lee, K.-
W. Huang, Tetrahedron 2010, 66, 9415-9420.
S. Sisodiya, A. Lazar, S. Shylesh, L. Wang, W. R. Thiel, A.
P. Singh, Chem. Commun. 2012, 25, 22-27.
S. Farsadpour, L. T. Ghoochany, S. Shylesh, G. Dörr, A.
Seifert, S. Ernst, W. R. Thiel, ChemCatChem 2012, 4,
401-407.
17
18
P. N. Liu, J. Li, F. H. Su, K. D. Ju, L. Zhang, C. Shi, H. H. Y. 34
Sung, I. D. Williams, V. V. Fokin, Z. Lin, G. Jia,
Organometallics 2012, 31, 4904-4915.
a)A. Jana, J. Mondal, P. Borah, S. Mondal, A. Bhaumik,
Y. Zhao, Chem. Commun. 2015, 51, 10746-10749; b)C.
Agnes, J.-C. Arnault, F. Omnes, B. Jousselme, M. Billon,
G. Bidan, P. Mailley, Phys. Chem. Chem. Phys. 2009, 11,
11647-11654.
a)J.-E. Bäckvall, J. Organomet. Chem. 2002, 652, 105-
111; b)X. Wu, J. Xiao, Chem.Commun. 2007, 24, 2449-
2466; c)S. E. Clapham, A. Hadzovic, R. H. Morris, Coord. 35
Chem. Rev. 2004, 248, 2201-2237; d)P. Albin, J. Blum, E.
Dunkelblum, Y. Sasson, J Org. Chem. 1975, 40, 2402-
2403.
a)B. Dervaux, F. E. Du Prez, Chem. Sci. 2012, 3, 959-
966; b)V. Bénéteau, A. Olmos, T. Boningari, J. Sommer,
P. Pale, Tetrahedron Lett. 2010, 51, 3673-3677; c)E.
Ozkal, S. Ozcubukcu, C. Jimeno, M. A. Pericas, Catal.
Sci. Technol. 2012, 2, 195-200.
19
a)G. Brieger, T. J. Nestrick, Chem. Rev. 1974, 74, 567-
580; b)R. A. W. Johnstone, A. H. Wilby, I. D. Entwistle, 36
Chem. Rev. 1985, 85, 129-170; c)P. K. Mandal, J. S.
McMurray, J Org Chem. 2007, 72, 6599-6601.
a)B. H. Lipshutz, B. R. Taft, Angew. Chem. 2006, 118,
8415-8418; b)M. Nasr-Esfahani, I. Mohammadpoor-
Baltork, A. R. Khosropour, M. Moghadam, V. Mirkhani,
S. Tangestaninejad, H. Amiri Rudbari, J. Org. Chem.
2014, 79, 1437-1443.
20
21
22
23
R. Tao, Y. Xie, G. An, K. Ding, H. Zhang, Z. Sun, Z. Liu, J.
Colloid. Interface Sci. 2010, 351, 501-506.
S. U. Sonavane, R. V. Jayaram, Synth. Commun. 2003
,
37
a)H. Sharghi, M. H. Beyzavi, A. Safavi, M. M.
Doroodmand, R. Khalifeh, Adv. Synth. Catal. 2009, 351,
2391-2410; b)H. Sharghi, R. Khalifeh, M. M.
Doroodmand, Adv. Synth. Catal. 2009, 351, 207-218.
B. C. Boren, S. Narayan, L. K. Rasmussen, L. Zhang, H.
Zhao, Z. Lin, G. Jia, V. V. Fokin, Journal of the American
Chemical Society 2008, 130, 8923-8930.
33, 843-849.
L. He, J. Ni, L.-C. Wang, F.-J. Yu, Y. Cao, H.-Y. He, K.-N.
Fan, Chem. – Eur. J 2009, 15, 11833-11836.
a)X. Wu, J. Liu, X. Li, A. Zanotti-Gerosa, F. Hancock, D. 38
Vinci, J. Ruan, J. Xiao, Angew. Chem., Int. Ed. 2006, 45,
6718-6722; b)A. Bényei, F. Joó, J Mol. Catal. A Chem.
1990, 58, 151-163.
39
a)A. Aranyos, G. Csjernyik, K. J. Szabo, J.-E. Backvall,
Chem. Commun. 1999, 351-352; b)R. L. Chowdhury, J.-
E. Backvall, Chem. Commun. 1991, 1063-1064; c)S.
Mazza, R. Scopelliti, X. Hu, Organometallics 2015, 34,
1538-1545.
24
25
26
27
28
a)T. Ikariya, A. J. Blacker, Acc. Chem. Res. 2007, 40,
1300-1308; b)F.-Z. Su, L. He, J. Ni, Y. Cao, H.-Y. He, K.-N.
Fan, Chem.Commun. 2008, 30, 3531-3533.
a)W. Ye, M. Zhao, W. Du, Q. Jiang, K. Wu, P. Wu, Z. Yu,
Chem. – Eur. J 2011, 17, 4737-4741; b)J. Toubiana, Y. 40
Sasson, Catal. Sci. Technol. 2012, 2, 1644-1653.
a)G. Z. Wang, J.-E. Backvall, Chem. Commun. 1992, 337-
339; b)Y. R. S. Laxmi, J.-E. Backvall, Chem. Commun.
2000, 611-612.
a)W. Ye, M. Zhao, Z. Yu, Chem. – Eur. J 2012, 18, 10843-
10846; b)S. Gladiali, E. Alberico, Chem. Soc. Rev. 2006
,
41
a)R. Langer, G. Leitus, Y. Ben-David, D. Milstein, Angew.
Chem. Int. Ed. 2011, 50, 2120-2124; b)A. Mikhailine, A.
J. Lough, R. H. Morris, J. Am. Chem. Soc. 2009, 131,
1394-1395.
35, 226-236.
a)P. Sharma, A. P. Singh, RSC Adv. 2014, 4, 58467-
58475; b)A. Lazar, W. R. Thiel, A. P. Singh, RSC Adv.
2014, 4, 14063-14073.
a)A. Lazar, C. P. Vinod, A. P. Singh, New J. Chem. 2016
,
40, 2423-2432; b)D. Zhao, J. Feng, Q. Huo, N. Melosh,
G. H. Fredrickson, B. F. Chmelka, G. D. Stucky, Science
1998, 279, 548-552.
29
A. Lazar, P. Sharma, A. P. Singh, Micropor. Mesopor.
Mat. 2013, 170, 331-339.
This journal is © The Royal Society of Chemistry 20xx
J. Name., 2018, 00, 1-3 | 11
Please do not adjust margins

Please do not adjust margins
Catalysis Science & Technology
Page 12 of 16
View Article Online
DOI: 10.1039/C7CY02619F
ARTICLE
Journal Name
Table 2. Optimization for multi component cycloaddition
reaction in homogeneous and heterogeneous medium.
S.No.
Catalyst
Ligand
Solvent
Yield
(%)
1.
2.
3.
4.
5.
6.
RuCl3
RuCl3
RuCl3
RuCl3
RuCl3
RuCl3
PPh3
PPh3
PPh3
PPh3
PPh3
DMAP
DMF
6
DMSO
Dioxane
Toluene
Water
24
26
5
48
32
Water
2-amino-
6-picoline
7.
8.
RuCl3
Water
Water
10
26
[Ru(p-
cym)Cl]2
--
--
SBA-15-Tz-
u(II)TPP
9.
Water
88
Reaction conditions: Phenyl acetylene (1 mmol), Benzyl bromide
(1.2 mmol), Sodium azide (1.2 mmol), Catalyst (Ruthenium 0.445
mol %) and solvent (3 mL).
Table 3. Solvent optimization for multi component cycloaddition
reaction.
Entry
Solvent
Time
(h)
24
12
12
12
24
12
24
Temperature
Yield
(%)
00
46
63
35
50
88
00
(oC)
RT
90
1.
2.
3.
4.
5.
6.
7.
8.
DMSO
DMSO
DMF
t-BuOH
EtOH
H2O
90
90
90
90
RT
90
H2O
THF
12
20
Reaction conditions: Phenyl acetylene (1 mmol), Benzyl
bromide (1.2 mmol), Sodium azide (1.2 mmol), SBA-15-Tz-
Ru(II)TPP Catalyst (15 mg, Ruthenium metal 0.445 mol %) and
solvent (3 mL).
Table 4: Multi component click cycloaddition using SBA-15-Tz-
Ru(II)TPP.
12 | J. Name., 2012, 00, 1-3
This journal is © The Royal Society of Chemistry 20xx
Please do not adjust margins

Please do not adjust margins
Catalysis Science & Technology
Page 13 of 16
View Article Online
DOI: 10.1039/C7CY02619F
Journal Name
ARTICLE
S.No.
Alkynes
Product
Yields (%)a
Entry
place of BnBr, c) 1-decyne as
alkyne, d) 1-Bromobutane was
used in place of BnBr.
1.
88
4a
4b
86
92
2.
3.
4c
4d
78
82
4.
5.
4e
77
86
4f
6.
7.
4g
70
76
89
4h
4i
4j
8.
9.
10.
11.
87b
85
4k
4l
12.
13.
73c
76d
4m
4n
14.
Reaction Conditions: Phenyl acetylene (1 mmol), Benzyl bromide
(1.2 mmol), Sodium azide (1.2 mmol), Catalyst SBA-15-Tz-
Ru(II)TPP (15 mg, Ruthenium metal 0.445 mol %) and solvent (3
mL), time period 12 h. a) Isolated Yields, b) PMB-Cl was used in
This journal is © The Royal Society of Chemistry 20xx
J. Name., 2018, 00, 1-3 | 13
Please do not adjust margins

Please do not adjust margins
Catalysis Science & Technology
Page 14 of 16
View Article Online
DOI: 10.1039/C7CY02619F
ARTICLE
Journal Name
Table 5: Base optimization for catalytic hydrogen transfer
reaction.
S.No.
1.
Base
NaOH
KOH
Yield (%)
100
98
2.
3.
K2CO3
NaHCO3
NEt3
50
4.
40
5.
10
Reaction conditions: SBA-15-Tz-Ru(II)TPP (30 mg, Ruthenium
metal 0.445 mol %), Alcohol (10 mL), carbonyl compound (2
mmol), base (0.5 mmol), 80°C Isolated yields; Product
analyzed by GC. Conversion based on GC area.
Table 6: Catalytic hydrogen transfer reaction using SBA-15-Tz-
Ru(II)TPP catalyst.
14
|
J. Name., 2012, 00, 1-3
This journal is © The Royal Society of Chemistry 20xx
Please do not adjust margins

Please do not adjust margins
Catalysis Science & Technology
Page 15 of 16
View Article Online
DOI: 10.1039/C7CY02619F
Journal Name
ARTICLE
S.No.
Carbonyl
compound
Alcohol
Product
Yield (%)
TON
Time (h)
1.
2.
3.
4.
5.
6
6
6
6
2
89
71
73
80
92
200
160
164
180
207
6.
7.
8.
2
2
1
97
85
95
218
191
213
9.
1.5
2
99
80
223
180
10.
Reaction conditions: SBA-15-Tz-Ru(II)TPP (30 mg, Ruthenium
metal 0.445 mol %), Alcohol (10 mL), carbonyl compound (2
mmol), NaOH (0.5 mmol), 80°C Isolated yields; Product analyzed
by GC. Conversion and yield based on GC area.
This journal is © The Royal Society of Chemistry 20xx
J. Name., 2018, 00, 1-3 | 15
Please do not adjust margins

Please do not adjust margins
Catalysis Science & Technology
Page 16 of 16
View Article Online
DOI: 10.1039/C7CY02619F
ARTICLE
Journal Name
Table of Content
Synthesis of Heterogeneous Ru(II)-1,2,3-Triazole catalyst
supported over SBA-15: Application to the Transfer Hydrogen
reaction and unusual highly selective 1,4-disbustituted traizole
formation via Multicomponent Click Reaction
Priti Sharma#[a]
, , , Pradeep
Jayant Rathod#[c] A.P. Singh*[b]
Kumar*[c] and Yoel Sasson*[a]
16
|
J. Name., 2012, 00, 1-3
This journal is © The Royal Society of Chemistry 20xx
Please do not adjust margins