CuI anchored onto mesoporous SBA-16 functionalized by aminated 3-glycidyloxypropyltrimethoxysilane with thiosemicarbazide (SBA-16/GPTMS-TSC-CuI): A heterogeneous mesostructured catalyst for: S -arylation reaction under solvent-free conditions

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Heterogeneous catalytic oxidation for lignin valorization into valuable

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ARTICLE

CuI-anchored onto mesoporous SBA-16 functionalized by aminated

3-glycidyloxypropyltrimethoxysilane with

thiosemicarbazide (SBA-16/ GPTMS-TSC-CuI): a heterogeneous

mesostructured catalyst for S-arylation reaction under solvent-free

conditions

Received 00th January 20xx,

Accepted 00th January 20xx

DOI: 10.1039/x0xx00000x

www.rsc.org/

Sara. S. E. Ghodsinia ^a, Batool Akhlaghinia^a,*

Herein we report a novel synthesis of Cu^I-anchored onto the cage-like mesoporous material SBA-16, which successfully

functionalized by aminated 3-glycidyloxypropyltrimethoxysilane with thiosemicarbazide (SBA-16/GPTMS-TSC-Cu^I) as an

efficient and highly recyclable heterogeneous catalyst. The as-synthesized mesostructured catalyst (SBA-16/GPTMS-TSC-Cu^I)

effusively characterized by different techniques such as FT-IR, FIR, SAXRD, XRD, XPS, BET, TEM, FE-SEM, EDX, EDX-mapping,

TGA, ICP-OES, and CHN analysis. SBA-16 with the unique “super-cage” structure efficiently controlled the formation of

dispersed organic and metal species in the mesoporous channels. These confined nanoparticles with a narrow particle size

distribution (3-7 nm) exhibited excellent catalytic activity in S-arylation reaction without the need of using toxic solvents

and/or expensive metal catalyst. Interestingly, the mesoporous catalyst was so stable under the reaction conditions and

could be easily separated by simple filtration and reused for at least seven recycle runs (without any appreciable loss of its

catalytic reactivity). Due to the inimitable structure of the above-mentioned mesostructured catalyst,the C-S coupling

products of aryl halides with S₈/ or thiourea under solvent-free conditions were obtained in good to excellent yields in

remarkably reduced reaction time in comparison to the previous reports.

reducing agents, strong unreusable bases, elevated temperatures,

environmental unfavorable, and odorous thiols as air sensitive,

Introduction

Today, the C‐S bond is arguably one of the most important functional

group with a wide range of applications in the expansion of novel

precursors or intermediates in organic synthesis [1]. Particularly, in

the last few years, its significance in making various arrangements of

target compounds including pharmaceutical to biological molecules

is its extraordinary application in biochemistry and material science

as the frontiers of modern synthetic organic chemistry [2, 3]. Among

aromatic sulfur-containing compounds occurred in abundance in

nature, diaryl thioethers are employed in various clinical applications

as antidiabetes, anti-inflammatory, anti-Alzheimer’s, anti-

Parkinson’s, anticancer, and anti-HIV [4,5]. Due to the importance of

these compounds, the search for new preparation methods of diaryl

thioethers is of strategic importance in synthetic chemistry, which

has received much current interest. The classical sulfide construction

involves reduction of aryl sulfones or aryl sulfoxides [6], thiol(ate)

alkylation or arylation [7–16] or the treatment of an organometallic

reagent with a disulfide molecule [17–21]. However, most of these

methods include some limitations such as the utilization of strong

volatile, and hazardous starting materials. Moreover, the common

drawbacks associated with these reactions are the great tendency

for the oxidative coupling of thiols to form (homocoupling sulfur-

sulfur) disulfides (as side-products which lead to environmental and

safety problems) as well as the capability of thiolate anion to

suppress the activity of the catalyst (has reverse effect in target

process). In order to overcome these shortcomings and to replace

the traditional method of C-S cross-coupling reaction, other sulfur

surrogates such as thiourea [22–26], potassium thioacetate [27],

carbon disulfide [28–32], metal sulfides [33,34], sulfonyl hydrazide

[35,36], ethyl xanthogenate [37], thiocyanate [38], thioacetamide

[39], S₈[40-49], and Na₂S₂O₃[50] are interestingly used as alternative

to thiols in recent years. Among sulfur‐transfer reagents S₈(since

antiquity has been known and recently become popular in chemical

industries) and thiourea presented an interesting breakthrough in

the field of thiol-free C–S bond formation, due to their low cost,

availability, safety, and being odorless [26, 51-52]. Owing to strong

coordination nature of the sulfur atom, the transition metal-

catalyzed C-S cross-coupling reaction is not much studied in

comparison to the other carbon-heteroatom bonds such as C-N, C-O

and C-P. Over the last decades, few methods for C-S bond formation

have gained much interest and improved employing transition

metals like Pd, Ni, Fe, Cu, Co, In and Bi [53]. Copper in particular

^a.Department of Chemistry, Faculty of Science, Ferdowsi University of Mashhad,

Mashhad 9177948974, Iran.

*E-mail: akhlaghinia@um.ac.ir, Tel.: +98-51-3880-5527.

Electronic Supplementary Information (ESI) available: [details of any supplementary

information available should be included here]. See DOI: 10.1039/x0xx00000x

This journal is © The Royal Society of Chemistry 20xx

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provides higher catalytic activity due to its special redox properties, reaction of II with thiosemicarbazide (TSC) afforded SBA-16/GPTMS-

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DOI: 10.1039/C8GC03931C

polarizability and cost-effectiveness than most of the other transition TSC (III) which upon treatment with ethanolic solution of CuCl under

metals [54]. The reported methods of copper-catalyzed S-arylation argon atmosphere produced Cu^I-anchored onto mesoporous SBA-16

include Cu-nanoparticle systems [55], ligand-free systems [56], functionalized by aminated 3-glycidyloxypropyltrimethoxysilane

ligand-based systems [57] and systems using various sulfur reagents with thiosemicarbazide (SBA-16/GPTMS-TSC-Cu^I(IV)) (with 1.18

[58].

wt.% of copper content according to the ICP-OES measurement).

Recently, heterogeneous catalysis due to economic and industrial Hence, as a part of our research program directed towards cross-

significance is of paramount importance in many areas [59-64]. The coupling reactions [85], and in view of the above fundamental

published reports indicate that heterogeneously catalyzed processes understandings regarding the C-S bond formation, we targeted our

scored over homogeneous catalysts. Nowadays immobilization of study to find out a new approach using SBA-16/GPTMS-TSC-Cu^I(IV)

metal active sites on solid supports, such as polymeric microspheres, for the synthesis of symmetrical diaryl sulfides from the cascade

microcapsules and resin [65-67], mesoporous materials [68, 69], reaction of aryl halides with S₈/ or thiourea with more operational

amorphous silica [70], and carbon nanofibers [71] have been simplicity, greater selectivity, higher product yield, and economic

developed extensively. Due to regularly arranged pore structure [72], viability, in addition to catalyst reusability as a welcome goal

narrow pore size distribution [73], high pore volume, large specific concerning the green chemistry demands. (Scheme 2)

surface area, and great hydrothermal stability, mesoporous

materials (especially SBA-type silica) have the great superiority

Results and Discussion

After preparation of Cu^I-anchored onto mesoporous SBA-16

among the other solid supports. Cubic-structured mesoporous silica

functionalized by aminated 3-glycidyloxypropyltrimethoxysilane

(nanocage interconnected three dimensionally to eight neighboring

with thiosemicarbazide (SBA-16/GPTMS-TSC-Cu^I(IV)) the

mesostructured catalyst was characterized by some microscopic and

spectroscopic techniques including Fourier transform infrared (FT-IR)

spectroscopy, far-infrared (FIR), small-angle X-ray diffraction (small-

angle XRD), X-ray powder diffraction (XRD), X-ray photoelectron

spectroscopy (XPS), Brunauer, Emmett and Teller (BET) surface area

cages through pore entrances which are more resistant to blocking)

e.g., SBA-16 as a novel mesoporous silica material with the large cage

Im3m structure [74] can accommodate metal, metal oxide, and

metal sulfide catalysts in situ up to the size of the cage [75]. SBA-16

improved the catalytic activities via reducing agglomeration of

particles and allowed smooth transport of reactants and products as

analysis, transmission electron microscopy (TEM), field emission

well. The migration of metal nanoparticles may be inhibited by the

scanning electron microscopy (FE-SEM), energy-dispersive X-ray

smaller pore entrances, which was limited the extent of sintering.

Furthermore, SBA-16 enhanced the stability of the catalyst as a

prerequisite for applications at high temperature, especially in the

presence of water [76, 77]. SBA-16 as a nanoreactor is superior to

other widely-used channel-like materials (e.g. MCM-41 and SBA-15).

Also, its good pore connectivity and unique structure for the grafting

and passage of large molecules such as organic reactants (various

linkers and ligands) and metal complexes made it a viable candidate

for designing of catalysts [78-80]. Generally, the high surface area in

combination with more active sites provide a highly dispersed system

[81]. Considering all the above reasons and following our recent

interests in development of new nanostructured catalysts [82,83], in

the present study we report the synthesis of Cu^I-anchored onto

(EDX), thermogravimetric analysis (TGA), inductively coupled plasma

atomic emission spectroscopy (ICP-OES), and elemental analysis

(CHNS) analysis.

Characterization of SBA-16/ GPTMS-TSC-Cu^I

Fourier transform infrared (FT-IR) spectroscopy was conducted for

every step of the as-synthesized mesostructured catalyst to verify

the successful functionalization of the SBA-16. Fig. 1 demonstrates

FT-IR spectra of SBA-16 NPs (I) (a), SBA-16/GPTMS NPs (II) (b), SBA-

16/GPTMS-TSC NPs (III) (c), SBA-16/GPTMS-TSC-Cu^INPs (IV) (d) and,

the 7^threused SBA-16/GPTMS-TSC-Cu^INPs (IV) (e). As presented in

Fig. 1a, the typical absorption bands, which are attributed to the

asymmetric, symmetric and bending vibrations of Si–O–Si, were

observed at 1087, 811, and 460 cm^-1, respectively [86]. The broad

absorption band at 3430 cm^-1and a distinctive band at 1630 cm^-1are

assigned to the stretching and bending modes of the surface-

attached hydroxyl groups (Si–OH) and the adsorbed water molecules

[87-89]. The asymmetric stretching vibration of Si-O-Si linkage, which

is overlapped with Si-O-C and Si-C bonds can be identified in the

range of 1200-1100 cm^-1. The absorption band at 965 cm^-1is assigned

to the stretching vibration of the silanol group (Si-OH bond). The

obtained results are in accordance with the previous literature data

[86]. The existence of the epoxy ring grafted to the SBA-16

framework was confirmed by the appearance of two distinctive

bands at 2949 and 2851 cm^-1, which are allocated to the asymmetric

and symmetric methylene C–H stretching vibrational frequencies,

respectively (Fig. 1b) [90, 91].

mesoporous

SBA-16

functionalized

by

aminated

3-

glycidyloxypropyltrimethoxysilane with thiosemicarbazide (SBA-

16/GPTMS-TSC-Cu^I) as a new heterogeneous catalyst via post-

synthetic stepwise manner illustrated in Scheme 1. Firstly, SBA-16 (I)

was synthesized by hydrothermal multi-step preparation method

[76, 84] includes the reaction of tetraethyl orthosilicate (as the silica

source) and a mixture of Pluronic F127 and P123 (as the templates)

under low acidic conditions (37%), and then calcination at 550°C for

10 h (to remove the templates). Thus, the final mesoporous silica

material was obtained. Afterwards, appropriate surface

functionalization of hydroxyl groups (on the surface) of the as-

synthesized SBA-16 (I) was performed by the treatment of I with 3-

glycidyloxypropyltrimethoxysilane (GPTMS) in refluxing toluene

which produced SBA-16/GPTMS (II). In the following step, the

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Scheme 1. Preparation of Cu^I-anchored onto mesoporous SBA-16 functionalized by aminated 3-glycidyloxypropyltrimethoxysilane with thiosemicarbazide (SBA-16/GPTMS-TSC-

Cu^I).

authenticated by the appearance of a new band at 3366 cm^-1

(corresponding to the asymmetric (N-H) vibration of the terminal

NH₂group), and two new bands at 3264 and 3181 cm^-1

(corresponding to the symmetric N-H vibrations of the amino groups)

[93]. The characteristic stretching vibration of O-H (attributed to

ring opening of the epoxy ring) is found in approximately the same

region, which covered by the absorption bands of amino groups in

thiosemicarbazide. The well-synthesized SBA-16/GPTMS-TSC NPs

(III) is further established by the attendance of two distinctive

absorption bands at 1644 and 1620 cm^-1which could be assigned to

N–H (secondary amine) bending vibrations (Fig. 1c). Interestingly, the

ring opening of epoxy with TSC leads to the appearance of two bands

located around 1244 and 802 cm^-1(corresponding to the (C=S)

stretching vibration and υ_s(CS) ) (Fig. 1c) [94-96]. The FT-IR spectrum

of SBA-16/GPTMS-TSC (III) after coordination with Cu^Iions (Fig. 1d)

revealed the coordination between the N and O atoms with Cu^Iions.

The stretching vibrations of OH and NH at 3366-3181 cm^-1shift to

3343-3129 cm^-1. Likewise, the bending vibrations attributed N–H

(secondary amine) at 1644 cm^-1and 1620 cm^-1shift to 1634 cm^-1and

1605 cm^-1, respectively. Decreasing in vibrational frequencies is the

result of interaction between the amine and hydroxyl groups with

Cu ions [97]. The strong metal-sulfur bond formation is also

confirmed by the shift of the υ_s(CS) from 802 cm^-1to 792 cm^-1.

Scheme 2. Synthesis of symmetrical diaryl sulfides from the cascade reaction of aryl

halides with S₈/ thiourea in the presence of SBA-16/ GPTMS-TSC-Cu^Iunder solvent-free

conditions.

Also, the ether linkage in the glycidoxy group is known in the same

region and it overlaps with the strong Si–O–Si absorption band (Fig.

1b) [92]. Successful modification process can be certified by

decreasing in the intensity of the bands at 3421 cm^-1and 1634 cm^-1

regions (corresponding to the O-H stretching and bending vibrations,

respectively), and at around 960 cm^-1(corresponding to Si-O-H

vibration) in the modified SBA-16 against the parent SBA-16 (see

dotted areas in Fig. 1b). The existence of the grafted TSC

(thiosemicarbazide) on the surface of SBA-16/GPTMS NPs (II) can be

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The coordination of the –NH, -OH and S gro u_Vp_ies_{w A}is_rticf_leu_Ort_nh_lie_ner

DOI: 10.1039/C8GC03931C

substantiated by the appearance of the additional bands at 420–302

cm^-1range corresponded to the stretching vibrations of Cu–N and

Cu–S [99-102] and a band at 620 cm^-1assigned to the vibration of Cu-

O [103]. The results show a reasonably good agreement with the

available literature data [104].

Small-angle X-ray diffraction (SAXRD) technique was implemented to

gain further insight into the structural properties of the pristine SBA-

16 (I) and SBA-16/GPTMS-TSC-Cu^I(IV) (Fig. 3).

As can be evident from Fig. 3a, the SAXRD pattern of the pure SBA-

16 exhibits an intense diffraction peak at 2θ = 0.55 ° indexed to the

(1 1 0) plane. Furtheremore two weak peaks at 2θ = 0.91 ° (2 0 0) and

1.2 ° (2 1 1) Bragg reflections are characteristic of the 3D-hexagonal

structure of the mesoporous materials [105, 106].

It is interesting to note that the highly ordered hexagonal structure

of SBA-16 is preserved even after the modification process. The only

observed difference was related to decreasing the peak intensity due

to the presence of the organic / or inorganic segments (ligand-

functionalization and further immobilization of the Cu^Icomplex) in

the pores (Fig. 3b). These results are also confirmed by N₂sorption

detection.

Fig. 1. FT-IR spectra of mesoporous silica SBA-16 (I) (a), mesoporous silica SBA-

16/GPTMS (II) (b), mesoporous silica SBA-16/GPTMS–TSC (III) (c), mesoporous silica

SBA-16/GPTMS -TSC-CuI (IV) (d) and 7^threused SBA-16/GPTMS -TSC-Cu^I(IV) (e).

Predictably, this band (809-730 cm^-1) is particularly diagnostic for

transition metal complexes of thiosemicarbazide and

thiosemicarbazones; hence, upon the coordination with metal, the

characteristic band at almost 100 cm^-1has shifted to the lower

frequencies (regarding the coordination of the copper ion to the S

atom) [98]. The results were also filtered with FIR and XPS analyses.

The above results implied the strong interaction of the organic

moieties with Cu^Icomplex.

Furthermore, far-IR spectrum was performed to achieve a better

comprehension of the Cu^Ispecies immobilization on the active sites

inserted onto mesostructured SBA-16 (Fig. 2). The far-IR confirms a

detailed description of the IR-active low-frequency modes

(frequency region below 700 cm^-1), and it can provide information on

metal-ligand vibrations.

Fig. 3. Small angle XRD patterns of SBA-16 (I) (a), SBA-16/GPTMS-TSC-Cu^I(IV) (b) and 7^th

reused SBA-16/GPTMS-TSC-Cu^I(IV) (c).

The X-ray diffraction patterns (XRD) of the pure SBA-16 and SBA-

16/GPTMS-TSC-Cu^Ishow a similar pattern (Fig. 4a and 4b). Fig . 4a

indicated the strong and broad diffraction peak at 2θ = 15°-35° can

be assigned to the amorphous structure of the SBA-16 [107]. In the

wide-angle XRD pattern (Fig. 4b), the diffraction peaks corresponding

to copper have not been observed for SBA-16/GPTMS-TSC-Cu^I(with

1.18 wt.% Cu loadings) in agreement with the high copper dispersion.

The absence of Cu diffraction peaks indicates the formation of finely

dispersed copper species on the mesostructured that are not

detectable by this technique (as copper loading is lower than 5 wt.%)

[108-110].Therefore, XRD results are in agreement with high copper

dispersion

To achieve a better insight to the oxidation state of the Cu ions and,

also evaluation the mechanism by which Cu^Icould coordinate with

the active units inserted onto functionalized mesostructured SBA-16,

we decided to carry out an X-ray photoelectron spectroscopy (XPS)

Fig. 2. Far-IR spectrum of SBA-16/GPTMS-TSC-Cu^I(IV).

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by the chemical environment of that atom (e.g.,_Via_ewlte_Arr_ta_ict_leio_On_nlinin_e

oxidation state or functional group). Thes^De^Oa^I:lt¹e⁰r^.a¹⁰ti³o⁹n^/Cs ⁸i^Gn^Cb⁰i³n⁹d³i¹n^Cg

energy are known as “chemical shifts” [111].

Detailed scrutiny in the XPS spectra allows more precise

identification to the copper species nature and the existence of

elements in the mesostructured catalyst.

The full-scan XPS spectra of fresh SBA-16/GPTMS-TSC-Cu^Iand 7^th

reused mesostructured catalyst were recorded as the results

illustrated in Fig. 5a and 5b. Clearly the peaks corresponding to

carbon, nitrogen, oxygen, sulfur, and copper have been detected in

the XPS elemental survey scan of the fresh mesostructured catalyst

at 287.08 eV (C 1s), 404.8 eV (N 1s), 536.08 eV (O 1s), 170.08 eV (S

2p), and 935.08 eV (Cu 2p), respectively (Fig. 5a).

The high-resolution XPS spectrum of C 1s revealed in Fig. 5c confirms

the presence of N-C=S, C-O-Cu/C-N-Cu and C-OH at binding energies

of 290.1, 288.8 and, 286.5 eV respectively. The high-resolution XPS

spectrum of N 1s in Fig. 5d, also display two peaks with binding

Fig. 4. Wide angle X-ray diffraction patterns of SBA-16 (I) (a) and SBA-16/GPTMA-TSC-

Cu^I(IV) (b).

analysis of SBA-16/GPTMS-TSC-Cu^I(Fig.5).

In fact, X-ray energy 401.06 and, 400.06 eV corresponding to N-Cu and N-C

photoelectron spectroscopy is one of the powerful surface analysis respectively. That is in agreement with the reported values for N

technique to identify the oxidation states of elements in various atoms in TSC by sharing the lone pair of electrons for the formation

compounds. The exact binding energy of core electrons is inﬂuenced of a covalent bond between N atoms and Cu^Iions. [112-114].

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Fig. 5. XPS elemental survey of the fresh mesoporous silica SBA-16/GPTMS -TSC-Cu^I(IV) (a) and 7^threused SBA-16/GPTMS -TSC-Cu^I(IV) (b), high resolution XPS spectra C 1s (c), N 1s

(d), O 1s (e), S 2p (f) Cu 2p (fresh SBA-16/GPTMS -TSC-Cu^I(IV)) (g) and Cu 2p (7^threused SBA-16/GPTMS -TSC-Cu^I(IV)) (h).

Similarly, the high-resolution XPS spectrum of O 1s in Fig. 5e shows a Table 1. Specific surface area (SBET), pore volume and mean pore diameter of SBA-16 (I)

peak with binding energy 533.6 eV may have resulted from the C-O (a) and SBA-16/GPTMS-TSC-Cu^I(IV) (b).

bond related to the hydroxyl group [115]. This result confirms that

the hydroxyl group in GPTMS has involved in Cu^Iadsorption, in which

Samples

BET Surface Area

(m²g^-1)

Total Pore Volume

(cm³g^-1)

Mean Pore

Diameter (nm)

oxygen atom donates a lone pair of electrons to the metal ions and

the resulting electron density decreases around the O atom [116].

Another close-up survey in the S 2p region (Fig. 5f) shows the

presence of two peaks at 164.68 and 163.3 eV, which are attributed

to the S 2p1/2 and S 2p3/2 states, respectively. It is also in good

agreement with the formation of Cu-S and slightly shifts to lower

values [117-118].

SBA-16 (I)

635.03

247.65

0.596

3.7544

3.5386

SBA-16/GPTMS-TSC-Cu^I

0.2191

(IV)

Decreasing the binding energy confirms the accumulation of

negative charge or the increasing the polarity on the surface of sulfur

to attract the positively charged copper ions [119]. All these peak

positions have been well matched with reported values in the

literature (after coordination of the Cu^Ionto the SBA-16/GPTMS-TSC,

there is a resulting shift for the peaks toward the lower binding

energy) [120]. The copper high-resolution XPS spectrum shows (Fig.

5g) the peaks at 952.5 and 932.5 eV ascribed to the binding energy

of Cu 2p1/2 and Cu 2p3/2, respectively, indicative of Cu^Iwith a peak

separation of 20 eV. It is noteworthy that both the peaks exhibit high

symmetry, which implies the attendance of Cu^Iin the formation of

Cu-S [113,117].

From the Cu spectrum, the absence of the peaks ascribed to metallic

Cu and the appearance of new peaks at 932.5 and 952.5 eV provide

further evidence that there is no metallic Cu as impurity and Cu

atoms are coordinated by organic ligands to form SBA-16/GPTMS-

TSC-Cu^I. As stated in the literature, metallic Cu exhibits two peaks at

953 and 933 eV, which can be assigned to the binding energy of Cu

2p1/2 and Cu 2p3/2, respectively, assigned to Cu^I[121].

FT-IR, far-IR and XPS analyses confirm the successful covalent

immobilization of Cu^Ionto the modified mesostructured SBA-16.

The nitrogen adsorption–desorption isotherms and the

corresponding BJH pore-size distribution curves of the pure SBA-16

(I) and SBA-16/GPTMS-TSC-Cu^I(IV) are shown in Fig. 6. According to

the IUPAC classification, the appearance of the H2-type hysteresis

loops at a relative pressure can be identified as type IV isotherms,

which is associated with the presence of the mesoporous cage-like

structure [122]. The nitrogen adsorption–desorption isotherm of

SBA-16 (I) contains asymmetrical and triangular branches, which are

Adsorption / desorption isotherm

180

120

60

450

300

150

0

I

(a) SBA-16 (I)

(b) SBA-16/GPTMS-TSC-Cu (IV)

0

0.0

0.5

p/p⁰

1.0

0.5

p/p⁰

1.0

ADS

DES

ADS

DES

BJH-Plot

0.09

0.06

0.03

0.00

(c) SBA-16

(d) SBA-16/GPTMS-TSC-Cu^I(IV)

0.2

0.1

0.0

1

10

100

1

10

100

r

/nm

p

r /nm

p

ADS

Fig. 6. Nitrogen adsorption–desorption isotherms (a and c) and pore size distribution

isotherms (b and d) of SBA-16 (I) and SBA-16/GPTMS-TSC-Cu^I(IV).

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characteristic of mesoporous materials with ink-bottle pores and

pore network connectivity. The respective average surface areas,

pore volumes and mean pore diameters of both pure SBA-16 (I) and

SBA-16/GPTMS-TSC-Cu^I(IV) are illustrated in Table 1. The BET

surface area, pore volume and pore diameter of the intact SBA-16 (I)

are 635.03, 0.596, and 3.7544, respectively, which were diminished

after the modification process. These results clearly verify the

successful functionalization of the mesoporous SBA-16 (I). In

addition, the BJH calculations demonstrated a uniform pore-size

distribution with a high-intensity peak, which proves the high

regularity of the mesostructure (Fig. 6 b and d).

View Article Online

DOI: 10.1039/C8GC03931C

Fig. 8. Particle size distribution histogram of the pure SBA-16 (I) (a), fresh SAB-

16/GPTMS-TSC-Cu^I(IV) (b).

The particle size and morphology of the mesoporous SBA-16 (I), SBA-

16/GPTMS-TSC-Cu^I(IV) and the 7^threused SBA-16/GPTMS-TSC-Cu^I

(IV) are defined by the transmission electron microscopy (TEM)

technique (Fig. 7). The images of SBA-16 (I) indicate a well-ordered

cubic mesoporous structure with the Im3m space group (Fig.7 a and

b) [123]. The particle size of SBA-16 (I) in regular geometric shape

was estimated to be 3–7 nm. As clearly seen in Fig.7 c, the ordered

hexagonal arrangement of uniform channels with a supreme

regularity of mesostructured catalyst were well conserved upon the

coordination process.

good agreement with the data obtained from TEM and SAXRD

analysis. To survey the types of present elements in the structure of

SBA-16/GPTMS-TSC-Cu^I(IV), the energy-dispersive X-ray (EDX)

spectrum was recorded and established in Fig. 10.

As can be seen, the presence of C, O, Si, N, S, Cu and Cl in the SBA-

16/GPTMS-TSC-Cu^I(IV) composition is confirmed by the EDX

spectrum (Fig. 10).

(b)

(a)

(c)

(d)

Fig. 9. FE-SEM images of SBA-16 (I) (a and b) and SBA-16/GPTMS-TSC-Cu^I(IV) (c and d).

Fig. 7. TEM images of the pure SBA-16 (I) (a and b), fresh SAB-16/GPTMS-TSC-Cu^I(IV) (b)

and 7^threcovered SAB-16/GPTMS-TSC-Cu^I(IV) (d).

Furthermore, distribution histograms of SBA-16 (I) and SBA-

16/GPTMS-TSC-Cu^I(IV)) reveal that the average

diameter of nanoparticles is 3-7 nm (Fig. 8). The attained TEM results

were in a very good agreement with the data obtained from the

small-angle XRD.

The field emission scanning electron microscopy (FE-SEM) technique

was exerted for further investigation on the size and morphology of

pure SBA-16 (I) and SBA-16/GPTMS-TSC-Cu^I(IV) (Fig. 9). As can be

concluded from Fig. 6, the as-synthesized mesostructured catalyst

exhibited a good dispersity with spherical morphology, which is in

Fig. 10. EDX spectrum of SBA-16/GPTMS-TSC-Cu^I(IV).

To further evaluate the composition of SBA-16/GPTMS-TSC-Cu^I(IV)

the EDX-mapping analysis was performed and the results are given

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in Fig.11. The attendance of C, O, Si, N, S, Cu and Cl was observed

with a uniform distribution.

View Article Online

SBA-16 (a)

SBA-16/GPTMS (b)

DOI: 10.1039/C8GC03931C

SBA-16/GPTMS-TSC-Cu^I(c)

100

80

7^threused SBA-16/GPTMS-TSC-Cu^I(d)

(a)

(b)

(d)

(c)

60

40

0

200

400

600

800

Temperature ( ^oC )

Fig. 12. TGA thermograms of SBA- (I) (a), SBA-16/GPTMS (II) (b), SBA-16/GPTMS-TSC-Cu^I

(IV) (c) and 7^threused SBA-16/GPTMS-TSC-Cu^I(IV) (d).

Fig. 11. EDX-mapping analysis of SBA-16/GPTMS-TSC-Cu^I(IV).

Table 2. Thermogravimetric analysis (TGA) and elemental analysis (EA) results.

Quantitative determination of the thermal stability and the amount

of organic moieties on the surface of the calcinated SBA-16 was

assessed by thermoavimetric analysis (TGA) at a heating rate of 10 °C

min^-1under nitrogen atmosphere in the temperature range of 25–

800 °C. The TGA thermograms of pure SBA-16 (I) (a), SBA-16/GPTMS

(II) (b), SBA-16/GPTMS-TSC-Cu^I(IV) (c) and the 7^threused SBA-

16/GPTMS-TSC-Cu^I(IV) (d) are presented by Fig. 12. As can be seen

in Fig. 12a, TGA of SBA-16 demonstrates one weight loss (11.02 %)

from 25 to 150 °C, which can be assigned to the thermodesorption

of physically adsorbed water existing on the surface and in the

channels of the mesoporous silica materials. Above this temperature

and up to 800 °C, no significant weight loss could be identified [124].

The good cross-coupling of the organic spacer groups (GPTMS) on the

surface of SBA-16 NPs was confirmed by depicted two-steps thermal

decomposition (Fig. 12b). The initial step of weight loss (2.94 %)

occurred from 25 to 150 °C, which can be attributed to the extrusion

of physically absorbed water from the pore interface. The second

weight loss (21.31%, 1.86 mmol/g) from 160 to 450 °C indicated the

total decomposition of the grafted epoxy group as reported by

Hosgör et al [125]. This result indicated that GTPMS had been

successfully grafted onto the surface of the SBA-16 (I). The well-

modified surface of SBA-16/GPTMS (II) with the TSC was

corroborated by the advent of four steps thermal degradation, as it

is evident in Fig. 12c. The first negligible weight loss (2.39%) from 25

to 150 °C was related to the removal of adsorbed water molecules.

The part of ligand TSC (–NH-CS-) (4.69%) was decomposed between

temperature range 190-265 °C. The third weight loss (15.48%) from

180 to 350°C confirmed the presence of GPTMS grafted onto the

surface of the SBA. The last weight loss (15.15%, 1.7 mmol/g) from

350 to 650 °C was caused by the decomposition of the rest part of

the TSC coating the surface of the SBA-16/GPTMS (Fig.12c) [128,

129]. Good agreement was observed between the elemental analysis

(CHNS) and TGA data, according to the results summarized in Table

2. These results clearly corroborated that organic functional groups

were successfully embedded on the surface of the pure SBA-16 (I).

Additionally, the exact loading amount of Cu on the modified

Samples

Weight loss

(w/w %)

Weight loss

(w/w %)

Organic

grafted

C

N

S

(%)

(w/w %)

(%)

150-600 °C

segments

150-600 °C

(mmol g^-1

)

SBA-16

11.02 ^a

-

SBA-

2.94 ^a

21.31

1.85

13.64

-

16/GPTM

SBA-

2.39 ^a

15.5 ^b

1.70

15.87

7.36

5.21

SBA-

16/GPTM-

TSC-Cu^I

a

b

Attributed to the removal of physically absorbed water from the pore interface.

Attributed to decomposition of TSC coating the surface of the SBA-16/GPTMS.

mesoporous SBA-16 (I) was determined to be 1.18 wt.% (1.86

mmol/g) based on the inductively coupled plasma (ICP) analysis.

The TGA curve and ICP analysis also proved the successful supporting

of the Cu and organic ligands onto the catalyst surface.

Likewise, the data obtained from XPS results determine the copper

loading in the functionalized mesostructured catalyst (1.95 wt.%).

The result is in good agreement with results obtained from ICP-OES

and EDX ( Fig. 10) analyses.

Catalytic studies

Here, to evaluate the efficiency of the SBA-16/GPTMS-TSC-Cu^I(IV)

NPs, the catalytic activity of this mesostructured catalyst was

investigated in the symmetrical S-arylation reaction (Scheme 2). At

the outset of the study, the reaction of iodobenzene (1 mmol) with

S₈/ or thiourea (0.5 mmol) were chosen as the model reaction (Table

2).

The optimal reaction conditions were investigated in terms of the

solvent, base, temperature and catalyst loading. For the first trial,

conducting the reaction with no addition of catalyst and / or base, in

DMSO at 120 °C does not lead to formation of diphenyl sulfide even

after long period of time (Table 3, entries 1-3) whereas the target

compound was obtained using SBA-16/GPTMS-TSC-Cu^I(IV) and KOH

8 | J. Name., 2012, 00, 1-3

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(Table 3, entry 4). To access the best optimal catalytic conditions, the to be the optimal reaction temperature (Table 3, entries 20-22). The

View Article Online

DOI: 10.1039/C8GC03931C

effect of various solvents on the model reaction was investigated in reaction also showed a strong dependence on the catalyst loading

depth. In surveying common solvents (DMF, DMSO, PEG, THF, (Table 3, entries 23-26). It is evident that the best result in the

toluene, 1,4-dioxane, H₂O), it was found that only poor yields were synthesis of symmetrical diaryl sulfides were achieved by carrying

obtained in solvents such as THF, toluene, PEG, 1,4-dioxane and H₂O out the reaction by applying KOH (4 mmol) and 1.3 mol% (1.86

while the yield and reaction rate was enhanced by applying DMSO in mmol/g) of mesostructured catalyst at 110 °C (Table 3, entry 25). The

this transformation (Table 3, entries 5-10). Afterwards, reaction was model reaction was further tested in the presence of SBA-16 (I), SBA-

scrutinized under neat conditions. Interestingly, it was found that 16/GPTMS (II), SBA-16/GPTMS-TSC (III) and CuCl aiming to elucidate

solvent free condition was the most suitable media for C-S coupling the effective catalytic activity of SBA-16/GPTMS-TSC-Cu^I(Table 3,

reaction in the presence of SBA-16/ GPTMS-TSC-Cu^I(IV) (Table 3, entries 27-30). It was found that comparatively the highest yield of

entry 11). Control experiments for the base and base loading diphenyl sulfide was obtained in the presence of SBA-16/GPTMS-

examination listed in entries 12-19 indicated that KOH as base was TSC-Cu^I(IV) in a short reaction time.

crucial for the reaction, and the base loading should be set as 4

mmol. Subsequently, upon temperature examination, 110 °C proved

Table 3. Synthesis of diphenyl sulfide from the reaction of iodobenzene with S₈/ or thiourea catalyzed by SBA-16/GPTMS-TSC-

Cu^Iunder different reaction conditions.

Entry

1

Catalyst

(mol %)

Solvent

DMSO

Base

(mmol)

Temperature

(°C)

Time (h)

S₈/ thiourea

Isolated Yield (%)

S₈/ thiourea

-/-

-

120

24/ 24

-/-

2

3

-

DMSO

KOH (4.0)

-

20

120

24 / 24

20 (min) / 1

1 / 3

1.3

DMSO

4

DMSO

KOH (4.0)

NaOH (4.0)

CaO (4.0)

K₂CO₃(4.0)

120

98 / 95

86 / 80

57 / 45

15 / 10

25 / 10

Trace / Trace

-/-

5

DMF

120

6

PEG

120

2.5 / 6

10 / 16

8 / 12

7

Toluene

Reflux

120

8

H₂O

9

1,4-Dioxane

24 / 24

20 (min) / 1

1 / 4

10

11

12

13

14

THF

-

98 / 95

85 / 78

95 / 90

35 / 30

120

1 / 2

120

3 / 9

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15

16

1.3

-

Na₂CO₃(4.0)

NaOEt (4.0)

K₃PO₄(4.0)

KOH (3.5)

KOH (3.0)

KOH (4.0)

120

130

110

100

110

3 / 9

30 (min) / 1.5

2 / 7

25 / 35

DOI: 10.1039/C8GC03931C

97 / 94

View Article Online

17

1.3

58 / 50

75 / 68

64 / 58

98 / 95

80 / 74

82 / 70

90/85

18

1.3

20(min) / 1

20 (min) / 1

1 / 4

19

1.3

20

1.3

21

1.3

22

1.3

23

0.65

0.78

1.3

24

40 (min) / 2.5

20 (min) / 1

10 / 18

25

-

98 / 95

22 /17

35 / 24

26

1.95

0.01 (g)

1.3

27 ^a

28 ^b

29 ^c

30 ^d

10 / 18

20 / 28

b

Reaction conditions: iodobenzene (1 mmol), S₈/ thiourea (0.5 mmol). ^aReaction was performed in the presence of SBA-16 (I) as catalyst. Reaction

c

d

was performed in the presence of SBA-16/GPTMS (II) as catalyst. Reaction was performed in the presence of SBA-16/GPTMS-TSC (III) as catalyst.

Reaction was performed in the presence of CuCl as catalyst.

To further develop the scope of C-S coupling reaction, motivated by iodides elevated the S-arylation reaction significantly faster than the

the accurate initial studies on the optimized conditions and having aryl bromides and aryl chlorides (Table 4, entry 1 vs. entries 6 and 9).

the obtained results, the substrate scope of the S-arylation reaction Using this catalytic system, 2‐bromothiophene as a heteroaryl halide

was extended on a variety of structurally divergent aryl halides. It was efficiently reacted and afforded the corresponding product in

consisted of electron-poor, electron-rich and heterocyclic aryl excellent yield (Table 4, entry 13). Another important aspect of this

halides with S₈/ or thiourea as sulfur transfer reagent to generate method is the successful reaction of 2-bromonaphthalene as a model

the symmetrical diaryl sulfides. As it could be seen from the of sterically hindered aryl halide to give the corresponding sulfide in

summarized data in Table 4, when aryl halides containing electron- high yield under the same reaction conditions (Table 4, entry 14).

donating substituents (such as methyl, methoxy, amino and hydroxyl Table 4 obviously demonstrates that SBA-16/GPTMS-TSC-Cu^I(IV) is

groups) were used, the slightly longer reaction times were required not only a highly efficient mesostructured catalyst to catalyze the

to obtain the respective diaryl sulfides (Table 4, entries 2-3, 7 and 11- present reaction but also is so notable to accelerate the C-S cross-

12). The lower reactivity of the electron-rich aryl halides in this coupling reactions of aryl bromides and unreactive aryl chlorides

system is probably associated with the difficulty of insertion of containing electron withdrawing and electron electron-donating

copper into carbon–halide bond compared to electron‐deficient groups. Formation of diaryl disulfide as by-product is one of the

ones [128]. It is important to note that the unprotected amino group major limiting factors in this reaction that can be due to the facile

in aryl halides were not hindered the reaction and no N‐arylating oxidation of thiols. Here, the NMR data confirmed that diaryl sulfide

products were detected in these cases (Table 4, entries 7 and 11).

was the only reaction product, and diaryl disulfide was not formed in

any of the cases. According to the established data in Table 4, the

symmetrical diaryl sulfides were obtained in good to excellent yields

in the presence of S₈as a nontoxic sulfur source, while thiourea

produced the corresponding products in the same yields after longer

reaction times comparatively.

Comparatively, electron-withdrawing substituents (such as nitro and

cyano) reacted more quickly than those with electron-rich aromatic

rings and the corresponding diaryl sulfides generated in excellent

yields (Table 6, entries 4-5, 8 and 10). As illustrated in Table 4, due to

the lower C-I bond strength against C-Br and C-Cl bonds, the aryl

10 | J. Name., 2012, 00, 1-3

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DOI: 10.1039/C8GC03931C

Table 4. Synthesis of diaryl sulfides from the coupling reaction of aryl halides with S₈/ or thiourea catalyzed by SBA-16/GPTMS-TSC-Cu^I.

Entry

Aryl halide

Product

Time (h)

Isolated Yield (%)

S₈/ thiourea

1

20 (min) / 1.00

98 / 95

82 / 70

85 / 74

91 / 84

89 / 84

90 / 84

86 / 82

89 / 85

75 / 70

1S

2S

3S

4S

5S

1S

6S

4S

1S

2

3

4

5

6

7

8

9

1.30 / 2.45

1.00 / 2.15

30 (min) / 1.45

20 (min) / 1.00

50 (min) / 2.30

3.00 / 3.30

1.30 / 2.20

2.00 / 3.30

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10

`11

12

2.15 / 3.45

77 / 73

71 / 68

68 / 59

85 / 74

DOI: 10.1039/C8GC03931C

4S

6S

6.30 / 8.00

7.30 / 8.45

3.30 / 4.15

7S

8S

13

14

7.00 / 8.30

72 / 75

9S

In the present study, the progress of S-arylation reaction was Molecular ion peaks of some selected products exhibited their

monitored by the disappearance of starting materials and further respective m/z, according to the mass spectrometric data. In

formation of the desired cross-coupled products on TLC. All of the addition, the structures of all of prepared products were well

1

synthesized compounds were known and isolated as oil or solid corroborated by surveying their high-field H NMR and ¹³C NMR

products. The obtained products were characterized by comparison spectral data. (Supporting Information)

of their melting points with those reported in the literature.

Scheme 3. Recommended mechanism pathway for the preparation of diaryl sulfide derivatives using aryl halides and S₈catalyzed by SBA-16/GPTMS-TSC-Cu^I.

12 | J. Name., 2012, 00, 1-3

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The proposed reaction pathway of C–S coupling reaction with S₈as a mechanism to C‐S coupling of aryl halides with thiourea was offered

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sulfur source based on the literature reports is outlined in Scheme 3 in Scheme 4. Initially, insertion of Cu^Ispecies^Din^Ot^Io^{: 1}t⁰h^.e¹⁰a³r⁹y^/l^Ch⁸a^Gli^Cd⁰e³b⁹o³n^1Cd

[129, 130]. Initially, it is hypothesized that metal disulﬁde I (K₂S₂) was (I) as an oxidative addition reaction produced intermediate II. The

produced upon the reaction of sulfur powder with KOH. Then the first step was considered as the most important step in determining

stable copper disulﬁde (intermediate II) [131] was produced from the the reaction rate according the results of Table 4. In the following

anion exchange reaction between SBA-16/GPTMS-TSC-Cu^Iand I. step, intermediate II (contains Cu^IIIspecies) reacted with thiourea to

Afterwards, oxidative-addition reaction of aryl halide to II afforded give intermediate III. Subsequently, reductive elimination of

III, which was followed instantly by aryl migration to generate intermediate III smoothly occurred to produce intermediate IV

intermediate IV. At that time, transformation of intermediate IV into alongside the re-generation of Cu^Icatalyst. Then, the obtained thiol

V and consequent oxidative-addition reaction with another aryl moiety (V) in alkaline media reacted with another molecule of

halide molecule provided the key intermediate VI. Eventually, intermediate II to give intermediate VI. Finally, the intermediate VI

reductive elimination reaction led to formation of the desired diaryl upon the reductive elimination process produced the desired diaryl

sulfide (VII) and re-generation of active catalytic species Cu^Ifor the thioether (VII) and the active catalytic species Cu^Ias well which re-

next run. There is no doubt that a more detailed study is required to enters the next catalytic cycle. Further investigations to elucidate the

completely understand the mechanism of the S-arylation reaction in details of the mechanism of S-arylation reaction are ongoing

(Scheme 4).

the presence of copper species (Scheme 3).

By the analogy of the previously reported mechanism in the

literature [129] and according to our investigations, a conceivable

Scheme 4. Recommended mechanism pathway for the preparation of diaryl sulfide derivatives using aryl halides and thiourea catalyzed by SBA-16/GPTMS-TSC-Cu^I.

From a green chemistry viewpoint, the reusability and long durability was monitored by TLC, the mesostructured catalyst was separated

of the metal catalyst are very significant factors, particularly for by the simple filtration, washed in turn with distilled water (to get rid

commercial and industrial applications. In this regard, to check the of the excess (KOH) base, and highly soluble thiourea), then ethanol

reusability behavior of Cu^Igrafted onto mesoporous SBA-16 (to remove trace amount of organic reactant molecules and S₈), and

functionalized by GPTMS-TSC, successive one-pot C–S coupling dried under vacuum at 60 °C overnight to remove residual solvents

reaction of iodobenzene with S₈/or thiourea was carried out under for the next run use.

the optimized reaction conditions. At the end of each reaction which

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The recycling efficiency has been plotted in Figs. 13 and 14. As motifs. More importantly, the small-angle XRD pa_Vtt_iee_wrn_Artio_clf_{e O}S_nB_liA_ne-

illustrated in these figures, it is noticed that the aforementioned 16/GPTMS-TSC-Cu^I(IV) after seven runs s^Dh^Oow^I:e¹⁰d^.10n³o^9/c^Co⁸n^Gs^Cid⁰e³r⁹a³b¹l^Ce

catalytic system is extremely reusable under the investigated broadening of peaks when compared with the small-angle XRD

reaction conditions since almost no significant deactivation of the pattern of the fresh catalyst (Fig. 3c). Moreover, in the XPS elemental

mesoporous catalyst occurred after several recovery processes (Figs. survey scan of the 7^threused SBA-16/GPTMS-TSC-Cu^I(IV) purely

13 and 14). However, the lower observed efficiency of the authenticated that the peaks corresponding to carbon, nitrogen,

regenerated mesoporous catalyst after seven cycles might be oxygen, sulfur, and copper conserved (Fig. 5b). In addition, the

principally due to the partial saturation of mesochannels containing oxidation state of Cu^Ispecies preserved even after seven recycle in

catalytic active sites during the reaction process. The almost similar the S-arylation reaction (Fig. 5h).

Interestingly, the TEM image of the 7^threcovered SBA-16/GPTMS-

TSC-Cu^I(IV) was inquired and the results showed that the well-

ordered arrangements cage-like structure of the 7^threcovered

mesoporous catalyst has remained some extent and no increase in

the particle size was observed (according to the data illustrated in

Fig. 7 d).

Furthermore, the TGA thermogram of the pristine and the 7^threused

SBA-16/GPTMS-TSC-Cu^I(IV) illustrated that no significant difference

was observed in the decomposition patterns, as it is obvious from

Fig. 12d. The only observed difference was related to decreasing the

Fig. 13. Synthesis of diphenyl sulfide of aryl halide with S₈in the presence of the reused

SBA-16/GPTMS-TSC-Cu^I(IV).

percentage weight loss from 40.8% in the fresh mesostructured

catalyst to 39.1% after seven cycles in the S-arylation reaction.

Accordingly, the amount of organic segments decreased from 1.85

to 1.7 mmol g^-1, which might be ascribed to the negligible losing of

the organic linkers anchored onto the support surface (due to

trapping of the organic segments within the cage‐like pores of

mesostructured SBA-16) during the reusing process. The results

demonstrated that the mesostructured catalyst is thermally stable

up to 800 ˚C and organic segments existed in the structure of the 7^th

recovered catalyst. Furthermore, the ICP-OES technique was

exploited to the assessing the exact amount of Cu^Iin the pristine and

the 7^threused SBA- 16/GPTMS-TSC-Cu^I(IV). According to the

Fig. 14. Synthesis of diphenyl sulfide of aryl halide with thiourea in the presence of the

reused SBA-16/GPTMS-TSC-Cu^I(IV).

obtained data, 1.3 and 1.23 mmol of copper were anchored onto

1.000 g of the pristine and the 7^threused mesostructured catalyst,

respectively. These results clearly proved that the negligible amount

of copper was leached from the surface of the mesoporous

structured catalyst during the recycling processes. The obtained data

from FT-IR, FIR, SAXRD, XRD, XPS, TEM, TGA, and ICP-OES analysis,

strongly confirmed the admirable structural and mechanical stability

of the reused catalyst after seven reusing cycles.

results in each cycle clearly infer that SBA-16/GPTMS-TSC-Cu^I(IV) is

not only active enough for S-arylation reaction but also is so stable

even after several recycle runs.

To clarify the structural stability of the SBA-16/GPTMS-TSC-Cu^I(IV) as

an important issue, after seven cycles in the reaction of aryl halides

with thiourea, any structural changes of the mesostructured catalyst

were investigated by FT-IR, XRD, TEM, TGA, and ICP-OES techniques.

As expected, in the FT-IR spectrum of 7^threused mesostructured

catalyst, all of the characteristic absorption bands are well preserved

in terms of the shapes, positions, intensities, and frequencies even

after seven recycle runs (Fig. 1e).

Heterogeneity Studies

To investigate the homogeneity or heterogeneity nature of the

mesoporous catalyst in the one-pot synthesis of symmetrical diaryl

sulfides under optimized conditions, hot filtration test was done and

discussed.

Additionally, in the small-angle XRD patterns of SBA-16 (I), fresh SBA-

16/ GPTMS-TSC-Cu^I(IV) and 7^threcovered mesostructured catalyst,

the presence of three well-resolved peaks below 2°, indexed as (1 1

0), (2 0 0) and (2 1 1) reflections, clearly confirmed the 3D-hexagonal

symmetry of these materials (Fig. 3). However, an overall

attenuation in the intensity of these three peaks (especially the

intensity of the (1 1 0) reflection) was noticed after the modification

process (Fig. 3b). This might be caused by the effect of pore-filling of

functional groups that can reduce the scattering contrast between

the framework of the SBA-16 support and the filled pores with the

organic moieties, which would be accompanied by the fractional loss

of the ordered silica structure due to the incorporation of organic

Hot filtration test

The hot filtration test as a strong test was conducted to evaluate the

heterogeneity nature of the catalytic species in the S-arylation

reaction under the optimal conditions through the possibility of

copper leaching into the reaction mixture. For this purpose, the

reaction of iodobenzene and thiourea was selected as a model

reaction and evaluated under the optimal conditions. Precisely, at

the halfway of the reaction (10 minutes), the mesostructured

catalyst was separated from the reaction mixture by filtration. In this

step, only 55% conversion was achieved. Subsequently, the rest

mixture was permitted to continue without a catalyst for another 10

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minutes under similar conditions. The reaction progress before and

after the separation was monitored by TLC. Assessment of the rate

of the desired product preparation indicates that no remarkable

increase in the conversion was observed even after an extended

time. This result clearly demonstrated that no leaching of active

species occurred from the surface of SBA-16/GPTMS-TSC-Cu^I(IV)

entire course of the reaction (less than 0.07 mol% according to the

ICP-OES analysis). The results established the strong coordination of

copper nanoparticles to SBA-16/GPTMS-TSC (IV) surface (Fig. 15). It

is worth mentioning that although a positive hot-filtration test

highlights the homogeneity of the catalyst, a negative test does not

pertain to the heterogeneous nature of the catalyst due to the reality

that in many circumstances, leached and soluble metal species can

be redeposited back on the insoluble support, during the hot

filtration stage. In this context, the catalytic pathway would proceed

through a “release-capture” mechanism [132]. By the way, we have

speculated that the respective mesostructured catalyst most likely

operated in a heterogeneous manner.

View Article Online

DOI: 10.1039/C8GC03931C

100

80

60

40

20

0

Fresh cycle

Hot filtration test

0

2

4

6

8

10

12

14

16

18

20

22

Time (min)

Fig. 15. Time-dependent correlation of the product yield in hot filtration test.

In this line of work, to illustrate the suitability of the present protocol

to other reported methods in the literature, the catalytic activity of desired product (Table 5, entries 1-8) and recovery and reusability

SBA-16/GPTMS-TSC-Cu^I(IV) was compared with some of the (Table 5, entry 1) as well as price and toxicity are the disadvantages

previously reported catalysts in the S-arylation of aryl-halides with S₈of some of these methods. Moreover, the newly synthesized

/ or thiourea (Table 5). Although all of the listed catalysts can mesostructured catalyst with the great catalytic efficiency is found to

produce the desired product in good to excellent yield, it is clearly be easily recovered from the reaction mixture using simple filtration.

seen that SBA-16/GPTMS-TSC-Cu^I(IV) as a heterogeneous and green These results well indicated the superiority of the current approach

mesostructured catalyst is more efficient than most of the well- to the previously reported methods. In this regard, SBA-16/GPTMS-

known supported catalyst systems with respect to the reaction TSC-Cu^I(IV) affords higher yield in short reaction time than the other

conditions. As shown in Table 5, the use of the homogenous catalytic reported catalysts.

systems, tedious product purification procedures (Table5, entry 1),

high temperatures (Table 5, entries 1-2 and 7-10), hazardous

solvents (Table 5, entries 4-11), long reaction times to obtain the

Table 5. Comparison of the catalytic activity of SBA-16/GPTMS-TSC-Cu^I(IV) with some literature precedents

S‑arylation reaction.

Entry

Catalyst

Solvent

Base

Temperature (°C)

Time (h)

Yield (%)

Ref.

1

2

CuI ^a

PEG-200

PEG-400

H₂O

Na₂CO₃

Cs₂CO₃

KOH

120

100

110

100

110

130

120

130

120

110

15

20.5

24

93

97

92

98

80

97

75

95

90

95

90

98

133

134

CuFe₂O₄MNPs ^b

a, c

3

mPANI/pFe₃O₄

135

4

CuO@GO a

Pd₂dba₃/ Triphose ^{a, d}

CuO nano ^a

DMSO

1,4-dioxane

DMSO

DMF.H₂O

DMF

Cs₂CO₃

KOH

12

136

5

18

23

6

15

137

7

Cu(II)-2-MPE@MCM-41^a

12

138

a

8

Magnetic nano CuFe₂O₄

K₂CO₃

KOH

12

139

9

ZrO nanoparticles ^b

GO-N-isatin-Ni (II) ^a

DMSO

-

2

140

10

11

12

NaOEt

KOH

4

141

Cu(II)-Vanillin-MCM-41^b

0.75

20 (min)

142

SBA-16/GPTMS-TSC-Cu^I

KOH

Present study

a

J. Name., 2013, 00, 1-3 | 15

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Page 16 of 22

ARTICLE

Journal Name

b

13

SBA-16/GPTMS-TSC-Cu^I

-

KOH

110

1

95

Present study

View Article Online

DOI: 10.1039/C8GC03931C

^aSynthesis of symmetric diaryl sulfides from reaction of aryl halides with thiourea. ^bSynthesis of symmetric diaryl sulfides from reaction of aryl

c

d

halides with S₈.

mesoporous polyaniline/porous magnetic Fe₃O₄.

Tris(dibenzylideneacetone)dipalladium(0)

/

1,1,1-tris

(diphenylphosphinomethyl)ethane.

Conclusion

with Cu Ka radiation ((λ = 0.154 nm) radiation. X-ray photoelectron

spectroscopy (XPS) was performed using the Thermo Scientifi,

ESCALAB 250 Xi Mg X-ray resource. BET surface area and pore size

distribution were measured on a Belsorp-mini II system at –196 °C

using N₂as the adsorbate. Transmission electron microscopy (TEM)

was performed with EM10C (100 kV) microscope (Zeiss, Germany).

FE-SEM images, EDS and EDS-mapping were recorded using a

TESCAN, Model: Sigma VP scanning electron microscope operating at

an acceleration voltage of 15.00 kV and resolution of about 500 nm

(Zeiss, Germany). Thermogravimetric analysis (TGA) was carried out

using a Shimadzu Thermogravimetric Analyzer (TG-50) in the

temperature range of 25–800 °C at a heating rate of 10 °C min^-1,

under N₂atmosphere. Inductively coupled plasma optical emission

spectroscopy (ICP-OES) wascarried out on a 76004555 SPECTRO

ARCOS ICP-OES analyzer. Mesoporous silica (SBA-16) was prepared

by the method reported in the literature [84].

In the present study, SBA-16/GPTMS-TSC-Cu^I(IV) NPs was

synthesized as a novel, efficient, and heterogeneous mesostructured

catalyst. The characterization results from various spectroscopic and

microscopic techniques such as FT-IR, FIR, SAXRD, XRD, XPS, BET,

TEM, FE-SEM, EDX, EDX-mapping, TGA, ICP-OES, and CHN analysis

showed SBA-16/GPTMS-TSC-Cu^I(IV) (with a mean size range of 3-7

nm) is ordered cubic mesostructured with the Im3m space group.

The catalytic efficiency of SBA-16/GPTMS-TSC-Cu^I(IV) as a new

mesostructured catalyst was investigated in the reaction of a wide

range of the aryl halides with S₈/ or thiourea as a sulfur source under

solvent-free conditions (by reducing reaction time and temperature

to avoid using DMSO or DMF as the expensive and toxic solvent) to

produce symmetrical diaryl sulfides. Interestingly, the unique stable

mesostructured catalyst (SBA -16/GPTMS-TSC-Cu^I(IV)) could be

easily separated by simple filtration from the reaction mixture and

reused for at least seven times with trace copper leaching and All the yields refer to isolated products after purification by thin layer

chromatography or recrystallization from ethanol.

without a significant reduction in the yields of the desired products

as well. Due to the inimitable structure of the above-mentioned

efficient, low-cost, low-toxic and intriguing mesostructured catalyst,

high yields of the symmetrical diaryl sulfides were obtained in short

reaction times. Further studies are underway in our laboratory to

extend this mesostructured catalyst to other coupling reactions.

Preparation of mesoporous silica SBA-16 (I)

A mixture of pluronic F127 (1.484 g) and P123 (0.238 g) were

completely dissolved in a solution of concentrated hydrochloric acid

(37%) (8.87 mL) in deionized water (60 mL). The resulting solution

was magnetically stirred at 35°C for 4 h before dropwise adding

tetraethylorthosilicate (TEOS) (25.08 mmol, 5.22 g). After being

magnetically stirred for 40 min, the suspension was transferred into

a Teflon autoclave. The autoclave was placed under static conditions

at the same temperature for 24 h. Afterwards, the temperature was

raised up to 100 °C and kept at this temperature for 32 h.

Subsequently, the solid was isolated by filtration, dried in air at room

temperature. Then, the white powder was calcined at 550 °C for 10

h to produce the final mesoporous silica SBA-16 (I).

Experimental

General

All chemical reagents and solvents were purchased from Merck and

Sigma-Aldrich chemical companies and were used as received

without further purification. The purity determinations of the

products and the progress of the reactions were accomplished byTLC

on silica gel polygram STL G/UV 254 plates. The melting points of the

products were determined with an Electrothermal Type 9100

melting point apparatus. The FT-IR spectra were recorded on an Preparation of mesoporous SBA-16 functionalized by 3-

glycidyloxypropyltrimethoxysilane (SBA-16/ GPTMS) (II)

AVATAR 370 FT-IR spectrometer (ThermaNicolet spectrometer, USA)

KBr Plates at room temperature in the range between 4000 and 400

cm^-1with a resolution of 4 cm^-1. The far-IR spectrum in the region

650–200 cm^-1was obtained using a Thermo Nicolet NEXUS 870 FT-IR

spectrometer (USA) equipped with DTGS/polyethylene detector and

a solid substrate beam splitter. The NMR spectra were recorded on

Brucker Avance 400 MHz instruments in CDCl₃and DMSO-d₆as

solvent. Elemental analyses were performed using a Thermo

Finnigan Flash EA 1112 Series instrument (furnace: 900°C, oven:

65°C, flow carrier: 140 mL min^-1, flow reference: 100 mL min^-1). Mass

spectra were recorded with a CH7A Varianmat Bremem instrument

at 70 eV electron impact ionization, in m/z (rel %).The crystalline

structure of the catalyst was analyzed by small-angle XRD using a

Mesoporous silica SBA-16 (I) (1g) was dispersed in dry toluene (50

mL) by magnetically stirring at 110 °C for 30 min. 3-

Glycidyloxypropyltrimethoxysilane (GPTMS) (9.05 mmol, 2.14 g) was

then added to the resultant suspension, maintaining the stirring for

another 24h under reflux conditions and nitrogen atmosphere.

Successively, SBA-16/ GPTMS (II) was filtered, washed with ethanol

(5×5 mL) until the additional amount of GPTMS had been removed

before drying at 100 °C under vacuum for 10 h.

Preparation of mesoporous SBA-16 functionalized by aminated 3-

glycidyloxypropyltrimethoxysilane with thiosemicarbazide (SBA-

16/ GPTMS-TSC) (III)

PANalytical Company X’Pert PRO MPD diffractometer operated at 40 To a suspension of the obtained SBA-16/ GPTMS (II) (1 g) in dry

kV and 40 mA, utilizing Cu Kα radiation (λ = 0.154 nm) (at a step size toluene (50 mL) (by sonication for 30 minutes), thiosemicarbazide

of 0.020˚ and step time of 2 s). X-ray powder diffraction (XRD) was (TSC) (5.49 mmol, 0.5 g) was added in the presence of a catalytic

performed on a PANalytical Company X'Pert Pro MPD diffractometer amount of Et₃N (7.17 mmol, 0.72 g). The resultant mixture was

16 | J. Name., 2012, 00, 1-3

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Green Chemistry

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refluxed under nitrogen atmosphere. After 28 h, SBA-16/ GPTMS-TSC [3] M. A. Fernández‐Rodríguez, J. F. Hartwig, J. Org. Chem . 2009, 74 ,

View Article Online

DOI: 10.1039/C8GC03931C

1663-1672.

(III) was filtered, washed with ethanol (5 ×5 mL) and dried at 100 °C

overnight.

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Preparation of Cu^I-anchored onto mesoporous SBA-16

functionalized by aminated 3-glycidyloxypropyltrimethoxysilane

with

(IV)

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thiosemicarbazide

(SBA-16/

GPTMS-TSC-Cu^I)

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To a solution of CuCl (0.3 mmol, 0.03 g) in absolute EtOH (5 mL), SBA-

16/ GPTMS-TSC (III) (0.5 g) was added at room temperature. The

reaction mixture was magnetically stirred under argon atmosphere

for 4h. Afterward, the resulting suspension was filtered and the

obtained pale green precipitate SBA-16/ GPTMS-TSC-Cu^I(IV) was

washed with ethanol (5 × 5 mL), before drying under vacuum at

ambient temperature overnight.

[7] M. E. Peach, in: S. Patai, ed., The Chemistry of the Thiol Group,

John Wiley & Sons, London, 1974, 721.

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Typical procedure for preparation of diphenyl sulfide in the

presence of SBA-16/GPTMS-TSC-Cu^I(IV)

A mixture of finely powdered KOH (4 mmol, 0.23 g), SBA-16/GPTMS-

TSC-Cu^I(1.3 mol%, 1.86 mmol/g) and S₈/or thiourea (0.5 mmol,

0.016 g/ 0.038 g) was ground together in a mortar using pestle for 3

min. Then, the solidified mixture was added to iodobenzene (1

mmol, 0.2 g) and the reaction proceeds exothermically with a

magnetically stirred and heated at 110 °C under solvent-free

conditions. After completion of the reaction which was monitored by

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2878–2884.

temperature and diluted with ethyl acetate (10 mL). Afterward, the

mesostructured catalyst was separated by simple filtration, washed

with distilled water (2 × 5 mL), ethanol (2 × 5 mL), dried under

vacuum at 60 °C for the next run use. The crude product was then

extracted with ethyl acetate (the unreacted S₈/ or thiourea was

removed by adding water to the filtrate) and the organic layer was

dried over anhydrous Na₂SO₄. After evaporation of the solvent, the

residue was purified by thin layer chromatography on silica gel (n-

hexane/ethyl acetate = 9: 1) to provide the desired product (diphenyl

sulfide from S₈(0.182 g, 98%) and thiourea (0.176 g, 95%)).

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Acknowledgements

[22] H. Firouzabadi, N. Iranpoor, M. Gholinejad, Adv. Synth. Catal.,

2010, 352, 119–124.

The authors gratefully acknowledge the partial support of this study

by Ferdowsi University of Mashhad Research Council (Grant no.

p/3/39491).

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DOI: 10.1039/C8GC03931C

Graphical Abstract

CuI-anchored onto mesoporous SBA-16 functionalized by aminated 3-

glycidyloxypropyltrimethoxysilane with thiosemicarbazide (SBA-16/ GPTMS-

TSC-CuI): a heterogeneous mesostructured catalyst for S-arylation reaction

under solvent-free conditions

Sara. S. E. Ghodsinia, Batool Akhlaghinia*

The catalytic activity of SBA-16/GPTMS-TSC-Cu^Ias a novel

and efficient heterogeneous catalyst was investigated for S-

arylation reaction under solvent-free conditions.

Article Doi

CuI anchored onto mesoporous SBA-16 functionalized by aminated 3-glycidyloxypropyltrimethoxysilane with thiosemicarbazide (SBA-16/GPTMS-TSC-CuI): A heterogeneous mesostructured catalyst for: S -arylation reaction under solvent-free conditions

DOI: 10.1039/c8gc03931c

Source and publish data:

Authors:

Article abstract of DOI:10.1039/c8gc03931c

Full text of DOI:10.1039/c8gc03931c

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