Molecular Catalysis 524 (2022) 112310

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Molecular Catalysis
journal homepage: www.journals.elsevier.com/molecular-catalysis

Nickel(II) phosphine-catalysed hydrodehalogenation of aryl halides under

mild ambient conditions
Sebastian Jun Kai Guek a, Li Ji b, James Wen Liang Loke b, Hwee Ling Koh a, Wai Yip Fan b, *
a
Department of Pharmacy, National University of Singapore, 18 Science Drive 4, 117543, Singapore
b
Department of Chemistry, National University of Singapore, 3 Science Drive 3, 117543, Singapore

A R T I C L E I N F O A B S T R A C T

Keywords: A convenient and low-cost hydrodehalogenation process catalysed by air-stable nickel(II) complexes containing
Hydrodehalogenation bidentate phosphine ligands has been developed under ambient conditions with sodium borohydride acting as
Nickel phosphines the reducing agent and hydrogen atom source. High conversions of aryl halides, including polyfluorinated
Aryl halides
substrates, into their hydrogenated counterparts have been achieved in dimethylformamide (DMF) and to a
Polyfluorinated arenes
Borohydride
moderate extent, in DMF/isopropanol (10:90% v/v) solvent mixture. A mechanism has been proposed to account
for the experimental data.

Introduction bromides has been shown to proceed smoothly with nickel pincer
complexes [13]. Hydrodehalogenation of aryl halides was also carried
Hydrodehalogenation is an important process utilised for the con­ out in refluxing tetrahydrofuran (THF) using a combination of Ni
version of aryl halides to arenes. This reaction has been proven to be (0)/N-heterocyclic carbene complex and an alkoxide [14,15]. Catalytic
useful in organic synthesis and a number of catalytic methods have been hydrodefluorination of aryl fluorides was also achieved using nickel(0)
developed including electrolysis, photocatalysis, enzymatic catalysis diphosphine compounds prepared in situ by reacting nickel(0) diphos­
and more commonly transition metal catalysis [1–5]. Catalytic hydro­ phine hydride with the respective fluoroarene [16]. Most of the pro­
dehalogenation has also been regarded as an effective remedy for cesses require air-sensitive reagents at elevated temperatures in order to
treating polychlorinated and polybrominated biphenyls (PCBs and treat aryl fluorides and chlorides, otherwise the conversion is only
PBBs) [6,7]. These biphenyls represent a class of persistent toxic com­ effective for aryl bromides.
pounds that accumulate in the environment and ecosystems, and may As our objective is to carry out catalytic hydrodehalogenation of aryl
pose severe health conditions related to immunotoxicity and neurolog­ halides under mild ambient conditions, we would like to report that
ical disorders [8–10]. Thus it is important to develop a cost-effective simple air-stable nickel(II) halide complexes containing phosphines or
method for their detoxification as earlier strategies such as incinera­ pyridines, some of which are commercially available, can indeed serve
tion produced even more toxic gaseous products. as convenient and efficient catalysts even for polyfluorinated arenes. A
While many metal-catalysed hydrodehalogenation processes have variety of aryl halides have been used as substrates with sodium boro­
been reported, a gap still exists in developing an inexpensive and hydride serving a dual purpose as a reductant and a hydrogen atom
convenient method which can operate under ambient conditions. Many donor. The catalysis can also be carried out with moderate efficiency in a
methods that have been studied usually involved the conversion of a greener solvent mixture containing isopropanol as the major solvent.
single type of aryl halides, in particular the bromides [5]. Some methods The concept of a “green” solvent here is measured according to a se­
also utilised hazardous reagents such as lithium aluminum hydride or lection guide based on the safety, health and environmental criteria of
precious metals such as palladium [11,12]. solvents [17]. Finally we have also proposed a nickel-catalysed hydro­
In this work, we have focused on the development of a homogeneous dehalogenation mechanism to account for our experimental
catalytic hydrodehalogenation system based on inexpensive nickel observation.
complexes. A number of nickel complexes previously used as catalysts
are briefly described here. Under mild heating, the conversion of aryl

* Corresponding author.
E-mail address: [email protected] (W.Y. Fan).

https://doi.org/10.1016/j.mcat.2022.112310
Received 8 March 2022; Received in revised form 7 April 2022; Accepted 14 April 2022
Available online 25 April 2022
2468-8231/© 2022 Elsevier B.V. All rights reserved.
S.J.K. Guek et al. Molecular Catalysis 524 (2022) 112310

Results and discussion From the initial screening, 1 and 2 afforded the highest yield hence
further optimisation of the catalytic process was carried out using either
Nine nickel(II) chloride complexes (1–9) containing different phos­ one of the catalysts. The effect of using different solvents, reaction time
phine and/or nitrogen centered ligands and nickel(II) chloride dihydrate and catalytic loading for 1 or 2 are shown in Table 2.
(10) were used for catalytic screening (see Table 1). Compounds 1, 3, 5, The hydrodehalogenation of 4,4′ -dibromobiphenyl proceeded with
7–10 were commercially available while lower yields, in particular with 2 as the catalyst (Entries 1–4), when
2, 4 and 6 were prepared in order to provide even more variations in shorter reaction periods of 3 and 9 h were used. A number of greener
the ligand properties. The compounds were then characterised in the solvents were also tested as long as the solvent was able to dissolve the
laboratory using established literature methods [18–20]. catalyst and substrate. The solvents chosen here are those that have been
For the initial optimisation, hydrodehalogenation was carried out ranked highly as green solvents in terms of their impact to the envi­
with a 10% catalytic mol loading (with respect to the aryl halide) of the ronment, safety and health issues [17]. Solvents such as isopropanol,
nickel complex at room temperature over 18 h in air. Two equivalents of dimethylcarbonate, ethyl acetate fall under the recommended category
sodium borohydride (NaBH4) per halogen atom were used for all the while acetonitrile and acetone are considered slightly more problematic.
substrates not only to substitute the halogen atom but also to reduce the All these solvents are still ranked much higher than DMF which falls in
nickel complex and to compensate for some loss due to reaction with the hazardous category. However DMF was still found to be superior
water in wet polar solvents. Dimethylformamide (DMF) was the initial when the respective product yield was compared (Entry 5 in Table 1 vs
solvent choice as all the substrates and catalysts were found to be soluble Entries 5–9 in Table 2). Significantly, the use of a mixed solvent con­
in this solvent. Other solvents were also tested during the screening sisting of 10% DMF in isopropanol (IPA) enabled a high yield to be
process since DMF is not considered to be green [17]. 4,4′ -dibromobi­ achieved (Entry 13) while at the same time may help to dilute the impact
phenyl was chosen as the substrate for screening as it bears resemblance of using DMF as the only solvent. When the catalytic loading of 1 or 2
to the PBB pollutants. The product yield determined using Gas was reduced, the respective product yield was found to decrease
Chromatography-Mass Spectrometry (GC–MS), was used as an indica­ whether the catalysis was carried out in DMF or 10% DMF in IPA (En­
tion of reaction efficiency. A summary of the optimisation results is tries 14–16). After assessing the three parameters (reaction time, sol­
shown in Table 1. vent, catalytic loading), we have kept 18 h as the reaction duration to be
As expected, hydrodehalogenation did not proceed in the absence of used for the hydrodehalogenation of other aryl halides with complex 1
a nickel catalyst (Entry 1). A hydrogen source was also needed, as no as the catalyst of choice. Together with DMF, the 10% DMF in IPA
reaction occurred in the absence of NaBH4 (Entry 2). Hydro­ mixture was also used as the greener solvent option with the catalytic
dehalogenation also did not occur when a phosphine ligand such as dppe loading fixed at 10%.
was used as the only catalyst (Entry 3). Compared to other ligands, A summary of the hydrodehalogenation of aryl bromides and aryl
nickel complexes containing bidentate phosphine ligands (Entries 4 and chlorides under the aforementioned optimised conditions is shown in
5) were most effective with biphenyl product yields approaching 100%. Table 3. As expected the aryl bromides underwent hydrodehalogenation
Surprisingly, bis-phosphine nickel chlorides gave lower yields (Entries 8, more easily because of the weaker C-Br bond. Interestingly, the con­
11 and 12) even when compared to a simple nickel salt (10) (Entry 13). version of aryl chlorides was only slightly more difficult. Our results
Nickel complexes bearing naphthyl, cyclopentadienyl or pyridine li­ appeared to show full conversion for naphthyl bromide and chloride
gands gave moderate yields (Entries 6,9 and 10). (compare Entry 1 and 2) but when the reaction time was shortened, a

Table 1
Catalyst screening using the hydrodehalogenation of 4,4′ -dibromobiphenyl as the testcase.

Entry Catalyst* Yield (%)

1 None 0
2 (dppe)NiCl2 1 without NaBH4 0
3 dppe only 0
4 (dppe)NiCl2 1 91
5 (κ2-triphos)NiCl2 2 99
6 (dmbpy)NiCl2 3 36
7 (dppf)NiCl2 4 70
8 (PPh3)2NiCl2 5 20
9 [(PNN)NiCl]+Cl− 6 69
10 Cp(PPh3)NiCl 7 0
11 (PCy3)2NiCl2 8 27
12 (1-Naphthyl)(PPh3)2NiCl 9 32
13 NiCl2•2H2O 10 56
*
dppe = 1,2-Bis(diphenylphosphino)ethane]
triphos = 1,1,1-Tris(diphenylphosphinomethyl)ethane),
dmbpy = 4,4′ -Dimethyl-2,2′ -bipyridine
dppf = 1,1′ -Bis(diphenylphosphino)ferrocene)
PPh3 = Triphenylphosphine
PNN = 2-((Di‑tert-butylphosphinomethyl)− 6-diethylaminomethyl)pyridine)
Cp = cyclopentadienyl
PCy3 = tricyclohexylphosphine.

2
S.J.K. Guek et al. Molecular Catalysis 524 (2022) 112310

Table 2
Optimising the reaction conditions with different catalytic load, solvent and/or reaction time in the presence of complex 1 or 2 as the catalyst.

Entry Catalyst Reaction time (h) Mole (%) Solvent Yield (%)

1 2 3 10 DMF 7
2 2 9 10 DMF 30
3 1 3 10 DMF 78
4 1 9 10 DMF 86
5 1 18 10 Dimethyl Carbonate (DMC) 11
6 1 18 10 Acetone 3
7 1 18 10 Ethyl Acetate (EA) 10
8 1 18 10 Acetonitrile (ACN) 21
9 1 18 10 Isopropanol (IPA) 64
10 1 18 10 10% DMF in DMC 50
11 1 18 10 10% DMF in EA 30
12 1 18 10 10% DMF in ACN 68
13 1 18 10 10% DMF in IPA 98
14 2 18 5 DMF 52
15 1 18 5 DMF 65
16 1 18 5 10% DMF in IPA 83

higher conversion was indeed observed for naphthyl bromide. Dibro­ however much slower for tetrafluorobenzene conversion to tri­
monaphthalene and dibromobenzene were also fully converted to fluorobenzene. A previous study showed that the addition of free
naphthalene and benzene, respectively. However hydrodehalogenation phosphines to the reaction mixture was able to improve the yield of
of dichlorobenzene did not fully remove the two chlorine atoms as defluorinated benzenes [16]. In our study we found that the yields for
monochlorobenzene was detected amongst the products. For arenes entries 1–3 did not improve even with the addition of up to five
containing both bromine and chlorine atoms (Entry 5 and 10), the equivalents of triphenylphosphine.
bromine atom was removed preferentially. In fact no aryl bromide in­ The hydrodefluorination of monofluorinated benzene was more
termediates were detected even at shorter time intervals. challenging. We instead observed the formation of 4-fluoroaniline when
Hydrodehalogenation also proceeded in the presence of different 1-fluoro-4-nitrobenzene was used as the substrate. It appears that the
functional groups on the arene (Entries 7–10) although the process nitro group was more readily reduced to amine under our experimental
appeared more sluggish in the presence of the nitrile and methoxy group conditions. Hydrodefluorination of fluoropyridine proceeded slowly to
(Entries 8 and 9). Coordination of either functional group to the nickel afford pyridine while the conversion of naphthyl fluoride to naphthalene
center of the catalyst could have provided some hindrance. As the tri­ was unsuccessful. Overall, conversion of aryl fluorides to arenes remains
fluoromethyl (CF3) group is not expected to behave similarly due to the challenging but the success of partial hydrodefluorination of poly­
unavailability of a lone pair for coordination, high conversion could be fluorinated benzenes may encourage the further development of cata­
achieved for aryl halides bearing the CF3 group (Entries 7 and 10). lytic hydrodehalogenation processes under mild conditions.
Interestingly, Entry 11 provided a noteworthy observation that steric Based on the experimental observations, the mechanism shown in
hindrance is an important factor affecting hydrodehalogenation. The Fig. 1 represents a consistent picture of how hydrodehalogenation of
yield of the xylene product was very low as the chlorine group flanked aryl halides catalysed by nickel chloride complexes was carried out.
by the two methyl substituents appeared to be protected from interac­ Complex 1 has been used as the testcase for illustrating the mechanism.
tion with the catalyst. The nickel(II) complex is first reduced by sodium borohydride to a Ni
The use of a mixed solvent (10% DMF in IPA) was successfully hydride intermediate. Although a nickel(II) dihydride species is depicted
applied to naphthyl bromide and chloride where almost complete in Fig. 1, we note that different forms of nickel hydrides comprising
hydrodehalogenation was observed for each case. In general, product bridged hydrides or even coordinated borohydrides are also possible
yields for the other aryl bromides and chlorides were lower compared to [21]. Through reductive elimination, hydrogen gas is released from the
reactions carried out in DMF. However the results were still considered nickel hydride to afford a solvated Ni(0) complex. Oxidative addition of
encouraging from the green chemistry point of view since a different the aryl halide then takes place at the Ni(0) center to give a Ni(II)
solvent could have easily inhibited the reaction completely. complex containing adjacent halide and aryl ligands. The halide is then
We have also investigated the possibility of hydrodefluorination in substituted by a hydride generated from sodium borohydride before
polyfluorinated benzene compounds under the same optimised condi­ reductive elimination releases the arene as the major product. The cat­
tions applied to the aryl bromides and chlorides (see Table 4). However alytic cycle is completed upon regeneration of the solvated Ni(0)
the reactions with the aryl fluorides were only carried out in DMF intermediate.
instead of the DMF-IPA mixture as preliminary product yields obtained Under our experimental conditions, the oxidative addition step is
for the latter solvent were very low. believed to be rate-determining primarily because carbon-halogen
Interestingly hexafluorobenzene could be converted to its major bonds of different strengths were broken at this point. Indeed, a stark
product pentafluorobenzene which in turn further defluorinate to tet­ difference in the product yields was observed between the aryl fluorides
rafluorobenzenes. We were unable to determine which tetra­ and the rest of the aryl halides.
fluorobenzene isomers were formed. The conversion of In the mechanistic scheme, we proposed that the dppe ligand re­
pentafluorobenzene as the initial substrate to tetrafluorobenzenes also mains coordinated to the metal center as depicted for all the nickel in­
proceeded albeit at a slightly lower rate. The corresponding process was termediates. Hence structural rigidity conferred by bidentate ligands

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S.J.K. Guek et al. Molecular Catalysis 524 (2022) 112310

Table 3
Summary of catalytic hydrodehalogenation of aryl bromides and aryl chlorides using 1 as the catalyst.

Entry Substrate Product Yield (%)DMF Yield (%)10% DMF in IPA

1 100 100

2 100 96

3 100 91

0 8

4 100 18

0 71

5 45 16

55 84

6 15
30

56
65

7 100 74

8 44 16
(continued on next page)

4
S.J.K. Guek et al. Molecular Catalysis 524 (2022) 112310

Table 3 (continued )

Entry Substrate Product Yield (%)DMF Yield (%)10% DMF in IPA

9 70 26

10 100 14

0 57

11 3 1

plays an important role in stabilising the intermediates. This is sup­ place. The generation of a Ni(dppe)2 species is believed to have occurred
ported by the fact that bis-phosphine nickel complexes such as based on previous observations on similar nickel complexes [22].
(PPh3)2NiCl2 acted as poorer catalyst due to the increased lability of the Interestingly we note that complex 9 could itself be an intermediate of
monophosphine ligands. An advantage of using diphosphine ligands also the catalytic cycle if naphthyl chloride and complex 5 were used as the
lies in their strong electron-donating properties which tend to favor substrate and catalytic precursor, respectively. This gave us the oppor­
oxidative addition onto the metal center. Amongst some of the ligands tunity to investigate the kinetics of the second step of the catalytic cycle
used, dppe and triphos would be considered as strong donors followed by reacting 9 with NaBH4 directly. Indeed a rapid reaction was observed
by dppf and bipyridine. Indeed complex 1 bearing the dppe ligand to afford a red solution presumably containing the analogous Ni(0)
performed most efficiently lending support to the important role played phosphine species again. This observation shows that halide substitution
by the oxidative addition step. In addition, we note that the rigidity of by hydride is fast and therefore unlikely to contribute to the
the pincer ligand surrounding the nickel center in 6 may also have rate-determining step.
reduced the exposure of the nickel center towards oxidative addition. The possibility of Ni nanoparticle catalysis is also explored as they
The difference in the catalytic efficiency observed for DMF and 10% can be formed upon direct borohydride reduction of the nickel(II)
DMF in IPA mixed solvent may be partly accounted for by considering complexes. These nanoparticles could account for the efficiency of
the structure of the solvated Ni(0) intermediate. The coordination of simple salts such as NiCl2 in the hydrodebromination of 4,4′ -dibromo­
DMF or IPA molecules onto the nickel center will influence the reactivity biphenyl. However the hydrodechlorination of naphthyl chloride did
of the intermediate. We propose that the stronger DMF coordination to not proceed with NiCl2 even in the presence of excess NaBH4. Although
the metal center leads to a longer-lived Ni(0) intermediate. Although the hydrodebromination can be partially accounted for by nanoparticles,
oxidative addition process would then be slower, the number of catalytic the molecular nickel complexes would still be required for the more
cycles would increase before the Ni(0) intermediate finally decomposes difficult hydrodechlorination and hydrodefluorination processes.
into some non-active species. Furthermore, the outcome of nanoparticle catalysis would be very
We have also carried out separate experiments to lend more insight similar regardless of the nickel precursor. However differences in the
into the mechanism. Upon addition of NaBH4 into a DMF solution catalytic efficiency were found when comparing across the nickel
containing only 1, an instantaneous colour change to dark red took phosphine complexes. For example, the facile dissociation of PPh3

5
S.J.K. Guek et al. Molecular Catalysis 524 (2022) 112310

Table 4 Experimental section

Summary of catalytic hydrodehalogenation of aryl fluorides using 1 as the
catalyst. Materials: All the substrates screened and starting materials used for
synthesis were purchased from Sigma-Aldrich (Singapore) and used as
received. Solvents used for synthesis, catalytic hydrodehalogenation and
spectroscopic characterisation were reagent grade. Compounds 2, 4 and
6 were prepared according to reported methods. The catalysts were
dissolved in either acetonitrile or dichloromethane and characterised
using Electrospray Ionisation (ESI) mass spectrometry on a Thermo
Scientific LCQ Fleet Mass Spectrometer. Elemental analyses (EAL) of
Entry Starting Material Product % Yield carbon and hydrogen were conducted using a ElemenVario Micro Cube.
1 65
Gas Chromatography-Mass Spectrometry (GC–MS) analyses were car­
ried out on an Agilent Technologies 7890A GC system fitted with a
7683B Series Injector (Split/Splitless inlet system) and coupled to an
Agilent Technologies 5975C Inert Mass-Selective Detector

20 Syntheses of nickel(ii) compounds

Compound 2: An equimolar amount of triphos (1.45 g, 2.31 mmol)

2 72 was added to 50 mL of THF solution of NiCl2•2H2O (0.383 g, 2.31
mmol), resulting in a colour change from green to orange. The mixture
was stirred at room temperature for 30 min and the solvent was removed
via a rotavapor. Yield: 1.39 g, 82.3%. ESI-MS: calcd for [C14H39Cl2NiP3 -
Cl]+ 717.28; found: 717.21. Anal. calcd: C, 65.29; H, 5.21; found: C,
3 8
65.21; H, 5.48.
Compound 4: 133 mg of NiCl2•2H2O (1.7 mmol) was added to 5 mL
ethanol in a 50 mL round bottom flask. Flask was sealed with a rubber
septum and sparged with nitrogen for 15 min. 942 mg of DPPF (1.7
4 4 mmol) (DPPF = 1,1′ -Bis(diphenylphosphino)ferrocene) was added in
one portion. Mixture was heated to 80 ◦ C for 30 min over an oil bath and
then cooled to room temperature. Deep green solid was collected by
vacuum filtration, washed with ethanol and drying under vacuum
yielded the product. Yield: 893 mg, 76.8%. ESI-MS: calcd for
[C34H30Cl2FeNiP2 - Cl]+ 648.58; found: 648.06. Anal. calcd: C, 59.70; H,
4.10; found: C, 59.98; H, 4.34.
5 0
Compound 6: 101.2 mg (0.5 mmol) of PNN ligand was added to a
methanol solution (8 mL) of NiCl2•2H2O (0.5 mmol, 82.8 mg) resulting
in a colour change to orange. Reaction mixture was stirred for 3 h.
Solvent was removed from mixture via a rotavapor. Residue washed
with diethylether and drying under vacuum yielded the product. Yield:
6 8
157.7 mg, 70%. ESI-MS: calcd for [C19H35Cl2N2NiP - Cl]+ 415.2; found:
415.68. Anal. calcd: C, 50.43; H, 7.74. Found: C, 51.20; H, 7.51.
Catalytic hydrodehalogenation experiments: All reactions were carried
out in air at room temperature. A 50 mL round-bottom flask equipped
with a magnetic stir bar was charged with 280.8 mg (0.90 mmol) of 4,4′ -
ligand from the nickel center would have produced more nanoparticles dibromobiphenyl (or 0.90 mmol of another aryl halide), 0.09 mmol of
and leads to more efficient catalysis. The opposite trend was however catalyst (10 mole%), 68.1 mg (0.18 mmol, 2.0 eq) of NaBH4 and 6 mL of
observed where the product yield for 4,4′ -dibromobiphenyl obtained in DMF (or other solvents) in room temperature. The reaction mixture was
the presence of PPh3 is relatively low. left to stir overnight for 18 h. Thereafter, 6 mL of deionised water was
added to stop the reaction by deactivating the excess NaBH4 in the
Conclusion mixture.

In this study, a low-cost and convenient catalytic system for the GC–MS analysis
hydrodehalogenation of aryl halides under ambient conditions has been
developed. From a number of nickel complexes screened for their cat­ Using a 1 mL Injekt® - F Solo syringe, 0.2 mL of the reaction mixture
alytic activity, air-stable nickel(II) diphosphine complexes turned out to was drawn and passed through a fitted microfilter into a 2 mL GC–MS
be most efficient in producing the highest product yields. A variety of vial. For the naphthalene and biphenyl substrates, DMF was used for
aryl bromides, chlorides and polyfluoride substrates have been con­ topping up the volume to 2 ml. For the monobenzene substrates, the
verted into their hydrogenated analogues in dimethylformamide and to DMF solvent was first removed via liquid-liquid extraction because its
a more moderate extent, in a greener solvent such as 10% DMF in iso­ retention peak overlaps with the retention peak of the monobenzene
propanol. A mechanism of how the nickel complex catalyses hydro­ products. Diethylether was added to top up the volume to 2 ml instead.
dehalogenation has been proposed to explain the experimental features. Internal standard calibrations were also done for the dehalogenated
products, by-products and unreacted starting materials to improve
precision of quantitative analysis. As an internal standard, dodecane (2
μL) was added into the 2 ml GC–MS vial before injection into the GC–MS
column.

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S.J.K. Guek et al. Molecular Catalysis 524 (2022) 112310

Fig. 1. Proposed reaction mechanism for the catalytic hydrodehalogenation of aryl halides (Ar-X where X = Br, Cl or F)) using complex 1 as the model catalytic
precursor. Sodium borohydride and the solvent molecule are depicted as H− and Solv, respectively.

Three different sets of parameters were used for the different groups Acknowledgment
of substrates. Biphenyls: The initial oven temperature of 40 ◦ C was
increased to 100 ◦ C at a rate of 30 ◦ C/min. The temperature was held for This publication was made possible by funding through a National
5 min before increasing to 250 ◦ C at a rate of 15 ◦ C/min and held for 4 University of Singapore research grant A-0004132-00-00 and the Na­
min. The total run time was 21 min inclusive of a 4 min solvent delay. tional University of Singapore final year project fund.
Naphthalenes: The initial temperature of 50 ◦ C was held for 5 min
before increasing to 110 ◦ C at a rate of 15 ◦ C/min. It was held for References
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