Synthesis, characterization and theoretical and fluorescence emission microscopy studies of new Pd/Pt–cyclopropa[60]fullerene complexes: Application of Taguchi method for optimization of parameters in Suzuki–Miyaura reaction

Article abstract of DOI:10.1002/aoc.4382

The reactions of unsymmetric phosphorus ylides of the type [Ph₂P(CH₂)_nPPh₂?C(H)C(O)C₆H₄-p-CN] (n?=?1 (Y¹); n?=?2 (Y²)) with C₆₀ and M(dba)₂ (M?=?Pd or Pt; dba?=?dibenzylideneacetone) are reported. Based on the various coordination modes of these ylides in complexation, the following new Pd/Pt–cyclopropa[60]fullerene complexes were obtained: P,C-coordinated [(η²-C₆₀)Pd(κ²-Y¹)] (1) and [(η²-C₆₀)Pt(κ²-Y¹)] (2) complexes and P-coordinated [(η²-C₆₀)Pd(Y²)₂] (3) and [(η²-C₆₀)Pt(Y²)₂] (4) complexes. These compounds were characterized using Fourier transform infrared, UV–visible and NMR (¹H, ¹³C and ³¹P) spectroscopies and scanning electron microscopy. Furthermore, cytotoxicity studies showed that nanoparticles of these complexes can be used as non-toxic labels for cellular imaging application. Also energy decomposition analysis results revealed that the percentage contribution of ΔE_elec in total interaction energy is considerably larger than that of ΔE_orb. Thus, in all complexes the (η²-C₆₀)M?(Y¹) bond is considerably more electrostatic in nature than the (η²-C₆₀)?M(Y¹) bond. Finally, by application of the Taguchi method for optimization of parameters in Suzuki–Miyaura reaction, the catalytic activity of Pd complexes 1 and 3 was investigated in the cross-coupling reaction of various aryl chlorides with phenylboronic acid. According to analysis of variance results, solvent has the highest F value and it has high contribution percentage (36.75%) to the yield of Suzuki–Miyaura reaction.

Full text of DOI:10.1002/aoc.4382

Received: 16 January 2018
DOI: 10.1002/aoc.4382
Revised: 9 March 2018
Accepted: 12 March 2018
F U L L P A P E R
Synthesis, characterization and theoretical and fluorescence
emission microscopy studies of new Pd/Pt–cyclopropa[60]
fullerene complexes: Application of Taguchi method for
optimization of parameters in Suzuki–Miyaura reaction
Seyyed Javad Sabounchei1
| Khadijeh Badpa1 | Ali Hashemi1 | Sadegh Salehzadeh1
|
Farahnaz Maleki1
| Leila Hosseinzadeh2
1 Faculty of Chemistry, Bu‐Ali Sina
University, Hamedan 65174, Iran
2 Pharmaceutical Sciences Research
Center, Kermanshah University of
Medical Sciences, Kermanshah, Iran
The reactions of unsymmetric phosphorus ylides of the type [Ph2P(CH2)
nPPh2¼C(H)C(O)C6H4‐p‐CN] (n = 1 (Y1); n = 2 (Y2)) with C60 and M(dba)2
(M = Pd or Pt; dba = dibenzylideneacetone) are reported. Based on the
various coordination modes of these ylides in complexation, the following
new Pd/Pt–cyclopropa[60]fullerene complexes were obtained: P,C‐coordinated
[(η2‐C60)Pd(κ2‐Y1)] (1) and [(η2‐C60)Pt(κ2‐Y1)] (2) complexes and P‐coordinated
[(η2‐C60)Pd(Y2)2] (3) and [(η2‐C60)Pt(Y2)2] (4) complexes. These compounds
were characterized using Fourier transform infrared, UV–visible and NMR
(1H, 13C and 31P) spectroscopies and scanning electron microscopy. Further-
more, cytotoxicity studies showed that nanoparticles of these complexes can
be used as non‐toxic labels for cellular imaging application. Also energy
decomposition analysis results revealed that the percentage contribution of
Correspondence
Seyyed Javad Sabounchei, Faculty of
Chemistry, Bu‐Ali Sina University,
Hamedan 65174, Iran.
Email: jsabounchei@yahoo.co.uk
Funding information
Bu‐Ali Sina University
ΔEelec in total interaction energy is considerably larger than that of ΔEorb
.
Thus, in all complexes the (η2‐C60)M―(Y1) bond is considerably more
electrostatic in nature than the (η2‐C60)―M(Y1) bond. Finally, by application
of the Taguchi method for optimization of parameters in Suzuki–Miyaura reac-
tion, the catalytic activity of Pd complexes 1 and 3 was investigated in the cross‐
coupling reaction of various aryl chlorides with phenylboronic acid. According to
analysis of variance results, solvent has the highest F value and it has high contri-
bution percentage (36.75%) to the yield of Suzuki–Miyaura reaction.
KEYWORDS
Pd/Pt–cyclopropa[60]fullerene complexes, Suzuki–Miyaura reaction, synthesis, Taguchi method,
theoretical studies
1 | INTRODUCTION
mechanical and electrical properties.[2–6] Moreover,
metalla‐cyclopropa[60]fullerenes, in which the fullerene
cage is attached to a metal centre to form corresponding
organometallic π‐complexes,[7–15] have become a current
focus of fullerene research into important roles in
After the discovery of C60 in 1985 by Kroto et al.,[1] fuller-
enes have attracted a tremendous amount of research
interest due to their interesting physicochemical, optical,
Appl Organometal Chem. 2018;e4382.
wileyonlinelibrary.com/journal/aoc
Copyright © 2018 John Wiley & Sons, Ltd.
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https://doi.org/10.1002/aoc.4382

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SABOUNCHEI ET AL.
biological and materials science.[16,17] Among such com-
plexes, Pd/Pt–cyclopropa[60]fullerene complexes that
contain phosphorus ligands have received less attention.
Thus, the search for improved methods for the synthesis
of these transition metal–fullerene complexes is of consid-
erable importance. Experimental and theoretical studies of
the reactivity and coordination chemistry of carbonyl‐sta-
bilized phosphorus ylides are an important research field
of our group.[18–23] Because of various coordination modes
of α‐keto‐stabilized phosphorus ylides in metal complexes
(P‐, C‐ and P,C‐coordination modes), these compounds
are attractive candidates for further development in Pd/
Pt–cyclopropa[60]fullerene complexes.[24,25]
During the past few years, significant progress has
been made in the use of Pt–cyclopropa[60]fullerene com-
plexes in some biological applications.[26–30] Based on
cytomorphological studies, Pt–cyclopropa[60]fullerene
complexes can be used as effective platforms for drug
delivery to molecular targets in tumour cells.[31,32] How-
ever, in vitro and in vivo detection of these nanomaterials
is particularly difficult using standard fluorescence
microscopy, because their solubility is low and
fluorescence is barely detectable.[33] Use of specific
Pt–cyclopropa[60]fullerene complexes for targeted deliv-
ery of drugs to tumour cells is one of the most appropriate
ways for reducing severe toxicity of conventional antican-
cer drugs towards normal tissues.[33]
phosphorus ylides in Taguchi‐optimized Suzuki–Miyaura
reactions. Herein, we report the synthesis, characterization
and theoretical and catalytic studies of new Pd/Pt–[60]ful-
lerene complexes of mono‐ and bidentate phosphorus ylides
(Figure 1).
2 | EXPERIMENTAL
2.1 | Materials and Methods
All synthetic reactions were carried out under an atmo-
sphere of dry nitrogen using standard Schlenk tech-
niques. C60 (+99.5%) and M(dba)2 (M = Pd or Pt;
dba = dibenzylideneacetone) were obtained from com-
mercial sources and used without further purification.
Phosphorus ylides Y1 and Y2 were synthesized and
characterized as previously reported.[36] Toluene and
n‐hexane were used as reagent grade and dried over Na/
benzophenone. NMR (1H, 13C and 31P) spectra were
recorded using 250 MHz Bruker and 90 MHz Jeol spec-
trometers with CDCl3 as solvent at 25 °C. Infrared (IR)
spectra were recorded with a PerkinElmer FT‐IR spectro-
photometer in the range 400–4000 cm−1 using KBr pel-
lets. UV–visible spectra were recorded between 200 and
800 nm using a Perkin voyager DE‐PRO spectrometer.
Scanning electron microscopy (SEM) was conducted
using a VEGA TESCAN instrument.
There are some reports in which Pd–cyclopropa[60]
fullerene complexes have been used as efficient catalysts
for a variety of reactions.[27] For example, Sulman and
co‐workers investigated experimentally and theoretically
the catalytic activity of η2‐C60Pd(PPh3)2 complex in selec-
tive hydrogenation of acetylenic alcohols.[34] Also, Veisi
et al. reported the synthesis of biguanide (metformine)‐
functionalized fullerene (C60‐Met/Pd2+) complexes and
their application in the Suzuki–Miyaura coupling reac-
tion of various aryl halides and phenylboronic acid. The
Suzuki–Miyaura reaction, one of the most popular and
powerful methods for the joining of aryl–aryl moieties,
is typically catalysed by palladium complexes containing
bulky and electron‐rich phosphine ligands. This reaction
appears to be affected by various parameters, including
solvent, base and catalyst loading, and a systematic study
of the optimization of these factors with the Taguchi
method makes it possible to investigate the contribution
percentage of desired parameters to the yield of the reac-
tion. The Taguchi method, a robust design approach, uses
many ideas from statistical experimental design for evalu-
ating and implementing improvements in processes[35]
and it can help in appropriate selection of conditions for
the Suzuki–Miyaura reaction.
2.2 | Synthesis of Pd/Pt–[60]Fullerene
Complexes
In a general procedure, a toluene solution of M(dba)2
(M = Pd or Pt; 0.05 mmol, 5 ml) was added to a toluene
solution of C60 (0.036 g, 0.05 mmol, 15 ml) and the
resulting black suspension was stirred in a 50 ml Schlenk
tube at ambient temperature. After 15 min, a solution of
ylide was injected into the system via a syringe pump
(0.05 mmol, 5 ml). The solution was further stirred for
2 h at room temperature. The solid product can be precip-
itated from the deep‐green solution with a non‐polar sol-
vent such as n‐hexane. The obtained solid was then
washed with diethyl ether to afford the desired pure
product.
Based on the above considerations, we aimed to use Pd–
cyclopropa[60]fullerene complexes bearing unsymmetric
FIGURE 1 Phosphorus ylides that were applied in this study as
ligands

SABOUNCHEI ET AL.
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2.2.1 | Data for [(η2‐C60)Pd(κ2‐Y1)] (1)
(C═O); 512 (C60). UV–visible in toluene (λmax, nm): 298,
1
334, 354. H NMR (CDCl3, δH, ppm): 2.81 (m, 4H, CH2);
Black solid; yield 0.051 g (91%); m.p. > 300 °C
(decomposed). Selected IR data (KBr, cm−1): 1650
(C═O), 524 (C60). UV–visible in toluene (λmax, nm): 300,
4.13 (m, 1H, CH); 7.06–7.99 (m, 24H, Ph). 13C NMR
(CDCl3, δC, ppm): 21.41 (m, CH2); 49.20 (d, CH); 119.11
(s, CN); 124.90–148.66 (Ph and C60); 182.75 (s, CO). 31P
NMR (CDCl3, δP, ppm): 16.73 (d, PCH); 17.69 (d, pph2).
1
314, 360. H NMR (250.13 MHz, CDCl3, δH, ppm): 4.26
(m, 2H, CH2); 5.53 (d, 1H, PCH); 6.71–7.93 (m, 24H,
Ph). 13C NMR (CDCl3, δC, ppm): 22.66 (s, CH2); 31.90
(d, PCH,); 119 (s, CN); 125.27–143.08 (Ph and C60);
187.1 (s, CO). 31P NMR (CDCl3, δP, ppm): 13.18 (d,
PCH, 2JP–P = 79.68 Hz); 31.26 (d, PPh2, 1JP–P = 79.68 Hz).
2.2.4 | Data for [(η2‐C60)Pt(Y2)2] (4)
Black solid; yield 0.043 g (87%); m.p. > 300 °C
(decomposed). Selected IR data (KBr, cm−1): 1617
(C═O); 524 (C60). UV–visible in toluene (λmax, nm): 302,
1
2.2.2 | Data for [(η2‐C60)Pt(κ2‐Y1)] (2)
334. H NMR (CDCl3, δH, ppm): 2.73 (m, 4H, CH2); 4.12
(d, 1H, CH); 7.07–8.34 (m, 24H, Ph). 13C NMR (CDCl3,
δC, ppm): 21.45 (m, CH2); 49.04 (d, CH); 119.08 (s, CN);
124.18–147.36 (Ph and C60); 182.94 (s, CO). 31P NMR
Black solid; yield 0.051 g (73%); m.p. > 300 °C
(decomposed). Selected IR data (KBr, cm−1): 1651
(C═O); 526 (C60). UV–visible in toluene (λmax, nm): 302,
1
(CDCl3, δP, ppm): 16.46 (td, PPh2, JPt–P = 3208.2 Hz):
1
2
322. H NMR (CDCl3, δH, ppm): 4.80 (m, 2H); 5.85 (d,
19.21 (td, PPh2, JPt–P = 3872.7 Hz).
1H, PCH); 6.98–8.59 (m, 24H, Ph). 13C NMR (CDCl3, δC,
ppm): 38.70 (s, CH2); 56 (d, PCH); 112.8 (s, CN);
127.2–141.2 (Ph and C60); 188.53 (s, CO). 31P NMR
2.3 | Cytotoxicity and Cellular Uptake
Assay
1
(CDCl3, δP, ppm): 13.27(td, PCH, JPt–P = 3920.8 Hz);
2
40.42 (d, PPh2, JPt–P = 66.6 Hz).
Human umbilical vein endothelial cells (HUVEC cell line)
were obtained from Pasteur Institute of Iran (Tehran,
Iran). Dulbecco's modified Eagle's medium (DMEM‐F12)
supplemented with foetal bovine serum (10% v/v) and 1%
penicillin (100 U ml−1)–streptomycin (100 U ml−1) was
used for cell growth at 37 °C in a humidified incubator
2.2.3 | Data for [(η2‐C60)Pd(Y2)2] (3)
Black solid; yield 0.075 g (75%); m.p. > 300 °C
(decomposed). Selected IR data (KBr, cm−1): 1618
SCHEME 1 Synthesis of metallo‐cyclopropa[60]fullerene complexes 1–4

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SABOUNCHEI ET AL.
containing 5% CO2. Cell proliferation was determined
using the 3‐(4,5‐dimethylthiazol‐2‐yl)‐2,5‐diphenyltetra-
zoliumbromide (MTT) assay. The cells were plated in 96‐
well cell culture plates at a cell density of 15 × 104 cells
per well. After 24 h the spent medium was replaced with
fresh medium containing increasing concentrations (0–
200 μM) of compounds 1 and 2. A negative control of
untreated cells was included. The cells were incubated
for a further 24 h, after which a 0.5 mg ml−1 MTT solution
(10 μl per well) was added and the cells incubated for an
additional 4 h. Then, the medium was removed, and the
purple
formazan
crystals
were
dissolved
in
dimethylsulfoxide (200 μl per well). Absorbance was
determined using an ELISA plate reader (Biotek H1 M)
with a test wavelength of 570 nm and a reference wave-
length of 630 nm to obtain sample signal
(OD570 − OD630). For evaluation of cellular uptake,
HUVECs were plated in 6‐well cell culture plates at a cell
density of 7 × 105 cells per well. After leaving overnight,
cells were treated with the compounds at a concentration
of 200 μM and then the plates were transferred to a 37 °C
incubator for 4 h. After that fluorescence images were
SCHEME 2 Proposed pathway for
synthesis of complexes 1–4
TABLE 1 Spectroscopic data for compounds Y1, Y2 and 1–4
Compound
IR; ν(CO) (cm−1
)
1H NMR; δ(PCH) (ppm)
13C NMR; δ(CO) (ppm)
31P NMR; δ(PCH) and (PPh2) (ppm)
Y1
1
1572
1650
1651
1570
1618
1617
4.33
5.53
5.85
4.26
4.13
4.12
183.18
187.1
15.35, −29.48
13.18, 31.26
13.27, 40.42
17.18, −12.83
16.73, 17.69
16.46, 19.21
2
Y2
188.53
188.79
182.75
182.94
3
4

SABOUNCHEI ET AL.
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obtained at ×100 magnification using a fluorescence
microscope (Micros, Austria) with imaging system. Cells
without any treatment were taken as a staining control.
2.4 | Suzuki–Miyaura Coupling Reaction
In a general procedure, to a round‐bottom flask
equipped with a magnetic stirring bar a mixture of
Pd–[60]fullerene complex (0.005 mmol), phenylboronic
acid (1 mmol), aryl chloride (0.75 mmol) and K2CO3
(1.5 mmol) in dimethylformamide (DMF; 2 ml) was
added. The mixture was heated to 130 °C for 2 h in
the presence of air and the progress was monitored by
TLC. After completing the cross‐coupling reaction, the
mixture was diluted with n‐hexane–water (50:50). The
organic layer was washed with brine (15 ml) and dried
over CaCl2. The solvent was evaporated and the crude
product purified by recrystallization from ethanol and
water or purified by silica gel column chromatography
(n‐hexane–EtOAc, 80:20).
2.4.1 | Data for 4‐nitrobiphenyl (5a)
M.p. 112–113 °C. 1H NMR (89.6 MHz, CDCl3, δH,
ppm): 7.26–8.34 (m, 9H, phenyl). 13C NMR
(62.89 MHz, CDCl3, δC, ppm): 147.68, 146.97, 128.92,
127.84, 124.10.
2.4.2 | Data for 4‐phenylbenzaldehyde (5b)
1
M.p. 89–91 °C. H NMR (89.6 MHz, CDCl3, δH, ppm):
9.91 (s, 1H, CHO), 7.30–7.86 (m, 9H, phenyl). 13C NMR
(100.62 MHz, CDCl3, δC, ppm): 191.91 (s, CO), 147.09,
139.60, 135.07, 130.21, 128.95, 128.41, 127.60, 127.29.
2.4.3 | Data for biphenyl (5c)
1
M.p. 67–69 °C. H NMR (89.6 MHz, CDCl3, δH, ppm):
7.01–7.51 (m, 10H, phenyl). 13C NMR (100.62 MHz,
CDCl3, δC, ppm): 141.29, 128.8, 127.30, 127.22.
FIGURE 3 SEM images of (a) C60, and (b) complex 3(1 μm) and
(c) complex 3 (500 nm)
FIGURE 2 The UV–Vis spectral data of complexes 1–4

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SABOUNCHEI ET AL.
reaction of ylide Y2 with (C60Pd/Pt)n polymer led to for-
2.4.4 | Data for 4‐phenylcarboxylic acid
mation of the P‐coordinated complexes
3 and 4
(5d)
(Scheme 1).
1
M.p. 223–226 °C. H NMR (89.6 MHz, CDCl3, δH, ppm):
A view of the proposed pathway for the synthesis
of the Pd/Pt–[60]fullerene complexes is depicted in
Scheme 2. (i) Firstly, the black and insoluble polymer
(C60Pd/Pt)n was obtained from the reaction of C60 and
M(dba)2.[39] (ii) Terminal PPh2 group of phosphorus
ylides was coordinated to metallic centre of (C60M)n.
In the case of phosphorus ylide Y1, this was followed
11.03 (s, COOH, 1H), 7.31–7.88 (m, phenyl, 9H).
13C NMR (100 MHz, CDCl3, δC, ppm): 163.3 (s, C═O),
144.8 (s, phenyl), 139.8 (s, phenyl), 129.58 (s, phenyl),
129.13 (s, phenyl), 127.47 (s, phenyl), 126.9 (s, phenyl),
124.3 (s, phenyl).
2.4.5 | Data for 4‐acetylbiphenyl (5e)
1
M.p. 117–118 °C. H NMR (300 MHz, CDCl3, δH, ppm):
8.02–8.05 (m, phenyl, 2H), 7.62–7.70 (m, phenyl, 4H),
7.26–7.50 (m, phenyl, 3H), 2.64 (s, CH3, 3H). 13C NMR
(100 MHz, CDCl3, δC, ppm): 197.5 (s, C═O), 145.8 (s, phe-
nyl), 139.7 (s, phenyl), 135.6 (s, phenyl), 128.83 (s, phenyl),
128.79 (s, phenyl), 128.11 (s, phenyl), 127.15 (s, phenyl),
127.10 (s, phenyl), 26.7 (s, CH3).
3 | RESULTS AND DISCUSSION
3.1 | Synthesis
The synthetic procedure for target compounds 1–4 con-
sists of two steps. (1) Reaction of [60]fullerene with
M(dba)2 (M = Pd or Pt) which resulted in facile displace-
ment of the dba ligand and formation of black–brown
insoluble (C60Pd/Pt)n polymer.[37,38] (2) Further reaction
of phosphorus ylides with (C60Pd/Pt)n polymer which
led to formation of deep‐green solution of Pd/Pt–[60]ful-
lerene complexes. It is worth mentioning that reaction
of phosphorus ylide Y1 with (C60Pd/Pt)n polymer gave
the P,C‐coordinated complexes 1 and 2, whereas similar
FIGURE 5 A) Effects of compound 2 and 4 on the Human
umbilical vein endothelial cells viability. HUVEC cells were
incubated with different concentrations of the compounds for 24 h.
The cell proliferation inhibition was determined by MTT assay as
described under materials and methods. Data are presented as
mean S.E.M (n = 3). B) Fluoroescence microscope images
demonstrating the intracellular nanoparticles distribution in
HUVEC cell line. (a) Control cells incubated without compound. (b)
Cells exposed to compound 1 and (c) compound 2 for 4 h
FIGURE 4 Effects of compound 2 and 4 on the Human umbilical
vein endothelial cells viability. HUVEC cells were incubated with
different concentrations of the compounds for 24 h. The cell
proliferation inhibition was determined by MTT assay as described
under materials and methods. Data are presented as mean S.E.M
(n = 3)

SABOUNCHEI ET AL.
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by chelation of the ylide through carbon and forma-
tion of P,C‐coordinated complexes 1 and 2. (iii) In
the case of phosphorus ylide Y2, formation of P,C‐che-
lated complex is not favourable and a second ligand
was added which led to formation of P‐coordinated
complexes 3 and 4.
FIGURE 6 The optimized structure of
(η2‐C60)M(Y1), (η2‐C60)M(Y2), (η2‐C60)
M(Y1)2 and (η2‐C60)M(Y2)2 (M = Pd and
Pt) complexes
TABLE 2 Results of EDA (kcal mol−1) at BP86‐D3/TZP//BP86/LANL2MB level
Complex
Fragments
ΔEint
ΔEPauli
ΔEelec
ΔEorb
ΔEdisp
(η2‐C60)Pd(Y1)
(η2‐C60)Pd...(Y1)
(η2‐C60)...Pd(Y1)
−73.86
−64.26
135.10
156.70
−128.47 (61.5%)
−113.73 (51.5%)
−62.73 (30.0%)
−92.92 (42.1%)
−17.77 (8.5%)
−14.32 (6.5%)
(η2‐C60)Pt(Y1)
(η2‐C60)Pd(Y2)2
(η2‐C60)Pt(Y2)2
(η2‐C60)Pt...(Y1)
−104.47
−84.13
204.24
194.96
−186.00 (60.3%)
−138.63 (49.7%)
−102.25 (33.1%)
−123.03 (44.1%)
−20.45 (6.6%)
−17.42 (6.2%)
(η2‐C60)...Pt(Y1)
(η2‐C60)Pd...(Y3)2
(η2‐C60)...Pd(Y3)2
−74.56
−71.16
90.14
172.83
−88.06 (53.5%)
−125.46 (51.4%)
−49.74 (30.2%)
−95.86 (39.3%)
−26.91 (16.3%)
−22.68 (9.3%)
(η2‐C60)Pt...(Y3)2
−101.68
−101.53
127.15
225.84
−118.50 (51.8%)
−164.61 (50.3%)
−79.91 (34.9%)
−136.45 (41.7%)
−30.42 (13.3%)
−26.31 (8.0%)
(η2‐C60)...Pt(Y3)2

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SABOUNCHEI ET AL.
coordination to metal complexes. 1H NMR spectra of
complexes 1 and 2 displayed a downfield shift in methinic
proton signals, which suggests P,C‐coordination of ylide
Y1 in the Pd/Pt–[60]fullerene complexes. In contrast, the
chemical shift values of this signal for complexes 3 and
4 did not show any significant change and confirms
P‐coordination mode of ylide Y2 in Pd/Pt–[60]fullerene
complexes (see supporting information).
3.2 | Characterization
The products were identified with NMR (1H, 13C and 31P)
and IR spectroscopic methods and the data are summa-
rized in Table 1. These results provide a useful compari-
son between the data relating to parent phosphorus
ylides Y1 and Y2 and compounds 1–4.
Analogously, the 13C NMR spectra of complexes 1 and
2 showed a downfield shift in carbonyl signals, which
suggests the ligand has coordinated to the metal centre
in P,C‐coordinated form. However, these signals in the
13C NMR spectra of complexes 3 and 4 did not show
detectable chemical shift changes compared to those
observed for the parent ylide Y2, which indicates P‐
3.2.1 | IR spectra
By paying attention to the changes of ν(CO) region in the
IR spectra of complexes 1 and 2 compared to ylide Y1, it is
confirmed that coordination of the ylide has occurred
simultaneously through the ylidic carbon and PPh2
groups.[40] However, the IR spectra of complexes 3 and
4 did not show any significant frequency shift compared
to parent ylide Y2 which suggests that the coordination
of the ylide occurs only through the PPh2 groups (see
supporting information). Also, it is worth mentioning
that the IR spectra of all complexes displayed the charac-
teristic absorption bands of C60 core at around 526, 579,
TABLE 3 Controllable factors and their levels
Factor Description
Level 1 Level 2 Level 3
Level 4
B
S
Base
K2CO3 Cs2CO3 NaOAC
NaF
Solvent
DMF
Toluene Methanol THF
1184 and 1435 cm−1
.
C
Catalyst (mol%) 0.1
0.01
0.005
0.0005
3.2.2 | NMR spectra
TABLE 4 L16 orthogonal array and experimental results for
Suzuki–Miyaura reaction of chloronitrobenzene and phenylboronic
acid
One of the best available techniques for the study of coor-
dination modes of phosphorus ylides in these compounds
is 31P NMR spectroscopy. P,C‐coordination mode of phos-
phorus ylides leads to a large chemical shift for both PPh2
and bonded PCH phosphorus groups. In contrast, in the
case of P‐coordination mode of phosphorus ylide, only
the PPh2 moiety shows a significant higher frequency shift.
The 31P NMR spectra of complexes 1–4 show a downfield
shift for the signals due to the phosphine group compared
to parent ylides Y1 and Y2, which implies coordination of
the ylides. The 31P NMR spectrum of complex 1 shows
two doublet peaks at around 13.18 and 31.26 ppm, which
are assigned to PPh2 and PCH, respectively. However,
these two doublet peaks appeared in the 31P NMR spec-
trum of complex 3 at around 16.73 and 17.69 ppm with
the difference in that the second‐order AB pattern. Also
the 31P NMR spectrum of complex 2 displayed two doublet
peaks at around 13.27 and 40.42 ppm, along with two sat-
ellites due to 195Pt–31P coupling, which are assigned to
PPh2 and PCH, respectively. The 31P NMR spectrum of
complex 4 shows a different pattern with two doublet
peaks at around 16.46 and 19.21 ppm, along with two sat-
ellite peaks due to 195Pt–31P coupling, which are assigned
to PPh2 and PCH, respectively.
Factor
Run
B
S
C
Yield (%) S/N ratio
1
K2CO3
K2CO3
K2CO3
K2CO3
Cs2CO3
Cs2CO3
Cs2CO3
Cs2CO3
DMF
0.1000
98
88
86
72
90
82
88
84
84
84
88
84
84
84
80
82
39.8245
38.8897
38.6900
37.1466
39.0849
38.2763
38.8897
38.4856
38.4856
38.4856
38.8897
38.4856
38.4856
38.4856
38.0618
38.2763
2
Methanol 0.0100
3
Toluene
THF
0.0050
0.0005
0.0050
4
5
DMF
6
Methanol 0.0005
7
Toluene
THF
0.1000
0.0100
0.0005
8
9
NaOAC DMF
10
11
12
13
14
15
16
NaOAC Methanol 0.0050
NaOAC Toluene
NaOAC THF
0.0100
0.1000
0.0100
NaF
NaF
NaF
NaF
DMF
1H NMR spectroscopy can also be used to determine
the coordination mode of the ligands in complexes 1–4.
To do this, it is necessary to evaluate the chemical shift
of the signals due to the methinic proton during
Methanol 0.1000
Toluene
THF
0.0005
0.0050

SABOUNCHEI ET AL.
9 of 15
FIGURE 7 Main effect of each factor by S/N ratios
coordinated form of the ligand (see supporting informa-
tion). Characterization of the [60]fullerene skeleton in
13C NMR spectra of all complexes was also confirmed
by observation of signals at around 141–147 ppm.
and 4 using the MTT method as described in Section 2.3.
As shown in Figure 4, neither compound was able to
induce cytotoxicity in normal HUVECs, up to a concen-
tration of 200 μM.
3.2.3 | UV–visible spectra
TABLE 5 Results of ANOVA
Electronic absorption spectra for solutions of the all
complexes suggest the complexation of Pd and Pt
through η2‐coordination on the C60 cage. Figure 2 shows
the UV–visible spectra of complexes 1–4. The most char-
acteristic bands observed in the spectra of complexes 1–4
are the metal‐to‐ligand charge transfer bands at 316, 324
and 364 nm.
Source DFa Seq. SSb Adj. SSc Adj. MSd Fe
ρ (%)
B
3
3
62.75
166.75
140.75
32.75
62.75
166.75
140.75
32.75
20.9167
55.5833
46.9167
7.5833
3.21374 13.83
6.45055 36.75
4.68132 31.02
S
C
3
Error
Total
3
15
453.75
aDF: degrees of freedom.
bSeq. SS: sequential sum of squares.
cAdj. SS: adjusted sum of squares.
dAdj. MS: adjusted mean of squares.
eF: variance ratio.
3.2.4 | Scanning electron microscopy
SEM images of pure C60 and complex 3 are presented in
Figure 3. It can be observed from the SEM image
(Figure 3a) that the C60 particles were irregular in shape.
The size of particles was inhomogeneous, covering a
range from 50 to 100 nm. The particles were so strongly
aggregated that discrete particles were impossible to find
and an average particle size was difficult to obtain. It
can be observed from the SEM image that the surface of
pure C60 crystals is quite smooth. However, the surface
of complex 3 (Figure 3b,c) is different and the entire sur-
face loses the smoothness.
3.3 | Cytotoxicity and Cellular Uptake
Assay
The viability of normal HUVECs was evaluated after 24 h
of exposure to various concentrations of compounds 2
FIGURE 8 Contribution percentageρ of factors for yield of
Suzuki‐Miyaura coupling reaction

10 of 15
SABOUNCHEI ET AL.
Pt–cyclopropa[60]fullerene complexes are used as a
similar to our previous work and based on experimental
observations for similar complexes, we have assumed that
the Pd atom is only attached to a [6,6]‐double bond.
In continuation, the ADF 2013 program with energy
decomposition analysis (EDA) was employed. We studied
the nature of the palladium–C60(fragment A), palladium–
Y(fragment B), platinum–C60(A) and platinum–Y(B)
bonds in (η2‐C60)Pd(Y1), (η2‐C60)Pd(Y3), (η2‐C60)Pd(Y1)2,
(η2‐C60)Pd(Y3)2, (η2‐C60)Pt(Y1), (η2‐C60)Pt(Y3), (η2‐C60)
Pt(Y1)2 and (η2‐C60)Pt(Y3)2 complexes at the BP86‐D3/
TZP//BP86/LANL2DZ level of theory. In general, EDA
decomposes the interaction energy between two consid-
ered fragments A and B into four terms which can be
interpreted in a chemically meaningful way. The four
terms are the quasi‐classical electrostatic interaction
between the frozen charges of the fragments (ΔEelec); the
exchange (Pauli) repulsion between electrons possessing
the same spin (ΔEPauli); the orbital interaction term
(ΔEorb); and the dispersion contributions (ΔEdisp).
platform for effective drug delivery to molecular targets
in tumour cells.[32] However, in vitro and in vivo detection
of these nanomaterials is limited by their very low fluores-
cence quantum yield. The accumulation of fullerene and
its derivatives in cells is particularly difficult to measure
using standard fluorescence microscopy because their
fluorescence is barely detectable as a result of their low sol-
ubility.[27] Use of specific Pt–cyclopropa[60]fullerene com-
plexes for targeted delivery of drugs to tumour cells is one
of the most appropriate ways for reducing the severe toxic-
ity of conventional anticancer drugs towards normal tis-
sues. In the current study, fluorescence microscopy
images after 4 h incubation at 200 μM showed almost
every cell was stained green with clear cell borders, indi-
cating a very effective uptake of these complexes
(Figure 5). Taken together, these results showed that the
new Pd/Pt–cyclopropa[60]fullerene complexes can be
used as non‐toxic labels for cellular imaging application.
The EDA results are presented in Table 2. Our calcula-
tions indicate that in all (η2‐C60)MY complexes (M = Pt or
Pd; Y = Y1 or Y3) the interaction energy values, ΔEint,
between (η2‐C60)M and Y fragment are larger than those
between (η2‐C60) and MY fragment. The results also show
that the total interaction energies, ΔEint, of both (η2‐C60)
―MY and (η2‐C60)M―Y bonds in Pt complexes are larger
than those in corresponding Pd complexes. As can be seen
in Table 2, the values of all ΔEPauli, ΔEelec, ΔEorb and ΔEdisp
terms for both (η2‐C60)―MY and (η2‐C60)M―Y bonds in Pt
complexes are larger than those in corresponding Pd com-
plexes. Indeed, the larger interaction energy in Pt com-
plexes, in comparison with Pd complexes, is the result of
the considerably larger values of ΔEelec and ΔEorb terms
for Pt complexes. On the other hand, the percentage contri-
butions of ΔEorb and ΔEelec in total interaction energy for Pt
complexes do not differ considerably from those for
corresponding Pd complexes. However, in both Pt and Pd
complexes the percentage contribution of ΔEelec in
total interaction energy is considerably larger than that of
3.4 | Theoretical Study
Recently, we investigated the nature of the metal–ligand
bond in some palladacyclopropa[60]fullerene complexes.
Herein, we study the nature of the bonding in some similar
palladium complexes using density functional theory. All
geometry optimizations in this study were performed with
the Gaussian 09 program.[41] Geometry optimization of
(η2‐C60)M(Y1), (η2‐C60)M(Y2), (η2‐C60)M(Y1)2 and (η2‐C60)
M(Y2)2 (M = Pd or Pt) complexes was carried out at the
BP86/LANL2MB level of theory and the optimized com-
plexes are shown in Figure 6. The Cartesian atomic coordi-
nates of all compounds are reported in the supporting
information. We note that in these complexes the Pd and
Pt atoms can be coordinated to two different types of
C―C bonds in the C60 molecule. In fact, in the C60 struc-
ture there are two types of bonds: the bonds at the junction
of two hexagons, [6,6]‐bonds, and those between one
pentagon and one hexagon, [5,6]‐bonds. In this study,
FIGURE 9 The response graph
illustrating the variation of the mean yield
values plotted against various extraction
parameters

SABOUNCHEI ET AL.
11 of 15
ΔEorb. Thus, in agreement with results of our previous stud-
ies, in all complexes the (η2‐C60)M―(Y1) bond is consider-
ably more electrostatic in nature than the (η2‐C60)―M(Y1)
bond.
this work, the orthogonal array, signal‐to‐noise ratio
and analysis of variance were employed to study the per-
formance characteristics on response.[42] The Taguchi
method is a statistical approach to optimize the process
parameters and expanded to improve the performance
of total quality control.[43] The Taguchi method involves
identification of appropriate control factors to obtain the
optimum results of a process. Orthogonal arrays were
used to conduct a set of experiments. To select an appro-
priate orthogonal array for conducting the experiments,
the degrees of freedom were computed. Three selected
As we saw in Section 2, the ylides Y1 and Y2 form P,C‐
and P,P‐coordinated complexes (η2‐C60)M(Y1) and
(η2‐C60)M(Y2)2, respectively. In order to explain the
difference between the complexes of Y1 and Y2 with
(η2‐C60)M, we studied reactions (1) and (2) for Pd com-
plexes and reactions (3) and (4) for Pt complexes:
À
Á
À
Á
À
Á
À
Á
η2−C60 Pd Y1 þ Y1→ η2−C60 Pd Y1
ΔE ¼ 7:53 kcal mol−1
(1)
(2)
(3)
(4)
2
À
Á
À
Á
À
Á
À
Á
η2−C60 Pd Y2 þ Y2→ η2−C60 Pd Y2
ΔE ¼ −4:25 kcal mol−1
2
À
Á À
Á
À
Á À
Á
η2−C60 Pt Y1 þ Y1→ η2−C60 Pt Y1
ΔE ¼ 15:27 kcal mol−1
2
À
Á À
Á
À
Á
À
Á
η2−C60 Pt Y2 þ Y2→ η2−C60 Pt Y2
ΔE ¼ 3:14 kcal mol−1
2
We note that in the above reactions Y1 and Y2 are
added to P,C‐coordinated (η2‐C60)M(Y1) and (η2‐C60)
M(Y2) (M = Pd or Pt) complexes and the P,P‐coordinated
(η2‐C60)M(Y1)2 and (η2‐C60)M(Y2)2 complexes are pro-
duced, respectively. As can be seen in the case of Y2 the
formation of P,P‐coordinated (η2‐C60)M(Y2)2 is more
favoured. Note that both the above reactions are
entropy‐disfavoured, thus only in the case of exothermic
reaction (2) can we be sure that the change of Gibbs free
energy of reaction has a negative value. Thus in the case
of ylide Y2 after formation of (η2‐C60)M(Y2) complex the
second molecule of ylide is added to the complex and a
P,P‐coordinated complex, (η2‐C60)M(Y2)2, is formed.
Indeed, the six‐membered P,C‐chelate ring in (η2‐C60)
M(Y2) complex is not stable enough and the second mol-
ecule of ylide will be easily added to the complex.
3.5 | Catalytic Activity
3.5.1 | Optimization of reaction using
Taguchi method
The catalytic activity of palladacyclopropa[60]fullerene
complexes 1 and 3 in Suzuki–Miyaura coupling reactions
of aryl chlorides with phenylboronic acid was then exam-
ined. Initially, we set up a systematic optimization of
reactions using a Taguchi L16 experimental design. In
FIGURE 10 Response surface plots for the interaction between
factors

12 of 15
SABOUNCHEI ET AL.
factors, base (B), solvent (S) and catalyst loading (C), were
used with their levels (Table 3).[44]
orthogonal experiment. To determine the optimum con-
ditions for yield of experiments, we used the relationship
between each parameter and the percentage contribution
ρ and ANOVA.[46–48] F‐statistics illustrates the signifi-
cance of each factor on the response quality.
The most suitable orthogonal array for experimenta-
tion is an L16 array as presented in Table 4. Therefore,
a total 16 experiments were carried out. In contrast, the
full factorial experimental design requires 34 = 81 differ-
ent experiments to evaluate the influencing factors.
Results of these experiments were used to analyse the
data and predict the quality of components produced.
Table 4 presents the required experiments to optimize
the batch system which were designed using the Taguchi
method. Initially, we carried out a model reaction to opti-
mize the reaction conditions including solvent, base and
catalyst loading. In each run, commonly used bases and
solvents, including organic and inorganic bases and polar
protic solvents and non‐polar aprotic solvents, were
investigated. Also, different amounts of catalyst loadings
(mol%) were used at different temperatures to find opti-
mum reaction conditions. All experiments were repeated
and the yield percentage of reaction was calculated for
each experiment.[45]
We applied the signal‐to‐noise (S/N) ratio to evaluate
the experimental data. The S/N ratio analysis chosen was
the‐larger‐the‐better.[45] According to the values of mean
S/N ratio shown in Table 4, the optimum level of each fac-
tor was determined from the highest value of S/N ratio and
the results are exhibited in Figure 7. The optimum condi-
tions were found to be base: K2CO3, Cs2CO3; solvent:
DMF, toluene; catalyst loading: 0.005, 0.01 and 0.1 mol%.
Analysis of variance (ANOVA) was used to evaluate
the response magnitude (%) of each parameter in the
Table 5 presents the ANOVA results obtained from
experimental data. The solvent with the highest F‐value
of 6.45 has the highest percentage contribution (36.75%)
to the yield. Moreover, catalyst loading and base play
important roles in the yield with F‐value and percentage
contribution. Based on Table 5, solvent has the largest
pure sum of squares and largest percentage contribution
to the yield of Suzuki–Miyaura coupling reaction. There-
fore, it was concluded that solvent is the most important
factor affecting the yield. The percentage contribution of
each factor is shown in Figure 8. Also, the variation of
the mean yield values against various extraction parame-
ters is shown in Figure 9.
The surface plots shown in Figure 10 should be of
help in better finding out the interaction effects of the
experimental factors on the yield percentage. The interac-
tion effect of solvent and catalyst loading, as shown in
Figure 10(a), indicates that polar solvents such as DMF
were more efficient for the yield of compounds up to
98%, while a polar aprotic solvent gave a comparatively
good yield and the lowest yield (72%) was obtained with
tetrahydrofuran (THF) as solvent. This could be due to
the reflux temperature of the solvent, and with an
increase in catalyst loading, the yield percentage
increased. Also, the interaction surface plot of the base
and catalyst loading is shown in Figure 10(b). The effect
TABLE 6 Suzuki–Miyaura coupling reaction of functionalized aryl chloridesa
Entry
R
Catalyst
Product
Yield (%)b
1
2
NO2
NO2
1
3
4‐Nitrobiphenyl (5a)
93
90
3
4
CHO
CHO
1
3
4‐Phenylbenzaldehyde (5b)
Biphenyl (5c)
97
92
5
6
H
H
1
3
85
80
7
8
COOH
COOH
1
3
4‐Phenylcarboxylic acid (5d)
4‐Acetylbiphenyl (5e)
95
92
9
10
COCH3
COCH3
1
3
90
86
aReaction conditions for Suzuki–Miyaura coupling reaction: aryl chloride (0.5 mmol), phenylboronic acid (0.75 mmol), K2CO3 (1 mmol), DMF (2 ml), catalyst
(0.005 mol%), 130 °C, 2 h, in air.
bIsolated yield.

SABOUNCHEI ET AL.
13 of 15
of various mineral bases on this reaction was investigated
and results showed that inorganic bases were much better
than organic ones, where K2CO3 was the best choice of
base and the yield of product could be increased to 98%.
The interaction effect of base and solvent is considered in
Figure 10(c). Therefore, the optimal conditions for
Suzuki–Miyaura coupling reaction of aryl chlorides and
phenylboronic acid catalysed by complexes 1 and 3 are
as follows: base: K2CO3; solvent: DMF; catalyst loading:
0.005 mol%.
3.5.2 | Suzuki–Miyaura coupling reaction
of functionalized aryl chlorides
In order to compare the catalytic activity of complexes of
1 and 3, they were applied using the same reaction condi-
tions. Functionalized aryl chlorides bearing electron‐
withdrawing groups reacted with phenylboronic acid,
and corresponding coupled products were obtained in
high to excellent yields (Table 6). As expected, reaction
of 4‐chlorobenzaldehyde with phenylboronic acid gave
the desired product in highest yield. Also, the lowest con-
versions were observed in reaction of phenylboronic acid
and 4‐chlorobenzene as a neutral aryl chloride which
does have not strong electron‐withdrawing groups. Each
of the pair of complexes 1 and 3 exhibited good catalytic
activity, attributed to the Pd(0) core of their molecular
structures, but the catalytic activity of 1 was higher than
that of 3. The fact that Pd(0) species in P,C‐coordinated
complex 1 is more efficient than that in P‐coordinated
complex 3 may be due to difference in coordination
modes of their phosphorus ylide ligands.
An implicit mechanism of the Suzuki–Miyaura cou-
pling reaction is proposed by comparison with literature
reports to illustrate the role of ligand in various observed
efficiencies (Scheme 3).[49–51] Initially, the complexes lose
C60 in solution necessary to generate coordinatively
unsaturated LnPd0 catalyst (A). This step is followed by
oxidative addition of the aryl chloride, which is often
the rate‐determining step in C―C coupling catalytic
cycles (B).[52,53] The phosphine is a σ‐donor/π‐acceptor
SCHEME 3 Proposed mechanism for Suzuki–Miyaura reaction
catalysed by 1 and 3
TABLE 7 Comparison of Suzuki–Miyaura coupling reaction of chlorobenzene and phenylboronic acid using complexes 1 and 3 with that
using other catalytic systems
Catalyst
Entry
Pd source
loading (mol%)
Condition
Yield (%)
Ref.
[58]
1
Binuclear palladated
triphenylphosphine
derivative
0.5
K2CO3, DMF/H2O, 100 °C, 1 h
85
[59]
[60]
2
3
4
Pd(II) complex of nitrogen‐
containing bis(phosphinite)
0.1
3
K3PO4, DMF, 25 °C, 24 h
K2CO3, DMA, 95 °C, 1.5 h
K2CO3, DMF, 130 °C, 2 h
90
97
93
Pd(II) complex of sulfonated
diimine
P,C‐coordinated
Pd–cyclopropa[60]fullerene
complex
0.005
This work
This work
5
P‐coordinated
0.005
K2CO3, DMF, 130 °C, 2 h
90
Pd–cyclopropa[60]fullerene
complex

14 of 15
SABOUNCHEI ET AL.
ligand and it can decrease electron density on the metal
with an additional π‐interaction (π‐backbonding).[54]
The carbene has strong σ‐donor and relatively weak π‐
acceptor interactions and it can increase the electron den-
sity on the metal centre,[55] which destabilizes the car-
bon–halogen bond, leading to faster cleavage and
eventually oxidative addition to Pd. The catalytic cycle
is continued by a transmetallation step, in which an aryl
group transfers to Pd centre from the organoboron com-
pound, activated by K2CO3 base (C).[56] Finally, reductive
elimination of intermediate C produces the desired cou-
pling product and regenerates the LnPd0 active catalyst
which starts another catalytic cycle.[57]
ACKNOWLEDGEMENT
Funding of our research from Bu‐Ali Sina University is
gratefully acknowledged.
ORCID
Seyyed Javad Sabounchei
9000-5304
Sadegh Salehzadeh http://orcid.org/0000-0003-2840-1896
Farahnaz Maleki http://orcid.org/0000-0002-5747-1319
Leila Hosseinzadeh http://orcid.org/0000-0003-0536-3209
http://orcid.org/0000-0001-
A comparison between the catalytic activities of the
present complexes and other Pd catalysts having different
ancillary ligands in Suzuki–Miyaura reaction was carried
out. The results indicated that the differences in catalytic
behaviour presented in Table 7 should be ascribed not
only to the differences in the experimental conditions
(e.g. effects of solvent, base, temperature and catalyst
loading), but also mainly attributed to the characteristic
differences in the Pd content. The donor atoms of ligands
have a substantial effect on stabilization and conse-
quently on the performance of Pd catalyst and the
ligand‐controlling conditions are clearly obvious in such
catalytic reactions carried out under similar experimental
conditions.
REFERENCES
[1] H. W. Kroto, J. R. Heath, S. C. Brien, R. F. Curl, R. E. Smalley,
Nature 1985, 318, 162.
[2] A. V. Eletskii, Physics‐Uspekhi 2000, 43, 170.
[3] R. J. Patterson, A. S. Catledge, Y. K. Vohra, Phys. Rev. Lett.
2000, 85, 5364.
[4] A. Goel, P. Hebgen, J. B. V. Sande, J. B. Howard, Carbon 2002,
40, 177.
[5] J. Bernholc, D. Brenner, M. B. Nardelli, V. Meunier, C. Roland,
Annu. Rev. Mat. Res. 2002, 32, 347.
[6] S. Bronnikov, A. Podshivalov, S. Kostromin, M. Asandulesa, V.
Cozan, Phys. Lett. A 2017, 381, 796.
[7] S. Filippone, N. Martin, in Encyclopedia of Polymeric
Nanomaterials, (Eds: S. Kobayashi, K. Müllen), Springer,
Berlin 2015 755.
[8] A. A. Popov, S. Yang, L. Dunsch, Chem. Rev. 2013, 113, 5989.
[9] D. Soto, R. Salcedo, Molecules 2012, 17, 7151.
4 | CONCLUSIONS
[10] T. M. Figueira‐Duarte, A. Gegouta, J. F. Nierengarten, Chem.
Commun. 2007, 109.
The present study describes the synthesis and characteri-
zation of new Pd/Pt–cyclopropa[60]fullerene complexes
containing unsymmetric phosphorus ylides. According
to the results of NMR (1H, 13C and 31P), IR, UV–visible
and SEM analyses, the structures of products were suc-
cessfully characterized experimentally and theoretically.
The results indicate that the phosphorus ylide Y1 coordi-
nates to Pd and Pt in P,C‐coordinated form, while phos-
phorus ylide Y2 coordinates to these metal centres
through free phosphorus atom as P‐coordinated form.
Also, the results of cytotoxicity and cellular uptake assay
of Pt complexes 2 and 4 showed that nanoparticles of
these complexes can be used as non‐toxic labels for cellu-
lar imaging application. Furthermore, Pd complexes 1
and 3 were applied as efficient catalysts in Taguchi‐opti-
mized Suzuki–Miyaura coupling reactions of various aryl
chlorides and phenylboronic acid, resulting in good to
excellent yields of coupled products. The results also indi-
cated that the Taguchi method is a suitable approach for
optimization of parameters in Suzuki–Miyaura coupling
reactions.
[11] J. M. Campanera, J. Munoz, J. Vazquez, C. Bo, J. M. Poblet,
Inorg. Chem. 2004, 43, 6815.
[12] B. C. Thompson, J. M. J. Fréchet, Angew. Chem. Int. Ed. 2008,
47, 58.
[13] L.‐C. Song, G.‐A. Yu, F.‐H. Su, Q.‐M. Hu, Organometallics 2004,
23, 4192–4198.
[14] L.‐C. Song, G.‐A. Yu, H.‐T. Wang, F.‐H. Su, Q.‐M. Hu, Y.‐L.
Song, Y.‐C. Gao, Eur. J. Inorg. Chem. 2004, 866.
[15] L.‐C. Song, G.‐A. Yu, Q.‐M. Hu, C.‐M. Che, N. Zhu, J.‐S.
Huang, J. Org. Chem. 2006, 691, 787.
[16] J. S. Fletcher, N. P. Lockyer, J. C. Vickerman, Surf. Interface
Anal. 2006, 38, 1393.
[17] R. Bakry, R. M. Vallant, M. Najam‐ul‐Haq, M. Rainer, Z. Szabo,
C. W. Huck, G. K. Bonn, Int. J. Nanomedicine 2007, 2, 639.
[18] S. J. Sabounchei, M. Ahmadi, Z. Nasri, E. Shams, S.
Salehzadeh, Y. Gholiee, R. Karamian, M. Asadbegy, S. Samiee,
C. R. Chim. 2013, 16, 159.
[19] S. J. Sabounchei, M. Hosseinzadeh, M. Panahimehr, D.
Nematollahi, H. R. Khavasi, S. Khazalpour, Transition Met.
Chem. 2015, 40, 657.

SABOUNCHEI ET AL.
15 of 15
[20] S. J. Sabounchei, H. Nemattalab, S. Salehzadeh, S. Khani, M.
[43] A. Schoonen, M. T. Schoonen, J. Colloid Interface Sci. 2014, 422, 1.
Bayat, H. R. Khavasi, Polyhedron 2008, 27, 2015.
[44] E. O. Doebelin, D. N. Manik, Measurement Systems: Applica-
tion and Design, Tata McGraw‐Hill, New Delhi 2007.
[21] S. J. Sabounchei, S. Samiee, M. Pourshahbaz, S. Salehzadeh, M.
Bayat, D. Nematollahi, R. Karamian, M. Asadbegy, J. Chem.
Res. 2014, 38, 35.
[45] J. Zolgharnein, N. Asanjarani, T. Shariatmanesh, Int. Biodeter.
Biodegr. 2013, 85, 66.
[22] S. J. Sabounchei, M. Zamanian, M. Pourshahbaz, M. Bayat, R.
[46] B. Ramavandi, G. Asgari, J. Faradma, S. Sahebi, B. Roshani,
Karamian, M. Asadbegy, J. Chem. Res. 2016, 40, 130.
Korean J. Chem. Eng. 2014, 31, 2207.
[23] S. J. Sabounchei, M. Sarlakif, S. Salehzadeh, M. Bayat, M.
[47] C. S. Chou, R. Y. Yang, J. H. Chen, S. W. Chou, Powder
Technol. 2010, 199, 264.
Pourshahbaz, H. R. Khavasi, Polyhedron 2012, 38, 131.
[24] E. P. Urriolabeitia, Dalton Trans. 2008, 42, 5673.
[48] N. J. Cox, J. Warburton, A. Armstrong, V. J. Holliday, Earth
Surf. Process. Landf. 2008, 33, 25.
[25] J. Vicente, M. T. Chicote, J. Fernandez‐Baeza, F. J. Lahoz, J. A.
Lopez, Inorg. Chem. 1991, 30, 3617.
[49] A. Suzuki, J. Org. Chem. 1999, 576, 147.
[26] N. F. Goldshleger, Fullerene Sci. Technol. 2001, 9, 255.
[50] S. Kozuch, J. M. L. Martin, ACS Catal. 2011, 1, 246.
[27] H. Veisi, R. Masti, D. Kordestani, M. Safaei, O. Sahin, J. Mol,
[51] C. Len, S. Bruniaux, F. Delbecq, V. S. Parmar, Catalysts 2017, 7,
Catal. A 2014, 385, 61.
146.
[28] A. Fihri, M. Bouhrara, B. Nekoueishahraki, J. M. Basset, V.
[52] R. Martin, S. L. Buchwald, Acc. Chem. Res. 2008, 41, 1461.
Polshettiwar, Chem. Soc. Rev. 2011, 40, 5181.
[53] M. G. Speziali, A. G. Marques da Silva, D. M. Vaz de Miranda,
A. L. Monteiro, P. A. Robles‐Dutenhefner, Appl. Catal. A 2013,
462, 39.
[29] F. Giacalone, V. Campisciano, C. Calabrese, V. La Parola, Z.
Syrgiannis, M. Prato, M. Gruttadauria, ACS Nano 2016, 10,
4627.
[54] M. P. Mitoraj, A. Michalak, Inorg. Chem. 2010, 49, 578.
[30] Z. Zhang, T. Sun, C. Chen, F. Xiao, Z. Gong, S. Wang, ACS
Appl. Mater. Interfaces 2014, 6, 21035.
[55] N. S. Antonova, J. J. Carbo, J. M. Poblet, Organometallics 2009,
28, 4283.
[31] R. R. Panchuk, S. V. Prylutska, V. V. Chumak, N. R.
Skorokhyd, L. V. Lehka, M. P. Evstigneev, I. Prylutskyy Yu,
W. Berger, P. Heffeter, P. Scharff, U. Ritter, R. S. Stoika,
J. Biomed. Nanotechnol. 2015, 11, 1139.
[56] J. M. Neely, M. J. Bezdek, P. J. Chirik, ACS Cent. Sci 2016, 2,
935.
[57] R. Jana, T. P. Pathak, M. S. Sigman, Chem. Rev. 2011, 111, 1417.
[58] S. Yasar, C. Sahin, M. Arslan, I. Ozdemir, J. Org. Chem. 2015,
776, 107.
[32] A. Andreoni, L. Nardo, M. Bondani, B. Zhao, J. E. Roberts,
J. Phys. Chem. 2013, 117, 7203.
[59] N. Shahnaz, B. Banik, P. Das, Tetrahedron Lett. 2013, 54, 2886.
[60] M. Thimmaiah, S. Fang, Tetrahedron 2007, 63, 6879.
[33] S. K. Sharma, L. Y. Chiang, M. R. Hamblin, Nanomedicine
2011, 6, 1813.
[34] I. Yanov, J. Leszczynski, E. Sulman, V. Matveeva, N. Semagina,
Quantum Chem. 2004, 100, 810.
SUPPORTING INFORMATION
[35] J. T. Tsai, T. K. Liu, J. H. Chou, IEEE Trans. Evol. Comput.
2004, 8, 365.
Additional Supporting Information may be found online
in the supporting information section at the end of the
article.
[36] S. J. Sabounchei, S. Samiee, S. Salehzadeh, Z. Bolboli Nojinib, I.
Erranc, J. Org. Chem. 2010, 695, 1441.
[37] Y. C. Lin, H. H. Hsueh, S. Kanne, L. K. Chang, F. C. Liu, I. J. B.
Lin, G. H. Lee, S. M. Peng, Organometallics 2013, 32, 3859.
How to cite this article: Sabounchei SJ, Badpa
K, Hashemi A, Salehzadeh S, Maleki F,
[38] M. R. Smith, Y. J. Jang, J. Y. Kim, M. A. Ciufolini, Tetrahedron
2013, 69, 10139.
Hosseinzadeh L. Synthesis, characterization and
theoretical and fluorescence emission microscopy
studies of new Pd/Pt–cyclopropa[60]fullerene
complexes: Application of Taguchi method for
optimization of parameters in Suzuki–Miyaura
reaction. Appl Organometal Chem. 2018;e4382.
https://doi.org/10.1002/aoc.4382
[39] L. Nagashima, H. Nakaoka, A. Tajima, S. Saito, Y. Itoh, Chem.
Lett. 1992, 21, 1361.
[40] M. Kalyanasundari, K. Panchanatheswaran, W. T. Robinson,
H. Wen, J. Org. Chem. 1995, 491, 103.
[41] M. J. Frisch, Gaussian 09, Revision A.02, Gaussian Inc.,
Wallingford, CT, 2009.
[42] S. Athreya, Y. D. Venkatesh, Int. Ref. J. Eng. Sci. (IRJES) 2012,
1, 13.