C-S cross-coupling reactions catalyzed by a non-symmetric phosphinito-thiophosphinito PSCOP-Ni(II) pincer complex

Article abstract of DOI:10.1016/j.tetlet.2018.07.063

A new non-symmetric phosphinito-thiophosphinito POCSP-Ni(II) pincer compound was synthetized and characterized. The molecular structure of [NiCl{C₆H₃-2-(OPPh₂)-6-(SPPh₂)}] (1) was unequivocally determined by single crystal X-ray diffraction analysis, showing the Ni center to be located into a slightly distorted square planar geometry. This compound was used as efficient catalyst in C-S couplings of disulfides with iodobenzenes, exhibiting good activity and selectivity as well as tolerance to different functional groups.

Full text of DOI:10.1016/j.tetlet.2018.07.063

Accepted Manuscript
C-S Cross-Coupling Reactions Catalyzed by a Non-Symmetric Phosphinito-
Thiophosphinito PSCOP-Ni(II) Pincer Complex
Juan M. Serrano-Becerra, Hugo Valdés, Daniel Canseco-González, Valente
Gómez-Benítez, Simón Hernández-Ortega, David Morales-Morales
PII:
S0040-4039(18)30956-0
https://doi.org/10.1016/j.tetlet.2018.07.063
TETL 50172
DOI:
Reference:
Tetrahedron Letters
To appear in:
Received Date:
Revised Date:
Accepted Date:
4 June 2018
17 July 2018
28 July 2018
Please cite this article as: Serrano-Becerra, J.M., Valdés, H., Canseco-González, D., Gómez-Benítez, V.,
Hernández-Ortega, S., Morales-Morales, D., C-S Cross-Coupling Reactions Catalyzed by a Non-Symmetric
Phosphinito-Thiophosphinito PSCOP-Ni(II) Pincer Complex, Tetrahedron Letters (2018), doi: https://doi.org/
10.1016/j.tetlet.2018.07.063
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C-S Cross-Coupling Reactions Catalyzed by
a Non-Symmetric Phosphinito-
Thiophosphinito PSCOP-Ni(II) Pincer
Complex.
Leave this area blank for abstract info.
Juan M. Serrano-Becerra, Hugo Valdés, Daniel Canseco-González, Valente Gómez-Benítez, Simón Hernández-
Ortega and David Morales-Morales

1
Tetrahedron Letters
C-S Cross-Coupling Reactions Catalyzed by a Non-Symmetric Phosphinito-
Thiophosphinito PSCOP-Ni(II) Pincer Complex.
Juan M. Serrano-Becerraa, Hugo Valdésa, Daniel Canseco-Gonzálezb,*, Valente Gómez-Benítezc, Simón
Hernández-Ortegaa and David Morales-Moralesa,*
aInstituto de Química, Universidad Nacional Autónoma de México, Circuito Exterior, Ciudad Universitaria, Ciudad de México, C.P. 04510, México.
bCONACYT-Laboratorio Nacional de Investigación y Servicio Agroalimentario y Forestal, Universidad Autónoma Chapingo, Texcoco de Mora, México.
cFacultad de Ciencias Químicas, Universidad Autónoma de Chihuahua. Circuito Universitario S/N. Chihuahua, Chihuahua, C. P. 31125. México.
ARTICLE INFO
ABSTRACT
Article history:
Received
Received in revised form
Accepted
A new non-symmetric phosphinito-thiophosphinito POCSP-Ni(II) pincer compound was
synthetized and characterized. The molecular structure of [NiCl{C6H3-2-(OPPh2)-6-(SPPh2)}]
(1) was unequivocally determined by single crystal X-ray diffraction analysis, showing the Ni
center to be located into a slightly distorted square planar geometry. This compound was used as
efficient catalyst in C-S couplings of disulfides with iodobenzenes, exhibiting good activity and
selectivity as well as tolerance to different functional groups.
Available online
Keywords:
2009 Elsevier Ltd. All rights reserved.
Keyword_1 PSCOP-pincer complex
Keyword_2 nickel complexes
Keyword_3 C-S cross-coupling
Keyword_4 non-symmetric pincer compounds
Keyword_5 thioetherification reaction
1. Introduction
compound and its use as efficient catalysts in C-S couplings of
disulfides with iodobenzenes.
Pincer complexes have played a protagonist role in catalysis
for the last two decades, this being greatly due to their high
stability and reactivity and easy functionalization. Thus, these
compounds have been widely used as efficient catalysts in
reactions where difficult to activate bonds are involved, standing
out their use in C-H activation processes and cross coupling
reactions, among many other applications.1-21 In spite if this, their
use as catalyst for C-S cross-coupling reactions has been little
explored.22-24
N
N
O
O
N
Ni
N
S
Ni
S
R2P
Ni
Cl
PR2
ArF
ArF
R
R
Cl
Cl
Cl
Cl
O
S
C-S cross-coupling is an important process for industry,
because these reactions can provide access to simple procedures
for the production of some biological and medicinal relevant
substances such as herbicides and drugs.25 This catalytic reaction
has been promoted by different transition metals like Co,26 Pd,27-
29 Cu30-32 and Ni33-36. In this line, our group has described some
relevant examples of catalysts based on pincer complexes
capable to promote C-S cross-coupling reactions. Figure 1 shows
some of them based on NNN,37,38 SNS,39 SPS40 and POCOP41
pincer complexes. However, in recent years a trend to use non-
symmetric pincer compounds16 as catalysts has become more
popular since this species may provide enhanced reactivities
compared to their symmetric counterparts, but their use has been
often hampered by the long and low yield synthetic procedures to
attain these species. Thus, following our continuous interest in
the development of pincer complexes and their applications as
efficient catalysts in different transformations, here we described
the facile, high yield synthesis and characterization of a new non-
symmetric phosphinito-thiophosphinito POCSP-Ni(II) pincer
Ph2P
Ni
PPh2
P
Cl
S Ni S
PAr3
(1)
this work
Figure 1. Examples of pincer complexes used for C-S cross-
coupling.
2. Results and discussion
2.1 Synthesis and characterization of [NiCl{C6H3-2-(OPPh2)-6-
(SPPh2)}] (1)42
The synthesis of the phosphinito-thiophosphinito POCSP-
Ni(II) pincer complex was performed in a single step starting
from 3-mercaptophenol (Scheme 1).43 The reaction of 3-
mercaptophenol with chlorodiphenylphosphine in the presence of
triethylamine affords the pincer ligand precursor (A) which upon

2
Tetrahedron
reaction with NiCl2 under reflux conditions produced complex
Figure 2. Molecular structure of (1). Selected bond lengths (Å): Ni–
C1A 1.913(7), Ni–C1B 1.867(11), Ni–Cl 2.198(1), Ni–P1 2.160(1),
Ni–P2 2.163(1), P1–O1A 1.649(8), P1–S1B 2.054(5), P2–S1A
2.149(2), P2–O1B 1.534(9). Selected bond angles (º): C1A–Ni–Cl
177.4(9), C1B–Ni–Cl 177.6(8), C1A–Ni–P1 83.6(5), C1B–Ni–P1
88.6(8), P1–Ni–P2 170.8(1), P1–Ni–Cl 94.8(1), P2–Ni–Cl 94.1(1).
(1) in good yields. Complex (1) was characterized by different
analytical techniques such as 1H, 13C{1H} and 31P{1H} NMR,
mass spectroscopy and elemental analyses. Besides this, the
structure of compound (1) was unequivocally determined by
single crystal X-Ray diffraction techniques.
SH
S
PPh2
S
PPh2
Ni Cl
The Ni-P distances are very similar among them, 2.160(1) Å
for Ni-P1 and 2.163(1) Å for Ni-P2. Because the molecular
structure is disordered, some lengths and angles are slightly
different. In all other senses the bond distances and angles are
similar to those reported for analogous compounds (however no
full comparison could be made due to the fact that values for
some bond distances and bond angles of this complex were not
given due to the strongly disordered POCSP ligand in the
refereed compound).46
Et3N, ClPPh2
toluene
NiCl2
OH
O PPh2
(A)
O PPh2
(1)
Scheme 1. Synthesis of [NiCl{C6H3-2-(OPPh2)-6-(SPPh2)}] (1)
Thus, the 1H NMR spectrum of (1) is not very informative, as
only shows signals due to the aromatic fragments in the typical
region expected for aromatic hydrogen atoms. However, more
informative results the 13C{1H} where the number of signals
expected for the proposed structure are observed in the expected
chemical shifts, being notable a characteristic signal due to the C-
2.2 Catalytic evaluation of [NiCl{C6H3-2-(OPPh2)-6-
(SPPh2)}] (1) in C-S cross-couplings.47
Ni bond that appears as doublet of doublets at 142.7 ppm (2JCP
25.5, 16.7 Hz). Also, of interest the 31P{1H} NMR spectrum
obtained, that displays two groups of signals as doublets. The
first one being located at 137.9 ppm (2JPP = 367 Hz)
=
The catalytic activity of complex (1) was evaluated in the C-S
cross-coupling reaction (Table 1). First, we carried out the
catalytic reaction using iodobenzene and diphenyl disulphide as
substrates, using 0.3 mol % of catalyst at 110 ºC for 4h. Under
these conditions a 26 % of conversion (Entry 1, Table 1) was
obtained. In order to improve this result, we decided to modify
the reactions conditions and increase the temperature and the
reaction time, attaining a 99 % of conversion at 140 ºC for 16.5 h
(Entry 2, Table 1), while at 130 ºC for 22h a 60 % of conversion
was produced.
corresponding to the phosphinito moiety, while the signal due to
the thiophosphinito moiety is observed at higher field at 66.4
ppm (2JPP = 367 Hz), signals which are also in agreement with
the non-symmetric nature of the phosphinito-thiophosphinito
PSCOP-Ni(II) pincer compound (1). Completing this
characterization, the analysis by mass spectrometry produced a
spectrum showing a peak due to the molecular ion at 586 m/z.
All these results and those of the elemental analysis agree with
the proposed structure.
Table 1. C-S cross-couplings catalysed by [NiCl{C6H3-2-(OPPh2)-6-
(SPPh2)}] (1)a
In addition, suitable crystals of (1) for their analysis by single
crystal X-ray diffraction techniques were obtained by slow diffusion
of diethyl ether into a concentrated solution of (1) in
I
S
R2
R2
0.3 mol % (1)
Zn, DMF
S
+
R2
S
R1
R1
Yieldd
%
dichloromethane. Allowing the unequivocal determination of the
structure of (1).44 Complex (1) crystallizes in the monoclinic crystal
system and P21/n space group. The molecular structure exhibits a
disorder in the central aromatic ring and bridge atoms (O, S). As can
be seen in Figure 2, the nickel atom is coordinated in a square-planar
fashion, with the POCSP pincer ligand coordinated in a typical
meridional tridentate manner and one chlorine ligand completing the
coordination sphere about the nickel. Noteworthy the fact that the
strain of one of the 5 membered metallocycles formed is partially
alleviated by the larger size of the sulphur atom.
Entry R1
R2
Product
I
S
1b
26
S
S
H
I
S
2c
S
S
99
H
I
S
3a
60 (58)e
70 (69)e
S
S
H
S
I
4a
S
S
H2N
H2N
S
S
I
O
5a
92 (89)e
91(89)e
72 (71)e
S
S
O
I
6a
S
S
O
O
O
S
I
7a
S
O
S
S
I
O
O
8a
50 (50)e
10 (8)e
S
S
O
S
I
S
9a
S
O

3
aReaction conditions: 2 mmol of the correspondingiodobenzene, 1 mmol
of the dialkyl or diaryl disulphide, 2 mmol of Zn, 3 mL of DMF, 0.3 mol %
of catalyst (1), 130 ºC for 22h. b110 ºC for 4h. c140 ºC for 16.5h.
dConversions obtained by GC-MS are based on residual iodobenzene and
are the average of two runs. eIsolated Yield.
3.
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The latter conditions were chosen to better observe the
potential effects of sterics and electronics on the yield of the
reactions. In terms of electronic effects, we did not make an
exhaustive comparison, however we compared three points
having as para substituents -H (0.0), -NH2 (-0.66) and -COCH3
(0.05) in terms of the Hammett parameter,48 although the amino
substrate was expected to show lower yields in comparison to -H
and -COCH3 we were glad to observe that even with this
substrate that typically hinders the reaction we got good yields
with the present catalytic system. Then, since the iodobenzene
para substituted with -COCH3 (4-Iodoacetophenone) produced
the best conversions we further evaluated the steric effect of
different substituents at the disulphide substrates on the C-S
coupling reactions using this substrate. In this study, we chose
functional groups with different size, namely phenyl, methyl, n-
butyl, sec-butyl and tert-butyl (Table 1). We observed that using
the substrate with less steric hindrance, dimethyl disulphide
(Entry 6, Table 1), the conversion was up to 91 %, while the
conversion with a more sterically demanding substrate, such as
di-tert-butyl disulphide, dramatically decreased to 10 %. Thus, it
is clear that the more steric hindrance of the disulphide
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3. Conclusions
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We have synthesized a new non-symmetric Ni(II)
phosphinito-thiophosphinito PSCOP pincer compound. Complex
(1) was fully characterized, including the elucidation of its
molecular structure by single crystal X-ray diffraction
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techniques. Complex (1) showed a good catalytic activity in C-S
couplings of iodobenzene with different disulfides. The catalytic
reaction was sensitive to the steric nature of the substrates
(disulfides), showing higher conversions with those having the
less sterically than with the more sterically hindered substituents.
Acknowledgments
We would like to thank Chem. Eng. Luis Velasco Ibarra, Dr.
Francisco Javier Pérez Flores, Q. Eréndira García Ríos, M.Sc.
Lucia del Carmen Márquez Alonso, M.Sc. Lucero Ríos Ruiz, Q.
María de la Paz Orta Pérez and Q. Roció Patiño-Maya for
technical assistance. H. V. would like to thank Programa de
Becas Posdoctorales-DGAPA-UNAM for postdoctoral
scholarships (Oficio: CJIC/CTIC/1060/2017). The financial
support of this research by PAPIIT (grant No. IN207317) is
gratefully acknowledged. J.D.C-G would like to thank Programa
de Cátedras CONACyT-PRY for generous support.
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Morales, Inorg. Chem. Commun., 2005, 8, 955–959.
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Morales, Adv. Synt. Catal., 2006, 348, 236–242.
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References and notes
1.
2.
D. Morales-Morales, Ed., Pincer Compounds. Chemistry and
Applications, Elsevier, 2018.
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2009, 6, 169–192.

4
Tetrahedron
40. V. Gomez Benitez, H. Valdés, S. Hernández Ortega, J. Manuel
program.45 The remaining atoms were located via a few cycles of
least squares refinements and difference Fourier maps. Hydrogen
atoms were input at calculated positions and allowed to ride on the
atoms to which they are attached. Thermal parameters were refined
for hydrogen atoms on the phenyl groups using a Ueq = 1.2 Å to
precedent atom. The final cycle of refinement was carried out on all
non-zero data using SHELXL-2014/7.45 Absorption correction was
applied using SADABS program. The fragment S-Ph-O, is
disordered and was modelled and refined anisotropically in two
positions using a variable site occupational factor (SOF). The ratio of
SOF was 60/40 %. 294 restraints were applied at the refinement, 240
for SIMU, 36 for DELU and 18 for SAME instructions respectively.
The ligand S-Ph-O is coplanar with metal center coordination,
however the phenyl rings are rotated by 61.2(4)° (C7 to C12),
66.2(14° (C13 to C18), 74.5(3)° for C19 to C24 and 74.2(4)° for C25
to C30.
Germán-Acacio and D. Morales-Morales, Polyhedron, 2018, 143,
144-148.
41. V. Gomez Benitez, O. Baldovino-Pantaleón, C. Herrera-Álvarez,
R. A. Toscano and D. Morales-Morales, Tetrahedron Lett., 2006,
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42. Synthesis of [NiCl{C6H3-2-(OPPh2)-6-(SPPh2)}] (1). Under
nitrogen atmosphere, a mixture of 3-mercaptophenol (6 mmol,
0.64 mL) and triethylamine (6.6 mmol, 1.8 mL) was stirred for 15
min. Then, 60 mL of toluene and chlorodiphenylphosphine (12
mmol, 2.25 mL) was added to the mixture. The reaction was
heated at reflux for 18h. After this time, the solution was filtered
through Celite® and NiCl2 (6 mmol, 778 mg) was added. The
solution was refluxed for 16 h. After this time, all the volatiles
were removed under high vacuum. The crude product was purified
by chromatographic column, using a 2:1 solution of
dichloromethane/pentane. Yield: 3.21 g (91%). Melting point: 247
ºC (280 ºC decomposes). 1H NMR (300 MHz, CDCl3) 8.01 – 7.94
(m, 8H, P-CHAr), 7.53 – 7.43 (m, 12H, P-CHAr), 7.01 – 6.95 (m,
1H, CHAr), 6.90 – 6.88 (m, 1H, CHAr), 6.70 – 6.60 (m, 1H, CHAr).
13C{1H} NMR (75 MHz, CDCl3) 166.3 (dd, C-O, 2JCP = 15.6, 7.6
45. G. M. Sheldrick. Acta Cryst. 2015, C71, 3-8.
46. P. Hasche, M. Joksch, G. Vlachopoulou, H. Agarwuala, A.
Spannenberg, T. Beweries. Eur. J. Inorg. Chem. 2018, 676-680.
47. Alkyl- and Arylthiolation of Iodobenzenes. Under an atmosphere
of nitrogen, a solution of 2 mmol of halobenzene, 1 mmol of the
corresponding alkyl- or aryldisulfide, 0.3 mol% of the catalyst in 3.0
mL of DMF, was introduced into a Schlenk tube containing a
magnetic stir bar and charged with 2 mmol of zinc dust. The tube
was sealed and fully immersed in a 130 oC silicon oil bath. After 22
h, the reaction mixture was cooled to room temperature and the
organic phase analyzed by gas chromatography (GC-MS)
(Quantitative analyses were performed on an Agilent 6890N GC
with a 30.0 m DB-1MS capillary column coupled to an Agilent 5973
Inert Mass Selective detector).
Hz), 154.8 (dd, CS, 2JCP = 22.2, 6.5 Hz), 142.7 (dd, C-Ni, 2JCP
=
25.5, 16.7 Hz), 133.5 (d, OP-CAr, 2JCP = 12.1 Hz), 132.3 (d, SP-
CAr, 2JCP = 12.6 Hz), 132.2 (dd, SP-CAr, 1,3JCP = 46.6, 4.6 Hz),
131.9 (d, OP-CAr, 4JCP = 2 Hz), 131.3 (dd, OP-CAr
,
J
=36.7,
1,3
CP
2Hz), 131.2 (d, SP-CAr, 4JCP = 2.3 Hz), 128.8 (d, SP-CAr, 3JCP
=
10.8 Hz), 128.7 (CAr), 117.7 (d, S-CAr, 3JCP = 15.6 Hz), 109.6 (d,
O-CAr, 3JCP = 14.4 Hz). 31P{1H} NMR (121 Hz, CDCl3) 137.9 (d,
OP, 2JPP = 367 Hz), 66.4 (d, SP, 2JPP = 367 Hz). EM-IE+: m/z 586
(56) [M]+, 550 (10) [M-HCl]+, 493 (100) [M-NiCl]+. Elem. Anal.
Calcd. for C30H23ClNiOP2S (587.66): C, 61.33; H, 3.69; S, 5.04.
Found: C, 61.38; H, 3.68; S, 4.99.
48. C. Hansch, A. Leo, R. W. Taft. Chem. Rev. 1991, 91, 165-195.
43. a) J. M. Serrano-Becerra. In Catálisis homogénea mediada por
complejos de Pd(II), Ni(II) y Au(I): algunas aplicaciones en síntesis
orgánica. Ph.D. Dissertation. Universidad Nacional Autónoma de
México. Instituto de Química. 2010. México b) J. M. Serrano-
Becerra, S. Hernández-Ortega, D. Morales-Morales. Inorg. Chim.
Acta. 2010, 363, 1306–1310.
44. Data collection and refinement for [NiCl{C6H3-2-(OPPh2)-6-
(SPPh2)}] (1). A Yellow and laminar crystal of (1), was grown
independently from CH2Cl/Et2O and mounted on glass fibres, then
placed on a Bruker Smart Apex II diffractometer with a Mo-target
X-ray source (λ = 0.71073Å). The detector was placed at a distance
of 5.0 cm from the crystal frames were collected with a scan width
of 0.5 in ω and an exposure time of 10 s/frame. Frames were
integrated with the Bruker SAINT software package using a narrow-
frame integration algorithm. Non-systematic absences and intensity
statistics were used in monoclinic P2(1)/n space group. The structure
was solved using Patterson methods using SHELXS-2014/7
Supplementary Material
Supplementary data for compound (1) has been deposited at
the Cambridge Crystallographic Data Centre. Copies of this
information are available free of charge on request from The
Director, CCDC, 12 Union Road, Cambridge, CB2 1EZ, UK
(Fax: +44-1223-336033; e-mail deposit@ccdc.cam.ac.uk or
www: http://www.ccdc.cam.ac.uk) quoting the deposition
numbers CCDC 1823658.
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5
Highlights
A new Ni(II) phosphinito-thiophosphinito
PSCOP pincer was synthesized.
The PSCOP-Ni(II) pincer complex
efficiently catalyses C-S couplings of
disulfides and iodobenzene.
The activity of the catalyst is strongly
related with the steric demand of the
substituent at the disulphide.