Alkyl- and arylthiolation of aryl halides catalyzed by fluorinated bis-imino-nickel NNN pincer complexes [NiCl2{C5H 3N-2,6-(CHNArf)2}]

Article abstract of DOI:10.1002/adsc.200505207

The synthesis of bis-imino nickel(II) NNN pincer complexes of the type [NiCl₂{C₅H₃N-2,6-(CHNAr_f) ₂}]; Ar_f= C₆H₃-2,3-F₂ (1), C₆H₃-2,5-F₂ (2), C₆H ₃-3,4-F₂ (3), C₆H₃-3,5-F₂ (4), C₆H₂-2,3,4-F₃ (5), C₆H ₂-2,3,6-F₃ (6), C₆H₂-2,4,5-F ₃ (7), C₆H₂-2,4,6-F₃ (8), has been achieved and their reactivity in alkyl- and arylthiolation reactions of halobenzenes examined. The use of fluorinated substituents Ar_f on the imines has allowed the tuning of the electronics in these complexes and the influence of these substituents and those of the disulfides in the thiolation reactions have been analyzed.

Full text of DOI:10.1002/adsc.200505207

FULL PAPERS
DOI: 10.1002/adsc.200505207
Alkyl- and Arylthiolation of Aryl Halides Catalyzed by
Fluorinated Bis-Imino-Nickel NNN Pincer Complexes
[NiCl2{C5H3N-2,6-(CHNArf)2}]
´
´
´
Oscar Baldovino-Pantaleon, Simon Hernandez-Ortega, David Morales-Morales*
´
´
´
Instituto de Química, Universidad Nacional Autonoma de Mexico, Cd. Universitaria, Circuito exterior, Coyoacan,
´
04510, Mexico, D. F.
Fax: (þ52)-55-56162217, e-mail: damor@servidor.unam.mx
Received: May 18, 2005; Accepted: October 7, 2005
Supporting Information for this article is available on the WWW under http://asc.wiley-vch.de/home/.
Abstract: The synthesis of bis-imino nickel(II) NNN allowed the tuning of the electronics in these com-
pincer complexes of the type [NiCl2{C5H3N-2,6- plexes and the influence of these substituents and
(CHNArf)2}]; Arf ¼C6H3-2,3-F2 (1), C6H3-2,5-F2 (2), those of the disulfides in the thiolation reactions
C6H3-3,4-F2 (3), C6H3-3,5-F2 (4), C6H2-2,3,4-F3 (5), have been analyzed.
C6H2-2,3,6-F3 (6), C6H2-2,4,5-F3 (7), C6H2-2,4,6-F3 (8),
has been achieved and their reactivity in alkyl- and ar- Keywords: C S cross-coupling; fluorinated ligands;
ylthiolation reactions of halobenzenes examined. The homogeneous catalysis; nickel; pincer complexes; thi-
use of fluorinated substituents Arf on the imines has olation
ꢀ
Introduction
since sulfur compounds have long been known to act
as catalyst poisons, often rendering the catalytic reaction
Recently, there has been an increasing demand for effi- to be totally ineffective.[9] Thus, recently several useful
cient, high-yield methods for the synthesis of diaryl thi- transformations of sulfur-containing compounds using
oethers and alkyl aryl thioethers owing to their impor- transition metal catalysts have been developed.[10] The
tance as structural motifs in a wide range of molecules metal-catalyzed synthesis of aryl sulfides has included
with numerous and important applications.[1] In addi- the cross-coupling of thiols with aryl halides using cop-
tion, the scope and application of organosulfur chemis- per or palladium catalyst under basic conditions,[11] how-
try in organic synthetic reactions has increased tremen- ever, the metal-catalyzed thiolation of aryl halides with
dously since sulfur-containing groups serve as important disulfides has rarely been done, despite the fact that the
auxiliary functions in synthetic sequences,[2] for instance, efficient use of (RS)2 in the catalytic thiolation of alkyl
in the reversal of the polarity (Umpolung), the enhance- halides has been reported.[12]
ꢀ
ment of the acidity of C H bonds, and the transfer of
We believe that a robust complex used as catalyst may
chirality from sulfur to carbon.[3] Furthermore, aryl sul- render a better performance in the alkyl- and arylthiola-
fides are a common functionality found in numerous tion of halobenzenes. Thus, following our continuous in-
pharmaceutically active compounds.[4] In fact, a number terest in the use of pincer type-compounds[13] for novel
of drugs in therapeutic areas such as diabetes and anti- organic transformations and the use of aromatic fluori-
inflammatory, immune, Alzheimerꢀs and Parkinsonꢀs nated substituents[13] for the tuning of steric and elec-
diseases contain the aryl sulfide functionality.[5] On the tronic properties, we report our findings in the use of flu-
other hand, transition metal complex-catalyzed reac- orinated bis-iminonickel(II) NNN pincer complexes
tions have made a great contribution to the recent [NiCl2{C5H3N-2,6-(CHNArf)2}] as efficient catalysts
growth of organic synthesis.[6] Considerable attention for the cross-coupling of (RS)2 and halobenzenes.
has also been focused on sulfur-containing transition
metal complexes as models of active sites of natural en-
zymes[7] and catalytic metal surfaces.[8] However, transi-
tion metal complex-catalyzed synthetic reactions using
sulfur-containing compounds remain open to study,
236
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Alkyl- and Arylthiolation of Aryl Halides
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Results and Discussion
proceed, neither in the absence of the nickel complex.
From all the compounds tested (Table 1), complex
The reaction of one equivalent of the potentially triden- [NiCl2{C5H3N-2,6-(CHNC6H2-2,3,4-F3)2}] (5) afforded
tate pincer NNN ligands with one equivalent of NiCl2 · the higher yields (90%), thus all the following experi-
6 H2O, affords the corresponding complexes [NiCl2{C5 ments were carried out using this complex as catalyst.
H3N-2,6-(CHNArf)2}]; Arf ¼C6H3-2,3-F2 (1), C6H3-2,5-
Using the same reaction conditions employed for the
F2 (2), C6H3-3,4-F2 (3), C6H3-3,5-F2 (4), C6H2-2,3,4-F3 methylthiolation of iodobenzene, the alkylthiolation of
(5), C6H2-2,3,6-F3 (6), C6H2-2,4,5-F3 (7), C6H2-2,4,6-F3 iodobenzene with different disulfides, using complex 5
(8) in high yields. Analysis by NMR reveal these com- as catalyst, was attempted (Table 2).
pounds to be paramagnetic, exhibiting broad signals in
From Table 2 it is evident that the performance of the
all cases. The magnetic moments for all complexes at reaction has a clear dependence on the steric hindrance
room temperature (297 K) are in the range of 2.8–3.4 of the substituents in the disulfide, thus affording similar
B. M. as expected for high-spin five-coordinate nickel- yields in the case of iso-propyl, n-butyl, sec-butyl and
(II) complexes, these values are in good agreement with phenyl (an average of 75% yield) and affording only
those reported in the literature.[14] Analysis of the pincer 60% yield in similar reaction times for the di-tert-butyl
compounds by FABþ-MS spectrometry affords in most disulfide. These results can be rationalized in terms of
of the cases the molecular ion minus one chloride [Mꢀ steric hindrance at the nickel center since, as will be dis-
Cl]þ, other important peaks include the consecutive cussed further, activation of the (RS)2 by the metal cen-
loss of the remaining chlorides. In all cases elemental ter is probably necessary first, this would probably give
analysis are consistent with the proposed formulations.
rise to a dithiolate nickel(II) complex which, in turn,
Crystals suitable for single crystal X-ray diffraction must further react with iodobenzene. From these as-
analyses (Table S1 in the Supporting Information) sumptions, it is clear that, as the size of the substituent
were obtained for complexes 4 and 7, the two structures in the (RS)2 increases, the facility with which further ad-
share a number of common features, the only difference dition of the halogenated compound could take place
being the fluorinated substituent. In both complexes the will decrease or even cease.
nickel centers are pentacoordinated in a distorted trigo-
Attempts to carry out the same transformation using
nal bypiramidal geometry (TBP), with the two chlorides chloro- or bromobenzene were unsatisfactory, affording
occupying the equatorial plane. The three nitrogens of only 4% yield in the case of bromobenzene and only
the NNN pincer ligands occupy the remaining coordina- traces in the case of chlorobenzene (Table 3). These re-
ꢀ
tion sites. The average Ni N bond distances of the NNN sults were expected given the energy requirements for
pincer ligand are of 2.109 Š (4) and 2.1207 Š (7), respec- the cleavage of the C Cl and C Br bonds being higher
ꢀ
ꢀ
ꢀ
ꢀ
tively. For both compounds the terminal Ni Nbond dis-
tances are somewhat longer than the central Ni(1) N(1)
in both cases that those required to break the C I bond.
In an attempt to explore the effect of the substituents
ꢀ
bond distances being 1.964(3) Š (4) and 1.952(2) Š (7), in the para-position for different bromobenzenes (Ta-
respectively. The variation of these distances can be re- bles 4 and 5), we carried out some methylthiolation ex-
lated to the packing of the molecules in the crystal lattice. periments, finding that indeed the presence of elec-
As in previous cases, we have focused on the use of tron-withdrawing groups in the aromatic ring favors
pincer-type ligands and their complexes for novel organ- the cross-coupling process, the best results being ob-
ic transformations, and the selection of these ligands has tained with p-HCO-C6H4Br (35% yield).
been done on the basis of the robustness that they confer
It has been proposed that these sorts of reactions with
to the transition metal complexes they form.[15] Given nickel must proceed through Ni(0)/Ni(II) intermedi-
the importance that cross-coupling reactions using pal- ates,[16] and it is possible that a similar mechanism may
ladium complexes have gained, we decided to attempt be working in the present case. Supporting proof for
cross-coupling reactions, using nickel complexes, for this assumption is that the analogous Ni(II) complex
an important process in organic chemistry, namely the (9) undergoes reversible redox processes from Ni(I)-
synthesis of mixed alkyl aryl sulfides. This reaction has Ni(II)-Ni(III).[17]
been previously reported using palladium or copper cat-
alysts as in the Ullmann process, however, in most of the
cases this reaction requires the use of the free thiol and
basic conditions with prolonged reaction times. We be-
lieve that given the robustness that the present com-
plexes offer, we may have a good chance to carry out
similar catalysis using disulfides (RS)2 instead of the
free thiol. Thus, all the series of complexes were initially
tested in the catalytic reaction of C6H5I with (MeS)2 in
the presence of zinc; the presence of zinc is fundamental
because in its absence the catalytic reaction does not
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Oscar Baldovino-Pantaleon et al.
FULL PAPERS
Table 1. Methylthiolation of iodobenzene by [NiCl2{C5H3N-
2,6-(CHNArf)2}] complexes.
Table 2. Alkyl- and arylthiolation of iodobenzene by
[NiCl2{C5H3N-2,6-(CHNC6H2-2,3,4-F3)2}] (5).
Yield [%][a]
90%
ꢀ
Complex
Ni(II) complexes
Yield [%][a]
70
Entry
1
RS SR
1
2
3
4
5
6
74%
75%
73%
60%
75%
2
3
57
85
4
5
6
68
90
70
[a]
Yields were determined by GC-MS and are based on C6H5I.
Table 3. Methylthiolation of aryl halides by [NiCl2{C5H3N-
2,6-(CHNC6H2-2,3,4-F3)2}] (5).
7
8
73
ꢀ
Ph X
Entry
1
Yield [%][a]
Traces
2
3
4%
75%
90%
[a]
Yields obtained by GC-MS are based on haloarene.
[a]
Yields obtained by GC-MS are based on haloarene.
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Alkyl- and Arylthiolation of Aryl Halides
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Table 4. Nickel-catalyzed coupling of dimethyl disulfide with
4-bromoaryl compounds by [NiCl2{C5H3N-2,6-(CHNC6H2-
2,3,4-F3)2}] (5).
Table 5. Nickel-catalyzed coupling of dialkyl and diaryl disul-
fides with 4-bromoaryl compounds by [NiCl2{C5H3N-2,6-
(CHNC6H2-2,3,4-F3)2}] (5).
Yield [%][a]
13%
Entry Bromides
1
RS-SR
Yield [%][a]
11
ꢀ
Entry
1
p-R C6H4Br
2
3
5%
2
3
4
5
10
35%
22
4
5
4%
Traces
20
traces
6
7
6%
3%
6
23
[a]
Yields obtained by GC-MS are based on haloarene.
7
26
It is also known that nickel complexes rapidly insert
into a disulfide bond to afford (RS)2Ni complexes.[18]
Thus, it would be logical to think that one of the first
steps in the catalytic process would be the reduction of
the Ni(II) complex by metallic zinc, further activation
8
19
ꢀ
by this new Ni(0) complex of the disulfide RS SR would
9
Traces
24
ꢀ
lead to the cleavage of the S S bond to afford a dithio-
late Ni(II) species. At this point it is important to men-
tion that as the size of the substituent in the thiolate in-
creases the (RS)2Ni complex becomes more stable;[19]
this fact would explain why the reaction with sterically
hindered disulfides affords lower yields, since the result-
ing intermediate would prefer to stay as a dithiolate spe-
cies rather than react further.
10
Once the nickel dithiolate complex has been formed,
the metallic zinc would reduce this Ni(II) species to a
Ni(I) thiolate complex of the type [Ni(I)(NNN)(SR)].
After this, the oxidative addition of iodobenzene may
produce a Ni(III) complex of the type [Ni(III)-
(NNN)(SR)(C6H5)(I)], elimination of the desired prod-
11
6
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FULL PAPERS
ware. Solvents were dried using standard procedures and distil-
led under dinitrogen immediately prior to use. The IR spectra
were recorded on a Nicolet-Magna 750 FT-IR spectrometer as
nujol mulls. The 1H NMR (300 MHz) spectra were recorded on
a JEOL GX300 spectrometer. Chemical shifts are reported in
ppm downfield of TMS using the residual solvent (CDCl3, d¼
7.27) as internal standard. 19F{1H} spectra were recorded with
complete proton decoupling and are reported in ppm using
C6F6 as external standard. Elemental analyses were deter-
mined on a Perkin-Elmer 240. Positive-ion FAB mass spectra
were recorded on a JEOL JMS-SX102A mass spectrometer
operated at an accelerating voltage of 10 kV. Samples were des-
orbed from a nitrobenzyl alcohol (NOBA) matrix using 3 keV
xenon atoms. Mass measurements in FAB are performed at a
resolution of 3000 using magnetic field scans and the matrix
ions as the reference material or, alternatively, by electric field
scans with the sample peak bracketed by two (polyethylene
glycol or cesium iodide) reference ions. Melting points were
determined in a MEL-TEMP capillary meltingpoint apparatus
and are reported without correction. GC-MS analyses were
performed on an Agilent 6890NGC with a 30.0 m DB-1MS ca-
pillary column coupled to an Agilent 5973 Inert Mass Selective
detector.
Table 5 (cont.)
Entry Bromides
12
RS-SR
Yield [%][a]
4
13
14
15
18
Traces
5
[a]
Yields obtained by GC-MS are based on haloarene.
Dialkyl and diaryl disulfides and halobenzenes were ob-
tained commercially from Aldrich Chem. Co. and used as re-
ceived without further purification. The bis-imino NNN pincer
ligands {C5H3N-2,6-(CHNArf)2} were synthesized according to
the published procedures.[20]
ꢀ
uct Ar SR would yield an unsaturated [Ni(II)-
(NNN)(SR)] species that, after a new reduction with
more metallic zinc, would restart the catalytic cycle all
over again (Scheme 1). However, the present mechanis-
tic proposal may have other logical variations that can-
not be ruled out at this point; hence experiments aimed
to validate the proposed mechanism are currently under
process and will be disclosed elsewhere.
General Procedure for the Synthesis of Complexes
[NiCl2{C5H3N-2,6-(CHNArf)2}]
All complexes were synthesized by the following method illus-
trated for the synthesis of [NiCl2{C5H3N-2,6-(CHNC6H3-2,3-
F2)2}] (1).
Conclusion
Synthesis of [NiCl2{C5H3N-2,6-(CHNC6H3-2,3-F2)2}] (1)
In conclusion, we have designed a high-yield one-pot
synthesis for asymmetrical alkyl aryl thioethers from di-
sulfides and iodobenzene in the presence ofmetallic zinc
as an indispensable reducing agent, this method can ef-
ficiently use (RS)2 as a thiol source under neutral condi-
tions. Experiments changing iodo- for bromo- and chloro-
benzene suggest that the system probably has to be more
robust to carry out the reaction at the higher tempera-
tures required to provide the necessary energy to acti-
vate the more robust C Br and C Cl bonds. Based on
the models we have employed successfully for the
Heck reaction, we are currently employing Ni(II)-phos-
phine and phosphinite pincer complexes of the type
[PCPNiCl], these results will be reported elsewhere.
A solution of the ligand {C5H3N-2,6-(CHNC6H3-2,3-F2)2}
(120 mg, 0.33 mmol) in anhydrous CH2Cl2 (10 mL) was added
to a stirred solution of NiCl2 ·6 H2O (0.078 g, 0.33 mmol) in ab-
solute methanol (10 mL). The resulting green solution was stir-
red at room temperature for 2 h. After this time an orange sus-
pension is noted and the solvent evaporated under vacuum.
The product was purified by recrystallization from MeOH;
the resulting precipitated was filtered and washed with hexane
(3ꢁ5 mL) and dried under vacuum. Crystals suitable for single
crystalX-ray diffraction studies wereobtained from adichloro-
methane/methanol (4:1) solution. An orange solid was ob-
tained; yield: 142 mg (88%); mp: 2408C (dec.).
ꢀ
ꢀ
Alkyl- and Arylthiolation of Halobenzenes
Under an atmosphere of nitrogen, a solution of 4.9 mmol of
halobenzene, 2.45 mmol of the corresponding dialkyl or diaryl
disulfide, 0.0057 mmol of the corresponding catalyst and
202 mg (0.924 mmol) of diethylene glycol di-n-butyl ether (in-
ternal standard) in 3.0 mL of DMF, was introduced into a
Schlenk tube containing a magnetic stir bar and charged with
4.9 mmol of zinc dust. The tube was sealed and fully immersed
Experimental Section
Materials and Methods
Unless stated otherwise, all reactions were carried out under an
atmosphere of dinitrogen using conventional Schlenk glass-
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Alkyl- and Arylthiolation of Aryl Halides
FULL PAPERS
Scheme 1. A mechanistic proposal for the thiolation of halobenzenes using fluorinated bis-imino-nickel NNN pincer com-
plexes [NiCl2{C5H3N-2,6-(CHNArf)2}].
in a 1108C or a 1608C silicon oil bath. After 4 h or 24 h, the re-
action mixture was cooled to room temperature and the organ-
ic phase analyzed by gas chromatography (GC-MS).
Crystallographic data for complex 4 and 7 have been depos-
ited 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: þ44-1223-336033; e-mail deposit@ccdc.cam.ac.uk
or www: http://www.ccdc.cam.ac.uk) quoting the deposition
numbers CCDC 267432 and CCDC 267433.
and Ma. de lasNieves Zavala fortheir invaluable help inthe run-
ning of the FABþ-mass, IR and 19F{1H} spectra, respectively.
The support of this research by CONACYT (J41206-Q), DGA-
PA-UNAM (IN114605) and UC-MEXUS-CONACYT (Grant
CN-03-100) is gratefully acknowledged.
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