Cobalt(II)-Mediated Desulfurization of Thiophenes, Sulfides, and Thiols

Article abstract of DOI:10.1021/acs.inorgchem.8b01588

Desulfurization of organosulfur compounds is a highly important reaction because of its relevance to the hydrodesulfurization (HDS) process of fossil fuels. A reaction system involving Co(BF₄)₂·6H₂O and the dinucleating ligands HBPMP or HPhBIMP has been developed that could desulfurize a large number of thiophenes, sulfides, and thiols to generate the complexes [Co₂(BPMP)(μ₂-SH)(MeCN)](BF₄)₂ (1a), [Co₂(BPMP)(SH)₂](BF₄) (1b), and [Co₂(PhBIMP)(μ₂-SH)(X)](BF₄)₂ [X = DMF (2a), MeCN (2c)], while the substrates are mostly converted to the corresponding alcohols/phenols. This convenient desulfurization process has been demonstrated for 25 substrates in 6 different solvents at room temperature.

Full text of DOI:10.1021/acs.inorgchem.8b01588

Communication
pubs.acs.org/IC
Cite This: Inorg. Chem. XXXX, XXX, XXX−XXX
Cobalt(II)-Mediated Desulfurization of Thiophenes, Sulfides, and
Thiols
Tuhin Ganguly, Ayan Das, Manish Jana, and Amit Majumdar*
Department of Inorganic Chemistry, Indian Association for the Cultivation of Science (IACS), 2A and 2B Raja S. C. Mullick Road,
Jadavpur, Kolkata 700032, India
*
S Supporting Information
regarding the complete removal of S/Se from dibenzothio-
phene/selenophene using low-valent Mo/W complexes at high
ABSTRACT: Desulfurization of organosulfur com-
pounds is a highly important reaction because of its
relevance to the hydrodesulfurization (HDS) process of
10,23
temperatures.
In general, the reaction conditions often
involved heating for a long period of time at high temperatures
9
,12,18,19
9
fossil fuels. A reaction system involving Co(BF ) ·6H O
4
2
2
(often ≥100 °C),
photolysis using UV light for 1 day, or
16
and the dinucleating ligands HBPMP or HPhBIMP has
been developed that could desulfurize a large number of
thiophenes, sulfides, and thiols to generate the complexes
irradiation with a high-pressure Hg lamp for 12−25 h. On the
other hand, Co(II)-mediated C−S bond cleavage of aliphatic
thiolates using the N,N,N′,N′-tetrakis[2-(1-ethylbenzimidazol-
24,25
[
[
Co (BPMP)(μ -SH)(MeCN)](BF ) (1a),
2 2 4 2
yl)]-2-hydroxy-1,3-diaminopropane (HN-Et-HPTB) ligand
Co (BPMP)(SH) ](BF ) (1b), and [Co (PhBIMP)(μ -
2
2
4
2
2
(Scheme 1) at ambient conditions has recently been reported by
SH)(X)](BF ) [X = DMF (2a), MeCN (2c)], while the
4
2
substrates are mostly converted to the corresponding
alcohols/phenols. This convenient desulfurization process
has been demonstrated for 25 substrates in 6 different
solvents at room temperature.
Scheme 1. General Reaction Scheme for the Desulfurization
Reactions
a
leavage of the C−S bond by transition metals is highly
C
important because of its relevance to the hydrodesulfuri-
1
−5
zation (HDS) process of fossil fuels,
which is one of the
largest-volume industrial catalytic applications of transition
metals. The process needs a supported molybdenum sulfide
catalyst containing cobalt and operates under high pressure
(
160−600 psi pressure of H ) and high temperature (300−450
2
°C). The HDS process reduces the sulfur content of oils by
removing sulfur from thiophenes and thiols as H S and thus
2
allows access to more readily processed and more cleanly
combusted hydrocarbon products. The level of difficulty in
removing sulfur in crude oil by HDS reactions generally
increases in the order alkyl mercaptans < aromatic mercaptans <
a
Also shown are the ligands.
6,7
26
diphenyl sulfide < thiophene, dibenzothiophene. Current
technology can desulfurize aliphatic and acyclic sulfur
compounds quite efficiently but remains relatively less successful
us. To the best of our knowledge, there is currently no
convenient method available for complete desulfurization of the
HDS substrates. Here we report a Co(II)-mediated complete
desulfurization process applicable for almost all of the relevant
substrate types of the HDS process at room temperature (RT) in
six different solvents.
6
,7
in treating aromatic thiols, thiophenes, and its derivatives.
Consequently, desulfurization reactions of aromatic thiols and
8
−10
thiophenes are being actively pursued.
Cleavage of the C−S bonds of various sulfur substrates
We initiated our investigation of C−S bond cleavage by using
mediated by transition metals (e.g., Co, Fe, Ni, Cu, W, Rh, Ir,
2,6-bis[[bis(2-pyridylmethyl)amino]methyl]-4-methylphenol
(HBPMP) ligand
addition of 2 equiv of Co(BF ) ·6H O into a mixture of NaS Bu,
HBPMP, and Et N (1:1:4) in N,N-dimethylformamide (DMF)
at RT initially resulted in a green solution, which changed to a
brown solution upon stirring for 2 days and subsequently yielded
a mixture of pink and green crystals. Molecular structure
1
1−19
27−29
Ru, Os, Pd, and Pt),
particular,
in general, and Co(II), in
(Scheme 1) and Co(BF ) ·6H O. The
4 2 2
1
1−14,20
t
has been reported previously. Coordination
4 2
2
of low-valent Mo with thiophenes, benzothiophenes, and
3
selenophenes and subsequent C−S bond cleavage are also
8
−10,21,22
available in the literature.
In most of these reports, only
the C−S bonds of coordinated ligands were involved and the
products were a result of metal insertion in the C−S bonds
instead of complete removal of the −SH functionality from the
organosulfur substrates. There are, however, at least two reports
Received: June 8, 2018
©
XXXX American Chemical Society
A
DOI: 10.1021/acs.inorgchem.8b01588
Inorg. Chem. XXXX, XXX, XXX−XXX

Inorganic Chemistry
Communication
3
0
determinations for the pink and green crystals confirmed their
identity as [Co (BPMP)(μ -SH)(MeCN)](BF ) (1a; CCDC
(HPhBIMP), which bears some structural similarities to both
HBPMP and HN-Et-HPTB (Scheme 1).
2
2
4 2
t
1
1
845105) and [Co (BPMP)(μ -OH)](BF ) (1c; CCDC
The use of HPhBIMP allowed C−S bond cleavage of NaS Bu
2
2
4 2
845102), respectively (Figure S1). The use of 2 equiv of
in the presence of Et N and Co(BF ) ·6H O in DMF (1:1:2:2)
3
4 2
2
t
NaS Bu in the above reaction yielded [Co (BPMP)(SH) ]-
at RT, and complex [Co (PhBIMP)(μ -SH)(DMF)](BF )
2
2
2 2 4 2
(
BF ) (1b; CCDC 1845103; Figure 1) along with 1c, thus
(2a; CCDC 1845108; Figure 1) was isolated as purple crystals
in 68% yield. Unlike the formation of 1b, the use of excess
NaS Bu in the above reaction did not change the identity or yield
4
t
of the product. Interestingly enough, the use of NaSPh in the
above reaction also yielded 2a in comparable yield (61%). The
t
formation of BuOH (47%) and PhOH (57%) during the
t
reactions involving NaS Bu and NaSPh, respectively, was
identified by gas chromatography (GC) analysis (Figure S4),
which further substantiated the desulfurization process.
In the next stage, the range of solvents suitable for the
desulfurization reactions was explored. MeCN is known to
undergo base-catalyzed partial hydrolysis to generate acetamide,
26
which, in turn, may coordinate to the dicobalt(II) unit. In the
absence of both Et N and thiol, the reaction in MeCN yielded a
3
solvent-coordinated complex, [Co (PhBIMP)(MeCN) ]-
2
2
(
BF ) (2b; CCDC 1845107; Figure S2), thus indicating that
4 3
a dinuclear Co(II) species may readily form in the reaction
system. The reaction of Co(BF ) ·6H O, HPhBIMP, and
4
2
2
t
NaS Bu/NaSPh in MeCN, finally, allowed C−S bond cleavage,
and the complex isolated was characterized as [Co (PhBIMP)-
2
(
μ -SH)(MeCN)](BF ) (2c; CCDC 1845104; Figure S2).
2 4 2
The desulfurization process in the presence of Et N was further
3
confirmed to be operative in tetrahydrofuran, methanol, ethanol,
and ethyl acetate (Table S3). Complex 2a was isolated in each
case, with yields ranging from 35 to 50% compared with 42%
and 68% in MeCN (2c) and DMF (2a), respectively. Therefore,
the desulfurization reaction could be carried out in six different
solvents, of which DMF comes out to be the best choice.
In the molecular structures of both 1a and 2a, the −SH group
forms an unsymmetrical bridge between the two Co(II) atoms
with short and long Co−S distances of 2.358(1) and 2.717(1) Å
(
for 1a) and 2.358(1) and 2.644(1) Å (for 2a), while the Co−
Co distances are 3.313 and 3.322 Å, respectively. The molecular
structure of 2c is almost identical with that of 2a with Co−S
distances of 2.339(2) and 2.730(2) Å. The terminal hydro-
sulfides in 1b showed relatively smaller Co−S distances
[
2.330(1) and 2.316(1) Å], while the Co−Co distance is
comparatively longer (3.344 Å) than that in 1a or 2a. The
presence of coordinated −SH groups in 1a, 1b, 2a, and 2c was
further confirmed by IR spectroscopy [ν = 2493 cm (1a),
Figure 1. Molecular structures (50% probability thermal ellipsoids) for
the cationic parts of 1b and 2a.
−
1
SH
−
1
−1
−1
1
t
2
489 cm (1b), 2491 cm (2a), 2514 cm (2c)] and H
confirming C−S bond cleavage of NaS Bu. Moreover, the initial
NMR spectroscopy [δS−H = 44.09 ppm (1a), 44.13 ppm (1b);
36.17 ppm (2a), 36.09 ppm (2c)], which are comparable with
green solution changed to pink within a day when the reaction
t
was performed using 1 equiv of NaS Bu in the absence of Et N,
3
the data for previously reported metal hydrosulfide com-
which subsequently yielded 1a. Also, the use of less Et N (∼1.5
3
31−34
plexes.
Analogous chloro complexes [Co (BPMP)(Cl) ]-
2 2
equiv) diminished the formation of 1c during the synthesis of
(
(
BF ) (1d; CCDC 1857215) and [Co (PhBIMP)(μ -Cl)-
4
2
2
1
b. We may therefore conclude that Co(BF ) ·6H O mediates
4 2 2
DMF)](CoCl ) (2e; CCDC 1857216; Figures S1 and S3)
4
the C−S bond cleavage of thiolates in the presence or absence of
were also synthesized for their use as control compounds for the
assignments of H NMR signals and IR stretching frequencies of
a base (here Et N). However, in the presence of a base,
1
3
−
generation of the OH ion in the solution may be promoted,
the coordinated SH groups of 1a, 1b, and 2a and 2c,
respectively.
II
II
thus generating a Co (μ -OH)Co species (1c) along with 1a/
2
1
b. Furthermore, 1c could also be converted to 1a in 46% yield
Inspired by such facile desulfurization of both aliphatic and
aromatic thiols, we carried out a systematic exploration for
desulfurization of a diverse series of 25 substrates in DMF.
Complex 2a was isolated in varying yields and was characterized
by unit cell determination of the single crystals in each case
(Table S4). A list of 10 different substrates arranged according
to the generally increasing difficulty level of desulfurization in
t
upon treatment with BuSH. However, it was soon realized that
a and 1b were somewhat difficult to isolate as analytically pure
crystalline solids. On the basis of the results obtained using
1
26
HBPMP (this work) and HN-Et-HPTB (earlier work), we
therefore moved our attention to 2,6-bis[bis[(N-1-methyl-4,5-
diphenylimidazoylmethyl)amino]methyl]-4-methylphenol
B
DOI: 10.1021/acs.inorgchem.8b01588
Inorg. Chem. XXXX, XXX, XXX−XXX

Inorganic Chemistry
Communication
6
,35−37
the HDS process
are provided in Scheme 2. The
which, upon standard workup, yielded 2a in 54% and 52% yield,
corresponding organic products (mostly alcohols/phenols)
respectively. These results indicate that the formation of a
II
−
Co (OH ) species (green) may be promoted by the addition
2
Scheme 2. Yields of 2a and Organic Products Obtained by
Desulfurization of 10 Representative Substrates
of Et N. Interestingly, while using thiophene as the substrate in
3
the absence of Et N, a few block-shaped pink crystals were
3
obtained along with the characteristic needle-shaped purple
crystals of 2a, and the pink compound was identified as
[
Co (PhBIMP)(H O) (DMF) ](BF ) (2d; CCDC 1845106;
2 2 2 2 4 3
Figure S3). The same reaction with thiophene in the presence of
Et N, however, yielded only 2a in 40% yield. A combination of
3
the results for both aliphatic and aromatic thiols, in general,
strongly suggests that a dicobalt(II) unit containing terminal
−
OH and H O (in the presence and absence of Et N,
2
3
2
6
respectively) may indeed be generated. Such a dicobalt(II)
complex may subsequently accommodate a terminal or bridging
−
thiolate group, followed by the attack of a nearby OH /H O at
2
the carbon center bearing the thiol group to yield 2a and the
corresponding phenol/alcohol.
In summary, a unique, Co(II) mediated, complete desulfur-
ization process of industrially relevant thiols, sulfides and
thiophene derivatives has been developed. Unlike all of the high-
temperature desulfurization reactions reported in the literature
so far, the current method may be operated at RT in six different
solvents. Additionally, this innovative synthetic strategy may
initiate further investigations involving other transition metals
such as Fe(II) for the synthesis of a new class of
diiron−hydrosulfide complexes and subsequent exploration of
their reactivity in future.
were identified by gas chromatography−mass spectrometry
ASSOCIATED CONTENT
(
GC-MS; Figures S4 and S5). Yields for the organic products
■
were also measured (Figures S6−S11) using GC and were found
*
S
Supporting Information
to be comparable with the respective yields of 2a (Table S4).
The Supporting Information is available free of charge on the
ACS Publications website at DOI: 10.1021/acs.inorg-
chem.8b01588.
1
The formation of 2a was further confirmed by H NMR, IR,
electronic absorption spectroscopy, and electrospray MS (ESI-
MS) of the purple crystalline solids obtained after desulfuriza-
tion of 10 representative substrates (Figures S27−S36).
Isolation of 2a in the case of sulfides and thiophene derivatives
Experimental details, molecular structures and spectro-
scopic data (PDF)
(
Scheme 2) confirmed the complete desulfurization of these
Accession Codes
substrates. In addition to one thiol group, the substrates 2-
mercaptophenol, 2-aminothiophenol, 4-mercaptopyridine, and
2
groups, which might potentially bind to the Co(II) centers and
thus might hinder the reaction. Successful desulfurization of
even those substrates in 22−62% yield therefore suggests
appreciable functional group tolerance.
CCDC 1845102−1845108 and 1857215−1857216 contain the
supplementary crystallographic data for this paper. These data
can be obtained free of charge via www.ccdc.cam.ac.uk/
data_request/cif, or by emailing data_request@ccdc.cam.ac.
uk, or by contacting The Cambridge Crystallographic Data
Centre, 12 Union Road, Cambridge CB2 1EZ, UK; fax: +44
-thiobarbituric acid feature additional N/O-donor functional
1223 336033.
Careful investigations revealed that the addition of 2 equiv of
t
Co(BF ) ·6H O into a reaction mixture of HPhBIMP, NaS Bu/
NaSPh, and Et N (1:1:2) in DMF initially resulted in the
formation of a green solution, presumably because of the
formation of a Co (OH ) species. In the case of NaS Bu, the
4
2
2
AUTHOR INFORMATION
Corresponding Author
*E-mail: icam@iacs.res.in.
■
3
II
2
−
t
green color changed to purple within 1 min, while for NaSPh, it
took ∼2 days for the visual color change to start taking place.
While multiple attempts were made to isolate the green
compound, only 2a was isolated after ∼5−6 days in 68% and
ORCID
Amit Majumdar: 0000-0003-0522-8533
Notes
The authors declare no competing financial interest.
6
1% yield, respectively. The facile conversion of the green
solution to the purple solution (Figure S14) justified the
problem encountered in isolation of the green species. The mass
spectrometric study of the green solution within 30 min of its
ACKNOWLEDGMENTS
■
A.M. acknowledges SERB (Project File No. EMR/2017/
000828) and CSIR, India for funding. T.G. and M.J. acknowl-
edges CSIR, India, and A.D. acknowledges UGC, India for
fellowships. The authors thank Mr. S. Paul (the J. G. group) and
Mr. A. Bera (the T. K. P. group), IACS, for help with the GC
experiments.
generation also indicated the presence of both [Co (PhBIMP)-
2
2
+
2+
(
SH)] and [Co (PhBIMP)(OH)] at m/z 649.96 and
2
6
42.45, respectively (Figure S17). Finally, in the absence of
3
t
Et N, the reaction mixtures containing either NaS Bu or NaSPh
immediately form a purple/pink solution (instead of green),
C
DOI: 10.1021/acs.inorgchem.8b01588
Inorg. Chem. XXXX, XXX, XXX−XXX

Inorganic Chemistry
Communication
Produced by C−S Bond Cleavage of Pyridyl-Substituted Dibenzothio-
phenes. Organometallics 2008, 27, 4475−4483.
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