Room-temperature carbon-sulfur bond formation from Ni(II) σ-aryl complex via cleavage of the S-S bond of disulfide moieties

Article abstract of DOI:10.1002/aoc.2975

The formation of ArSY (Y: C(= S)NMe₂, Ph, P(= O)(OEt) ₂) by reductive elimination from σ-aryl complexes (M(PPh ₃)₂PhBr, M = Ni, Pd), associated with disulfides (YS-SY, Y: C(=S)NMe₂ (1), Ph (2), P(=O)(OEt)₂ (3)), at ambient temperature, has been investigated. Various mechanistic features of disulfide bond (S-S) cleavage have been elucidated using disulfide 1 by ³¹P NMR spectroscopy and matrix-assisted laser desorption/ionization-time of flight mass spectrometric investigations. Based upon the results of nucleophilic cleavage of the S-S bond by PPh₃, studies of the reductive elimination process show that when M(PPh₃)₂PhBr is mixed with disulfide 1, competitive reactions occur between the PPh₃ ligand, disulfide 1 and a trace amount of water, leading to low C-S coupling yields; an oxidation reaction of PPh₃ with disulfide and water occur prior to C-S cross-coupling, and phosphonium ion intermediates are likely involved. However, when the disulfide 1 is pretreated with PPh₃, the Ni(II) σ-aryl complex affords the C-S coupling product nearly quantitatively at room temperature. The pretreatment method is also effective for the coupling reaction of disulfide 2 and Ni(II) σ-aryl complex. The difference between Ni(II) and Pd(II) σ-aryl complexes on C-S bond formation by reductive elimination can be explained by the affinity of metal for the thiolate ligands derived from the cleaved disulfide. Copyright 2013 John Wiley & Sons, Ltd. The formation of ArSY (Y: C(= S)NMe₂, Ph, P(= O)(OEt)₂) by reductive elimination from σ-aryl complexes (M(PPh₃)₂PhBr, M = Ni, Pd) at ambient temperature, has been investigated, a result that shows an effective C-S cross-coupling reaction. Copyright

Full text of DOI:10.1002/aoc.2975

Special Issue Article
Received: 12 December 2012
Revised: 8 January 2013
Accepted: 17 January 2013
Published online in Wiley Online Library
(wileyonlinelibrary.com) DOI 10.1002/aoc.2975
Room-temperature carbon–sulfur bond
formation from Ni(II) s-aryl complex via
cleavage of the S–S bond of disulfide moieties
Ken Okamotoa,b, Jeremy B. Housekeepera,c and Christine K. Luscombea,b*
ABSTRACT: The formation of ArSY (Y: C(= S)NMe2, Ph, P(= O)(OEt)2) by reductive elimination from s-aryl complexes (M(PPh3)
2PhBr, M = Ni, Pd), associated with disulfides (YSꢀSY, Y: C(=S)NMe2 (1), Ph (2), P(=O)(OEt)2 (3)), at ambient temperature, has
been investigated. Various mechanistic features of disulfide bond (SꢀS) cleavage have been elucidated using disulfide 1
by 31P NMR spectroscopy and matrix-assisted laser desorption/ionization–time of flight mass spectrometric investigations.
Based upon the results of nucleophilic cleavage of the SꢀS bond by PPh3, studies of the reductive elimination process show
that when M(PPh3)2PhBr is mixed with disulfide 1, competitive reactions occur between the PPh3 ligand, disulfide 1 and a trace
amount of water, leading to low CꢀS coupling yields; an oxidation reaction of PPh3 with disulfide and water occur prior to CꢀS
cross-coupling, and phosphonium ion intermediates are likely involved. However, when the disulfide 1 is pretreated with
PPh3, the Ni(II) s-aryl complex affords the CꢀS coupling product nearly quantitatively at room temperature. The pretreatment
method is also effective for the coupling reaction of disulfide 2 and Ni(II) s-aryl complex. The difference between Ni(II) and Pd
(II) s-aryl complexes on CꢀS bond formation by reductive elimination can be explained by the affinity of metal for the thiolate
ligands derived from the cleaved disulfide. Copyright © 2013 John Wiley & Sons, Ltd.
Keywords: CꢀS cross-coupling; nickel complex; disulfide; room temperature reaction
complexes to access carbon–sulfur bond formation under room
temperature conditions.
Aromatic carbon–sulfur bond formation is an important synthetic
Introduction
organic transformation.[1,2] In the past few decades carbon–
sulfur coupling reactions based on nickel,[3–7] palladium[8–19] or
copper[20–27] catalysis have become popular methods for the
synthesis of functional aryl sulfides, which are of particular interest
in organic electronics, such as high refractive index polymers,[28,29]
and in bioactive compounds.[30,31] Other transition metal-catalyzed
systems (namely iron-[32] or cobalt-based[33,34] systems) have also
been reported to catalyze CꢀS bond formation.
Results and Discussion
Mechanistic Aspects of SꢀS Bond Cleavage
First, we conducted studies on the SꢀS bond cleavage process.
The nucleophilic cleavage of the SꢀS bond by PPh3 and its
usability in synthesis of unsymmetrical disulfide have been
documented, where the nucleophilic attack by Ph3P on ArSSAr
is thought to form the benzene thiolate anion (ArSꢀ) and
thiophenoxyphosphonium ion Ph3P+ꢀSAr.[40,41] Meanwhile, the
disulfide moiety has also been found to react with transition
metal ions in several different pathways. For example, disulfides
can (i) form simple adducts or coordination complexes[42–44]
and (ii) undergo oxidation SꢀS bond cleavage reactions from
the transition metal.[36–38,44–49] Such oxidative SꢀS bond cleav-
age can sometimes involve homolysis of the SꢀS bond and it is
well known that the homolysis step is assisted by high
Although disulfides are more desirable to use as thiolation
reagents compared to thiols because of their stability and
because they are less pungent than the corresponding thiols,
classic Ni- and Pd-catalyzed coupling systems[4,35] with disulfides
have required high reaction temperatures and long reaction
times. More recently Ananikov et al. reported the reaction of
dichalcogenides with Ni(0) or Pd(0), and their application in the
catalytic addition reaction of dichalcogenides to alkynes at high
temperatures.[36–38] To the best of our knowledge, disulfide-
derived carbon–sulfur coupling at room temperature has rarely
been studied.[39] Furthermore, little is known about CꢀS cross-
coupling with a variety of disulfides except for diphenyl disulfide.
To achieve the goal of attaining a cross-coupling reaction
that affords CꢀS bond formation at room temperature as shown
in Scheme 1, the catalytic cycle would include the following
stages: (i) oxidative addition of an organic halide (RꢀX);
(ii) reaction of the disulfide with the M(II) complex; and (iii)
C-heteroatom reductive elimination. This report concentrates
on the process of disulfide reaction with the M(II) complex and
the proceeding reductive elimination with Ni(II) or Pd(II) s-aryl
*
Correspondence to: Christine K. Luscombe, Department of Materials Science and
Engineering, University of Washington, Seattle, WA 98195–2120, USA. E-mail:
luscombe@u.washington.edu
a Department of Materials Science and Engineering, University of Washington,
Seattle, WA 98195-2120, USA
b Molecular Engineering and Sciences Institute, University of Washington, Seattle,
WA 98195-1652, USA
c
Department of Chemistry, University of Washington, Seattle, WA 98195-1700, USA
Appl. Organometal. Chem. (2013)
Copyright © 2013 John Wiley & Sons, Ltd.

K. Okamoto et al.
M = Ni or Pd
ArX
LnM0
Ar-SR
l
iii. Reductive
Elimination
@RT
i. Oxidative
Addition
Cl
X
SR
LnMII
Ar
LnMII
Ar
insoluble
insoluble
Gray: well-known elementary process
Black: this work
l
ll
yellow
Cl
Cl
RS-, X-
RS-SR
ii. Ligand Exchange
@RT w/o base
Scheme 3. (i) Metal-free SꢀS bond cleavage reaction with PPh3;
(ii) reaction of M(II)(PPh3)2Cl2 metal complex with disulfide 1.
Scheme 1. Typical catalytic cycle of aryl halide and disulfide cross-
coupling reaction.
temperatures (>100 ꢁC).[46] In our case, there are three possible
pathways that for the cleavage of disulfide by the group 10 metal
complexes: redox-driven homolysis (path A), heterolysis (path B)
and phosphine-ligand-assisted heterolysis (path C) as shown in
Scheme 2. These paths A, B and C can be called oxidative
cleavage, radical-assisted cleavage, and nucleophile-assisted
cleavage, respectively. The first two pathways may afford M(0)
as an intermediate;[36–38,50–52] meanwhile pathway C does not
affect the oxidation state of the M(II) metal center. In order to
clarify the role of PPh3 and the metal during SꢀS bond cleavage
in disulfides, two reactions as shown in Scheme 3 were tested.
The reaction of disulfide 1 and PPh3 yielded S=PPh3, O=PPh3
a)
1
and tetramethylthiuram (Fig. 1a for 31P NMR and Fig. 1b for H
NMR). The nucleophilic attack by PPh3 on disulfide 1 most likely
forms the thiolated phosphonium ion (PPh+3ꢀS(CS)NMe2) and
the thiolate anion (ꢀS(CS)NMe2) as intermediates.[40] Nucleophilic
attack of the thiolate anion to the phosphonium ion would result
in the formation of tetramethylthiuram and S=PPh3. The
thiolated phosphonium ion can also react with the trace amount
of water in the deuterated chloroform to from O=PPh3 as shown
in Scheme 4.[40,53]
b)
The reaction of disulfide 1 with Ni(PPh3)2Cl2 (Scheme 3(ii))
afforded a green insoluble precipitate, O¼PPh3 and S=PPh3
(supporting information, Fig. S1). The insoluble precipitate was
analyzed using matrix-assisted laser desorption/ionization–
time of flight mass spectrometry (MALDI-TOF-MS) and
a
thiocarbamate-coordinated complex, Me2NCS2-NiPPh3Cl, was
detected (supporting information, Fig. S2). We also examined
31P NMR and MALDI-TOF mass spectra for the Pd complex and
the results were similar to the Ni analogue (supporting informa-
tion, Figs S3 and S4) although an additional complex, Me2NCS2-
Pd-SPPh3Cl, was also detected. The formation of O¼PPh3 and
S¼PPh3 presumably occurs via a similar mechanism as described
Figure 1. (a) Crude 31P NMR spectrum of reaction of disulfide 1 with
PPh3[54]; (b) crude 1H NMR spectrum of reaction of disulfide 1 with PPh3.[55]
Path A
Path B
Path C
Y
Y
Y
Y
Y
Y
Y
Y
X
X
X
S
S
S
S
S
S
X
S
S
X M2+
-PPh3
+PPh3
X M2+
X M2+
X M2+
P
Ph3P+-SY SY- + H2O
Ph3P+-SY Br- + H2O
Ph3P=O + 2YSH
P
P
P
Ph
Ph
Ph
Ph
Ph
Ph
Ph
Ph
Ph
Heterolysis
with redox reaction
Ph
Ph
Homolysis
Ph
Ph3P=O + YSH + HBr
Heterolysis with PPh3
[ArMX] + Ph3P+-SY SY-
anion exchange
[ArMSY] + Ph3P+-SYX-
+ H2O
Scheme 4. Possible reaction for the formation of O=PPh3.[40,53]
between PPh3 and disulfide
through metal center
+ H2O
above for the reaction in Scheme 3(i). However, in this case the
released thiolate anion can coordinate to the metal centers, pro-
viding the complexes observed in MALDI-TOF-MS.
[M(SY)2] + Ph3P=O + 2HX
[MXSY] + Ph3P=O + HX + HSY
: coordination bond
The two test reactions strongly suggest the involvement of
PPh3 in the room temperature cleavage of the disulfide bond,
Scheme 2. Possible disulfide bond cleavage mechanisms.
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Copyright © 2013 John Wiley & Sons, Ltd.
Appl. Organometal. Chem. (2013)

Room temperature C–S bond formation using Ni(II) and disulfides
which shows that the most feasible pathway for SꢀS bond cleav-
age is Scheme 2 path C. Ananikov et al. also observed the forma-
tion of E¼PPh3, where E = S or Se when reacting dichalcogenides
in the presence of Ni or Pd catalysts at high temperatures.[36,37]
However, in their case, M(SY)2 species was observed not MXSY
that we observe, suggesting that at high temperatures path A
or B is operating.[36] Although we cannot completely eliminate
paths A and B in our case, we believe that it is unlikely that these
paths are operating because high temperatures are typically re-
quired for such reactions.[56]
Table 1. Comparison of the yield of the carbon–sulfur bond forma-
tion with various disulfides with and without PPh3 pretreatment
Disulfide
Without PPh3
pretreatment
yield (%)a
With PPh3
pretreatment
yield (%)b
Ni
32
Pd
Ni
Pd
1
2
3
Tracec
Tracec
0
90
0
0
0
Tracec
92
93d
9
aThe yield was estimated by 1H NMR using tri(o-tolyl)phosphine as an
internal standard.
bIsolated yield.
CꢀS Cross-Coupling
cTrace amount of CꢀS coupling product was detected by GC-MS.
As noted above, ligated and/or unligated PPh3 can behave as a
trigger for the SꢀS bond cleavage in disulfides at room temper-
ature. Next, we selected several disulfides (1–3) and performed
reactivity screening with the Ni(II) or Pd(II) s-aryl complexes
(4, 5) in dichloromethane at room temperature with and without
pretreatment of the disulfide with PPh3 as shown in Scheme 5 to
study the reductive elimination step. Table 1 summarizes the
yields of the CꢀS coupling product. In most cases, where the
disulfide was not pretreated with PPh3, their restructured
phosphine compounds such as O¼PPh3 and S¼PPh3 were
observed via 31P NMR spectroscopy (see supporting information
Figs S5–10 for details) showing that the ligated PPh3 or the disso-
ciated PPh3 ligand was cleaving the SꢀS bonds. The reaction of
disulfide 1 or 3 with Ni complex 4 afforded low yields of CꢀS
coupling products, while the reaction with disulfide 2 only gave
trace amounts of the desired CꢀS coupling product as detected
by GC-MS. In comparison with Ni complex (4), Pd complex (5)
was not effective for CꢀS cross-coupling. In order to prevent loss
of the metal complex via reaction of the reagents with the PPh3
ligand, comparison reactions with the Ni complex and disulfide
1 and 2 pretreated with PPh3 were carried out, which afforded
the desirable CꢀS coupling product almost quantitatively
(Scheme 5c and Table 1). However, the Pd complex did not afford
dPotassium thiolate was used instead of pretreatment method.
the CꢀS coupling products even with the pretreated disulfide.
This is not surprising because most of the reported Pd-catalyzed
CꢀS coupling reactions require a bidentate phosphine ligand
with a large bite angle.[9,10,12] Moreover, several square planar
Pd(II) s-aryl complexes which have PPh3 and thiolate as ancillary
ligands are fairly stable and they do not catalyze CꢀS bond
formation.[18,57–61]
Unfortunately, it was very difficult to treat with disulfide 3 and
PPh3 owing to its high reactivity.[54] Thus potassium thiolate 6
was used instead of pretreated disulfide 3. The reaction of Ni
complex 4 and thiolate 6 gave CꢀS coupling product in good
yield. Again, Pd complex 5 did not afford CꢀS coupling product.
Conclusion and Scope
We have clarified the SꢀS bond cleavage process that occurs be-
tween disulfides and metal complexes at room temperature. The
presence of PPh3 is the key component in the heterolytic SꢀS
bond cleavage. Since phosphonium salt formation reaction
occurs prior to the CꢀS cross-coupling reaction, if the disulfide
is not pretreated with PPh3, the resulting product consists mainly
of phosphine oxide which is derived from the phosphonium salt
and water. On the other hand, once the disulfide is pretreated
with PPh3, the formed thiolate anion can react with the Ni(II)
s-aryl complex to afford the CꢀS coupling product in high
yield. We believe this finding will assist with further improve-
ments of room-temperature nickel or palladium-catalyzed CꢀS
coupling reactions.
a)
Disulfides
S
O
EtO
OEt
S
P
S
NMe2
S
P
O
Me2N
S
Ph
S
EtO
OEt
S
Ph
S
1
2
3
disulfide
(YSSY)
2 equiv.
b)
PPh3
Br
PPh3
M
SY
DCM, RT
Y = Ph, C(=S)NMe2, P(=O)(OEt)2
Low yield
M = Ni (4), Pd (5)
c)
d)
pretreated disulfide
with PPh3
Experimental
SY
4 or 5
1H, 13C, and 31P NMR spectra were recorded on Bruker AV-300
and AV-400 spectrometers using CDCl3 as a solvent and
tetramethylsilane as an internal standard for 1H NMR spectra
(0.00 ppm), and 31P{1H} spectra were referenced to external
H3PO4 (0.00 ppm). All reactions were carried out under a nitrogen
atmosphere using standard Schlenk techniques. However, CꢀS
coupling reactions could be carried out in an air atmosphere also.
Bromobenzene, PPh3, NiBr2, Pd(PPh3)4, Ni(PPh3)2Cl2, Pd(PPh3)2Cl2,
diethylphosphite, tetramethylthiuram disulfide, diphenyl disul-
fide, sulfur, K2CO3, all solvents (THF, dichloromethane, CDCl3)
were purchased from Aldrich and used without further purifica-
tion. Disulfide 3 was prepared in two-step syntheses according
DCM, RT
Y = Ph, C(=S)NMe2
High yield
OEt
KS
6
P
OEt
O
4 or 5
SY
THF/DCM, RT
Y = P(=O)(OEt)2
High yield
Scheme 5. (a) Structure of disulfides tested; (b) reaction of the disulfides
with the s-aryl complexes; (c) reaction of PPh3-pretreated disulfides with
s-aryl complexes; (d) reaction of potassium thiolate 6 with s-aryl
complexes.
Appl. Organometal. Chem. (2013)
Copyright © 2013 John Wiley & Sons, Ltd.
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K. Okamoto et al.
to the literature[62] and modification of disulfide formation reac-
tion.[63] Ni complex (4)[64] and Pd complex (5)[65] were prepared
according to a previously established procedure.
Acknowledgments
The work was supported by the NSF (CAREER DMR 0747489 (CKL),
CCI Center for Selective C–H Functionalization CHE 1205646 (partial
support for KO), SOLAR award DMR 1035196 (JH), and EFRI-SEED
1038165), and AFOSR Syn Chem Program FA9550-10-1-0430
(partial support for KO). The authors declare no competing finan-
cial interest.
Reaction of Disulfide 1 and PPh3
An NMR tube was charged with disulfide 1 (0.05 mmol) and PPh3
(0.05 mmol) in CDCl3 (1ml). The resulting phosphorus compounds
were tracked by 31P NMR until the PPh3 peak disappeared from
the spectra (72 h).
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