Nickel(II) thiolates derived from transmetallation reaction of [Zn(Tab)4](PF6)2 with Ni(II) ions and their catalytic activity toward the CN coupling reactions

Article abstract of DOI:10.1016/j.inoche.2014.05.035

Reactions of NiCl₂·6H₂O or Ni(ClO ₄)₂·6H₂O with 2,2′-bipyridine (2,2′-bipy), or 2-bis(diphenylphosphino)ethane (dppe) or 1,4-bis(diphenylphosphino)butane (dppb) followed by addition of [Zn(Tab) ₄](PF₆)₂ (1) resulted in the formation of one trinuclear cationic complex [(2,2′-bipy)₄Ni₃(μ- Tab)₄]Cl_0.5(PF₆)_5.5 (2), one mononuclear cationic complex [Ni(Tab)₂(dppe)](PF₆) ₂ (3), and one dinuclear cationic complex [Ni₂(dppb)(μ- Tab)₂(Tab)₂](PF₆)₂(ClO ₄)₂ (4). Complexes 2-4 were characterized by elemental analysis, IR, UV-vis, ¹H and ³¹P NMR, and single-crystal X-ray diffraction. In the [(2,2′-bipy)₄Ni₃(μ-Tab) ₄]^{6 +} hexacation of 2, the central Ni(II) atom is connected to two [Ni(2,2′-bipy)₂]^{2 +} fragments by two pairs of μ-Tab ligands, forming a linear trinuclear cationic structure. The Ni(II) center of the dication of 3 is tetrahedrally coordinated by two S atoms from two Tab ligands and two P atoms of one dppe ligand. Complex 4 has a dimeric cationic structure in which two [(Tab)Ni]^{2 +} species are linked by a pair of μ-Tab ligands and one dppb ligand. Complexes 2-4 displayed high catalytic activity toward the cross-coupling reactions of arylboronic acids and amines to produce N-arylated amines.

Full text of DOI:10.1016/j.inoche.2014.05.035

Inorganic Chemistry Communications 46 (2014) 159–162
Contents lists available at ScienceDirect
Inorganic Chemistry Communications
journal homepage: www.elsevier.com/locate/inoche
Nickel(II) thiolates derived from transmetallation reaction of
[
Zn(Tab) ](PF ) with Ni(II) ions and their catalytic activity toward the
4
6 2
C\N coupling reactions
a
a
a,
a
a,
a
Jing Shi , Fu-Ling Li , Hong-Xi Li ⁎, Fan Wang , Hong Yu ⁎, Zhi-Gang Ren ,
a
a,b,
Wen-Hua Zhang , Jian-Ping Lang ⁎⁎
College of Chemistry, Chemical Engineering and Materials Science, Soochow University, Suzhou 215123, Jiangsu, People's Republic of China
a
b
State Key Laboratory of Organometallic Chemistry, Shanghai Institute of Organic Chemistry, Chinese Academy of Sciences, Shanghai 200032, People's Republic of China
a r t i c l e i n f o
a b s t r a c t
Article history:
Reactions of NiCl ·6H O or Ni(ClO ) ·6H O with 2,2′-bipyridine (2,2′-bipy), or 2-bis(diphenylphosphino)eth-
2
2
4
2
2
Received 31 March 2014
Accepted 6 May 2014
Available online 29 May 2014
ane (dppe) or 1,4-bis(diphenylphosphino)butane (dppb) followed by addition of [Zn(Tab)
in the formation of one trinuclear cationic complex [(2,2′-bipy) Ni (μ-Tab) ]Cl0.5(PF 5.5 (2), one mononuclear
cationic complex [Ni(Tab) (dppe)](PF (3), and one dinuclear cationic complex [Ni (dppb)(μ-Tab) (Tab)
PF (ClO (4). Complexes 2–4 were characterized by elemental analysis, IR, UV–vis, H and P NMR, and
single-crystal X-ray diffraction. In the [(2,2′-bipy) hexacation of 2, the central Ni(II) atom is con-
4 6 2
](PF ) (1) resulted
4
3
4
6
)
2
)
6 2
2
2
2
]
1
31
(
6
)
2
4 2
)
Keywords:
Nickel(II) thiolate complex
6
+
4
Ni
fragments by two pairs of μ-Tab ligands, forming a linear trinuclear cationic
structure. The Ni(II) center of the dication of 3 is tetrahedrally coordinated by two S atoms from two Tab ligands
3
(μ-Tab)
4
]
2
+
2
nected to two [Ni(2,2′-bipy) ]
4-(Trimethylammonio)benzenethiolate
Transmetallation
Crystal structure
Catalysis
2
+
and two P atoms of one dppe ligand. Complex 4 has a dimeric cationic structure in which two [(Tab)Ni] species
are linked by a pair of μ-Tab ligands and one dppb ligand. Complexes 2–4 displayed high catalytic activity toward
the cross-coupling reactions of arylboronic acids and amines to produce N-arylated amines.
©
2014 Elsevier B.V. All rights reserved.
Over the past decades, nickel thiolate compounds have received
much attention due to their rich redox chemistry [1], and structural
diversity [2], and their potential applications in biological systems [3],
advanced materials [4], and catalytic processes [5]. Thiolates are
known to coordinate at nickel centers via various bonding modes such
of various N-ligands could afford a series of Co(II) or Co(III) thiolate
complexes [15]. Could this method be used to prepare some Ni thiolate
complexes through the transmetallation reaction of nickel ions with 1?
On the other hand, N-arylated amines are ubiquitous in biochemical,
biological, and medicinal structures and functions [16]. The Pd-, Rh-, Cu-,
Ni- or Co- [17] catalyzed arylation of amines with aryl halides is one of
the most efficient methods for the synthesis of N-arylated amines.
In 1998, the groups of Chan, Evans, and Lam et al. developed the Cu-
mediated oxidative amination of arylboronic acids with amines and
other nucleophiles [18], providing a valuable alternative to traditional
cross-couplings in the construction of C\N bonds. However, other
types of transition metal complexes that could catalyze the Chan–Lam re-
action have been less explored [19]. Recently, we have found that Cu(I)
thiolate complexes showed high catalytic activity toward the cross cou-
pling reaction of N-heterocycles and arylboronic acids [20]. Could nickel
thiolates catalyze analogous cross-coupling reactions? With these ques-
tions in mind, we carried out the transmetallation reactions of 1 with
nickel ions and N-, or P-donor ligands. One trinuclear cationic complex
2 3
as η-S, μ-S, μ -S, μ -S, etc.. It is noted that the nickel thiolate complexes
have mono- [6], di- [7], tri- [8], tetra- [9], penta- [10], hexa- [11], and
poly-nuclear [12] to polymeric structures [13]. These complexes were
mainly prepared by protonolysis, metathesis, oxidation–reduction and
precursor reactions [2b]. However, another approach, namely,
transmetallation reaction of Ni(II) ion with the transition metal thiolate
complexes, has been less employed to synthesize nickel thiolates [14].
Recently, we have been interested in the syntheses and properties of
metal thiolate complexes and found that the transmetallation reaction
is a useful route to construct metal thiolates [2b,15]. For example,
reactions of a mononuclear complex [Zn(Tab)
4
](PF
6
)
2
(Tab = 4-
2
+
(
trimethylammonio)benzenethiolate) (1) with Co in the presence
[
(2,2′-bipy)
nuclear cationic complex [Ni(Tab)
3·CH Cl ·0.5MeOH), and one dinuclear cationic complex [Ni
dppb)(μ-Tab) (Tab) ](PF (ClO ·2(CH Cl 0.5 (4·2(CH Cl 0.5) were
4
Ni
3
(μ-Tab)
4
]Cl0.5(PF
6
)
5.5·2.5MeCN (2·2.5MeCN), one mono-
2
(dppe)](PF ·CH Cl ·0.5MeOH
6
)
2
2
2
⁎
Corresponding authors. Tel.: +86 512 65882865; fax: +86 512 65880328.
(
(
2
2
2
⁎
⁎ Correspondence to: J. -P. Lang, College of Chemistry, Chemical Engineering and
2
2
6
)
2
4
)
2
2
2
)
2
2
)
Materials Science, Soochow University, Suzhou 215123, Jiangsu, People's Republic of
China. Tel.: +86 512 65882865; fax: +86 512 65880328.
isolated therefrom. Complexes 2–4 did exhibit high catalytic perfor-
E-mail address: jplang@suda.edu.cn (J.-P. Lang).
mances in the cross-coupling reactions of arylboronic acids and amines
http://dx.doi.org/10.1016/j.inoche.2014.05.035
1387-7003/© 2014 Elsevier B.V. All rights reserved.

160
J. Shi et al. / Inorganic Chemistry Communications 46 (2014) 159–162
to produce various N-arylated amines. Herein we report their syntheses,
crystal structures and catalytic properties.
Å) [8b]. The average Ni\N bond length (2.074(2) Å) is close to that
observed in [Ni (sppm) ](BPh (2.065(3) Å) [8c].
Compound 3·CH Cl ·0.5MeOH crystallizes in the monoclinic space
group P2/c, and its asymmetric unit contains one discrete [Ni(Tab)
3
4
4 2
)
As shown in Scheme S1, treatment of NiCl
,2′-bipy followed by addition of one equiv. of 1 in MeOH and MeCN
at room temperature afforded one trinuclear cationic complex 2 in
0% yield. Analogous reactions of NiCl ·6H O with dppe and
Zn(Tab) ](PF or Ni(ClO ·6H O with dppb and [Zn(Tab) ](PF
2 2
·6H O with 2 equiv. of
2
2
2
2
(dppe)]2 dication, two PF
+
−
anions, one CH Cl
2 2
solvent molecule and
6
8
2
2
half a MeOH solvent molecule. In the dication of 3, the Ni(1) center
has a square planar environment, coordinated by two S atoms from
two Tab ligands and two P atoms of a dppe ligand (Fig. 2). The average
Ni\S bond distance (2.2090(12) Å) in 3 (Table S2) is comparable to
those found in square planarly-coordinated Ni(II) complexes such as
[
4
6
)
2
4
)
2
2
4
6 2
)
under the similar reaction conditions afforded a mononuclear cationic
complex 3 in 85% yield and a dinuclear cationic complex 4 in 87%
yield. The reason that the above three metal and ligand substitution
reactions could be realized may be due to the facts that Ni(II) in 2–4
may have the higher thiolate binding ability than Zn(II) in 1 and the
N- or P-donor ligands (2,2′-bipy, dppe, dppb) in 2–4 are stronger than
Tab in 1. Complexes 2–4 are stable toward oxygen and moisture. They
[Ni(SAr)
Ar = 2-methylphenyl) [6a], [(dppe)Ni(Me)(SPh)] (2.2016(12) Å) [5],
and [Ni(SC HF (dppe)] (2.2112(15) Å) [6c]. The Ni\P bond length
(2.1820(12) Å) is close to that observed in [Ni(SC HF (dppe)]
(2.1766(14) Å) [6b], but shorter than those found in [Ni(SPh) (PMe
2 3 2
(PMe ) ] (2.2138(5) Å for Ar = phenyl; 2.2116(7) Å, for
6
4 2
)
6
4 2
)
are insoluble in toluene, hexane, and Et
2
O, but soluble in MeCN,
2
3 2
) ]
MeOH, DMSO and DMF. Their elemental analyses were consistent
with their chemical formula. The electronic spectrum of 2, 3 or 4 in
MeCN exhibited a strong and broad adsorption at 295 nm (2), 303 nm
(2.2199(7) Å) [6a]. The S(1)\Ni(1)\S(2) and P(1)\Ni(1)\P(2) bond
angles (99.40(4)° vs 86.36(4)°) in 3 are enlarged compared with those
of the corresponding ones of the similar Ni(II) complex [Ni(SC HF )
6 4 2
(
(
3), or 299 nm (4) (Fig. S1), which might be ascribed to the ligand
Tab)-to-metal charge transfer (LMCT) [21].
(dppe)] (92.31(6)° vs 85.78(5)°) [6b].
2 2
Compound 4·2(CH Cl )0.5 crystallizes in the triclinic space group Pī,
+
Compound 2·2.5MeCN crystallizes in the triclinic space group Pī,
and its asymmetric unit consists of one [Ni
2
(μ-Tab)
anions, and two halves of
solvent molecules. The tetracation of 4 consists of a dimeric
structure in which two [(Tab)Ni] fragments are connected by a pair of
μ-Tab ligands and one dppb ligand (Fig. 3). The resulting Ni core
structure is similar to those found in other dinuclear nickel(II) com-
plexes such as [Ni {(2,6-Ph PCH S} ][PF [7]. Ni(1) or Ni(2)
2 2
(Tab)
(dppb)]4
6
+
−
−
and its asymmetric unit contains one [Ni
hexacation, five and one-half of PF
3
(μ-Tab)
4
(2,2′-bipy)
4
]
tetracation, two PF
CH Cl
6 4
anions, two ClO
−
−
6
anions, one-half of a Cl ion, and
2
2
two and one-half of MeCN solvent molecules. The internal Ni(2) atom
in this hexacation is connected to two Ni(II) atoms, Ni(1) and Ni(3),
by two pairs of bridging Tab ligands, forming a trinuclear linear struc-
ture (Fig. 1). The central Ni(2) center adopts a square planar coordina-
tion geometry, coordinated by four S atoms of four μ-Tab ligands,
while the terminal Ni(1) or Ni(3) center is octahedrally coordinated
by two S atoms from two μ-Tab ligands and four N atoms from two
2 2
S
2
2
2
)
2
C
6
H
3
2
6 2
]
center in 4 again takes a square planar coordination geometry, coor-
dinated by three S atoms from one terminal and two μ-Tab ligands
and one P atom from one dppb ligand. The mean Ni–μ–S bond dis-
tance (2.2236(17) Å) (Table S2) in 4 is slightly longer than the cor-
responding one of 2. The Ni\P bond length (2.172(5) Å) in 4 is
2
,2′-bipy ligands. The mean terminal Ni–μ–S bond distance
2.4419(11) Å) (Table S2) is slightly longer than those of the corre-
sponding ones in complex [Ni (sppm) ](BPh (2.401(3) Å; sppm =
2-sulfanylphenyl)bis(pyrazolyl)methane) [8c]. This elongation may
(
3
4
)
4 2
2 2 2 2 6 3 2 6 2
close to those observed in [Ni {(2,6-Ph PCH ) C H S} ][PF ]
(
(2.183(2) Å) [7], but longer than that in 3. The terminal Ni\S bond
length (2.185(5) Å) is shorter than the corresponding value in 3.
The Ni(1)⋯Ni(2) contact is 2.8199(12) Å, which is much shorter
be due to large steric hindrance caused by the bulky 2,2′-bipy ligand
and the Tab ligand. The mean Ni(2)–μ–S bond length (2.2153(10) Å)
is shorter than that of [Ni
parable to those found in [{Ni(μ-SiPr)(μ-mtet)}
methylthioethanethiolate), [Ni{Ni(NH CH
3
(sppm)
4
](BPh
4
)
2
(2.270(3) Å) [8c], but com-
] (2.210(1) Å; mtet =2-
CH S) }]Cl (2.212(4)
than those observed in 2 and [Ni
2
{(2,6-Ph
2
PCH
2
)
2
C
6
H
(bss)
3
S}
2
][PF
](BF
6
]
2
6
(3.1959(12) Å) [7], but longer than that found in [Ni
(2.784(2) Å) [8a].
3
4
4
)
2
2
2
2
2
2
Fig. 1. View of the [Ni
scheme and 50% thermal ellipsoids. All H atoms were omitted for clarity.
3
(Tab)
4
(2,2′-bipy)
4
]6+ hexacation structure of 2 with a labeling
Fig. 2. View of the [Ni(Tab)
50% thermal ellipsoids. All H atoms were omitted for clarity.
(dppe)]2+ dication structure of 3 with a labeling scheme and
2

J. Shi et al. / Inorganic Chemistry Communications 46 (2014) 159–162
161
or dppb) generated one trinuclear complex 2, one mononuclear
complex 3 and one dinuclear complex 4. Complexes 2–4 displayed
high catalytic activity toward the Chan–Lam coupling reaction of amines
and arylboronic acids to produce the corresponding N-arylated amines
with high yields while 2 exhibited a better catalytic activity than 3 and
4. It is anticipated that the synthetic methodology reported here could
be applied to the rational design and assembly of other Ni(II)/thiolate
complexes with new structures and higher catalytic activities. Further
studies on this respect are underway in our laboratory.
Acknowledgments
The authors thank the National Natural Science Foundation of China
(
21171124, 21171125 and 21371126), State Key Laboratory of Organo-
metallic Chemistry, Shanghai Institute of Organic Chemistry, Chinese
Academy of Sciences (201201006) for financial supports. J.P. Lang also
highly appreciate the support for the Qin-Lan Project and the “333” Pro-
ject of Jiangsu Province, the Priority Academic Program Development of
Jiangsu Higher Education Institutions, and the “SooChow Scholar”
Program of Soochow University. The authors also greatly thank the
helpful comments from the editor and the reviewers.
Appendix A. Supplementary data
2 2 2
Fig. 3. View of the [Ni (μ-Tab) (Tab)
(dppb)]4+ tetracation structure of 4 with a labeling
scheme and 50% thermal ellipsoids. All H atoms were omitted for clarity.
CCDC 983485–983487 contain the supplementary crystallographic
2 2 2 2
data for 2·2.5MeCN, 3·CH Cl ·0.5MeOH and 4·2(CH Cl )0.5. These
data can be obtained free of charge via http://www.ccdc.cam.ac.uk/
conts/retrieving.html or from the Cambridge Crystallographic Data Cen-
tre, 12 Union Road, Cambridge CB21EZ, UK; fax: (+44) 1223 336 033;
or e-mail: deposit@ccdc.cam.ac.uk. Supplementary data to this article
can be found online at http://dx.doi.org/10.1016/j.inoche.2014.05.035.
These data include MOL files and InChiKeys of the most important com-
pounds described in this article.
Phenylamine with phenylboronic acid was chosen as the model sub-
strate to optimize the N-arylation reaction conditions including reaction
temperature, solvent, and base. According to the optimization results
(
Table S3), the optimal reaction conditions were identified as follows: cat-
alyst loading ([Ni] = 20 mol%), 2 equiv. of 1,8-diazabicyclo[5.4.0]undec-
-ene (DUB) (as the base), and MeCN (as a solvent) along with a reaction
7
temperature of 60 °C. With these conditions in mind, a variety of amines
were chosen as the substrates in the cross-coupling N-phenylation reac-
tions (Table S4). The C\N bond formation reactions were performed
well for all the primary amines examined, and the expected products
were isolated in good yields. Relative to those with electron-deficient
substituent groups, the electron-donating p-substituted aryl amines
were found to proceed in higher yields. For example, reactions with aro-
matic amines bearing electron-donating substituent groups (methyl and
methoxyl) gave the cross-coupling products in higher yields (Table S4,
entries 2 and 5) compared with those carrying electron-withdrawing
ones (nitryl or chloro) (Table S4, entries 6 and 7). Aliphatic amines also
worked well (Table S4, entries 8 and 9), while diethylamine was surpris-
ingly reluctant (Table S4, entry 10). To our delight, poorly nucleophilic
amides also underwent such a C\N cross-coupling reaction in a medium
yield (Table S4, entry 11 using 2 as a catalyst). The steric hindrance of
aromatic amine may also affect the yields of the coupling products. The
lower yield (52%) was obtained for o-toluidine (Table S4, entry 4).
Encouraged by the efficiency of the N-phenylation reaction of amines
with phenylboronic acid described above, we also examined the substrate
scope of boronic acids. The arylation of aniline with different boronic acids
including o-/m-/p- tolylboronic acids, (4-methoxyphenyl)boronic acid
and (4-nitrophenyl)boronic acid catalyzed by 2 under the standard
reaction conditions afforded the corresponding products in relatively
good yields (Table S4, entries 12–16). Based on the results presented in
Table S4, complex 2 exhibited more efficient catalytic performance on
the cross-coupling reaction of amines with arylboronic acid than 3 and
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