Inorganic Chemistry Communications 8 (2005) 955–959

www.elsevier.com/locate/inoche

Thiolation of iodobenzene catalyzed by fluorinated

bis-imino nickel NNN pincer complexes
Oscar Baldovino-Pantaleón, Simón Hernández-Ortega, David Morales-Morales *

Instituto de Quı́mica, Universidad Nacional Autónoma de México, Cd. Universitaria, Circuito Exterior. Coyoacán 04510, México DF, Mexico

Received 2 June 2005; accepted 14 July 2005

Available online 30 August 2005

Abstract

The synthesis of bis-imino nickel(II) NNN pincer complexes of the type [NiCl2{C5H3N-2,6-(CHNArf)2}]; Arf = C6H3-2,3-F2 (1),
C6H3-2,5-F2 (2), C6H3-3,4-F2 (3), C6H3-3,5-F2 (4), C6H2-2,3,4-F3 (5), C6H2-2,3,6-F3 (6), C6H2-2,4,5-F3 (7), and C6H2-2,4,6-F3 (8),
has been achieved and its reactivity explored proving these compounds to be efficient in the alkyl and aryl thiolation of iodobenzene.

2005 Elsevier B.V. All rights reserved.

Keywords: Thiolation; C–S coupling reactions; Pincer complexes; Nickel complexes; Catalysis; Crystal structures

In the recent years, there has been an increasing de-
mand on efficient and high yield methods for the synthe-
sis of diarylthioethers and alkylarylthioethers owing to
their importance as structural motifs in a wide range
of molecules with numerous and important applications
[1]. Moreover, the scope and application of organosulfur
chemistry in organic synthetic reactions has increased
tremendously since sulfur-containing groups serve as
an important auxiliary function in synthetic sequences
[2], for instance, in the reversing of the polarity (Umpo-
long), the enhancement of the acidity of C–H bonds,
and the transfer of chirality from sulfur to carbon [3].
In addition, arylsulfides are a common functionality
found in numerous pharmaceutically active compounds
[4]. In fact, a number of drugs in therapeutic areas, such
as diabetes and anti-inflammatory, immune, Alzhei-
mer
s, and Parkinson
s diseases, contain the aryl sulfide
functionality [5]. On the other hand, transition metal
complex-catalyzed reactions have made a great contri-
bution to the recent growth of organic synthesis [6].
Considerable attention has also been focused on sul-
*
Corresponding author. Tel.: +52 55 56224514; fax: +52 55
56162217.
E-mail address: damor@servidor.unam.mx (D. Morales-Morales).
fur-containing transition metal complexes as model
compounds of both active sites of natural enzymes [7]
and catalytic metal surfaces [8]. However, transition
metal complex-catalyzed synthetic reactions using sul-
fur-containing compounds remain open to study, since
sulfur-containing compounds have long been known to
act as catalyst poisons because of their strong coordinat-
ing properties and often rendered the catalytic reaction
totally ineffective [9]. In recent years, several useful
transformations of sulfur-containing compounds using
transition metal catalysts have been developed [10].
Thus, the metal-catalyzed synthesis of arylsulfides has
included the cross coupling of thiols with aryl halides
using copper or palladium catalyst under basic condi-
tions [11], however, the metal-catalyzed thiolation of
arylhalides with disulfides has rarely been done, despite
the fact that the efficient use of (RS)2 in the catalytic thi-
olation of alkyl halides has already been reported [12].
We believe that a robust complex used as catalyst
may render a better performance in the alkyl and aryl
thiolation of halobenzenes, thus following our continu-
ous interest, on one hand, in the use of pincer type li-
gands [13] and their transition metal complex for novel
organic transformations and the use of aromatic fluori-
nated substituents [13] for the facility with which steric

1387-7003/$ - see front matter
2005 Elsevier B.V. All rights reserved.
doi:10.1016/j.inoche.2005.07.011
956 O. Baldovino-Pantaleón et al. / Inorganic Chemistry Communications 8 (2005) 955–959
and electronic properties can be tuned by changing fluo-
rine substitution in the aromatic ring. We would like to
report our findings in the use of fluorinated bis-imino
nickel(II) NNN pincer complexes, [NiCl2{C5H3N-2,6-
(CHNArf)2}], as efficient catalyst for the cross coupling
of (RS)2 and halobenzenes (Scheme 1).
The reaction of one equivalent of the potentially
tridentated pincer NNN ligands [14] with one equiva-
lent of NiCl2 Æ 6H2O affords in high yield the corre-
sponding complexes [NiCl2{C5H3N-2,6-(CHNArf)2}];
Arf = C6H3-2,3-F2 (1), C6H3-2,5-F2 (2), C6H3-3,4-F2
(3), C6H3-3,5-F2 (4), C6H2-2,3,4-F3 (5), C6H2-2,3,6-F3
(6), C6H2-2,4,5-F3 (7), and C6H2-2,4,6-F3 (8). Analysis
of these complexes by 1H NMR reveals these com-
pounds to be paramagnetic, exhibiting broad signals,
in all cases. Analysis of the pincer compounds by
FAB+ spectrometry affords in most of the cases the
molecular ion, other important peaks include the con-
secutive loss of chlorides. In all cases, elemental analysis
are consistent with the proposed formulations [15].
Crystals suitable for single crystal X-ray diffraction
analyses were obtained for complex 3 [16]. In this case,
the nickel center is found in a pentacoordinated dis-
Arf
N tially tested in the catalytic reaction of C6H5I with
Cl
N Ni Cl
N tion does not proceed, neither in the absence of the
I S
Arf
+ 1/2 RS-SR
Zn
Scheme 1.
Fig. 1. An ORTEP representation of the structure of [NiCl2{C5H3N-2,6-(CHNC6H3-3,4-F2)2}] (3) at 50% probability level showing the atom
labeling scheme.
torted trigonal bipyramidal geometry (TBP), with the
two chlorides occupying the equatorial plane. The three
nitrogens of the NNN pincer ligand occupy the remain-
ing coordination sites. The average Ni–N bond distances
of the NNN pincer ligand are of 2.1135 Å and the termi-
nal Ni–N bond distance is somewhat longer than the
central Ni(1)–N(1) bond distances being of 1.957(3) Å.
The variation of these distances can be related to the
packing of the molecules in the crystal lattice Fig. 1.
As in previous cases, we have been focussing our
attention on the use of pincer type ligands and their
complexes for novel organic transformation, the selec-
tion of these ligands has been due to the robustness that
they confer to the transition metal complexes they form
[17]. Given the importance that in recent years the cross
coupling reactions using palladium complexes have
gained, we decided to attempt a cross coupling reaction
of an important process in organic chemistry for the
synthesis of mixed alkyl–aryl sulfides using nickel com-
plexes. This reaction has been previously reported using
palladium or copper catalysts as in the Ullmann process,
however, in most of the cases these reactions require the
use of the thiol and basic conditions for prolonged reac-
tion times. We believe that given the robustness that the
present complexes offer, we may have a good chance to
carry out similar catalysis using disulfides (RS)2 instead
of the thiol. Thus, all the series of complexes were ini-
(MeS)2 in the presence of zinc [18], the presence of zinc
is fundamental because in its absence the catalytic reac-
nickel complex. From all the compounds tested, complex
R
[NiCl2{C5H3N-2,6-(CHNC6H2-2,3,4-F3)2}] (5) afforded
the higher yield (90%), thus all the following experi-
ments were carried out using this complex as catalyst.
 O. Baldovino-Pantaleón et al. / Inorganic Chemistry Communications 8 (2005) 955–959
Using the same reaction conditions employed for the
methylthiolation of iodobenzene with complex 5, the
alkylthiolation of iodobenzene with different disulfides
was attempted (Table 1).
From Table 1, it is evident that the performance of
the reaction has a clear dependence on the steric hin-
drance of the substituents in the disulfide, thus affording
similar yields in the case of iso-propyl, n-butyl, sec-butyl
and phenyl (an average of 75% yield) and affording only
60% yield in similar reaction times for the di-tert-buty-
ldisulfide. This result can be rationalized in terms of ste-
Table 1
Alkyl- and arylthiolation of iodobenzene by [NiCl2{C5H3N-2,6-(CHN-
C6H2-2,3,4-F3)2}] (5)
I S
(NNN)NiCl2/Zn
+ 1/2 RS-SR
DMF, 110 oC, 4h.
Entry RS-SR Yield (%)a
1 90
S S
2 74
S S
3 75
S S
4 73
S S
5 60
S S
6 75
S S
a
Yields were determined by GC-MS and related to C6H5I.
957
ric hindrance in the nickel center, where it is probably
necessary first the activation of the (RS)2 by the metal
center, this probably would give place to a dithiolate
nickel(II) complex which in turn must further react with
the iodobenzene. From these assumptions, it results
clear that as the size for the substituent in the (RS)2 in-
creases the facility with which the further addition of
PhI would take place will be more difficult or even not
taking place.
Attempts to carry out the same transformation using
chloro or bromo-benzene were poor, affording only 4%
yield in the case of bromobenzene and only traces in the
case of chlorobenzene. These results were expected given
the fact that the energy requirements for the cleavage of
the C–Cl and C–Br bonds are higher than those required
for the breaking of the C–I bond.
R It has been proposed that this sort of reaction using
nickel must proceed through a Ni(0)/Ni(II) intermediate
[19], and it is possible that a similar mechanism may be
working in the present case.
In conclusion, we have designed a high yield one
pot synthesis for asymmetrical alkyl–aryl-thioethers
from disulfides and iodobenzene catalyzed by robust
nickel NNN pincer complexes in the presence of metal-
lic zinc as an indispensable reducing agent, this meth-
od can efficiently use (RS)2 as a thiol source under
neutral conditions. Experiments changing iodo for bro-
mo and chlorobenzene suggest that the system has to
be probably more robust to carry out the reaction at
higher temperatures to be able to provide the energy
necessary to activate the more robust C–Br and C–Cl
bonds.
Supplementary material
Supplementary data for complex 3 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: +44 1223 336033;
e-mail deposit@ccdc.cam.ac.uk or www: http://www.
ccdc.cam.ac.uk) quoting the deposition number CCDC
267431.
Acknowledgments
O.B.-P. thanks CONACYT for financial support. We
thank Chem. Eng. Luis Velasco Ibarra and M. Sc. Fran-
cisco Javier Pérez Flores, QFB. We also thank Ma del
Rocı́o Patiño and Ma. de las Nieves Zavala for their
invaluable help in the running of the FAB+-Mass, IR
and 19F{1H} spectra, respectively. The support of this
research by CONACYT (J41206-Q) and DGAPA-
UNAM (IN114605) is gratefully acknowledged.
958 O. Baldovino-Pantaleón et al. / Inorganic Chemistry Communications 8 (2005) 955–959
References
[1] (a) S.V. Ley, A.W. Thomas, Angew. Chem. Int. Ed. 42 (2003)
5400;
(b) T. Kondo, T. Mitsudo, Chem. Rev. 100 (2000) 3205.
[2] A. Thuillier, P. Metzner, Sulfur Reagents in Organic Synthesis,
Academic Press, New York, 1994.
[3] B. Zwanenburg, A.J.H. Klunder, I Perspectives in Organic
Chemistry of Sulfur, Elsevier, Amsterdam, 1987.
[4] (a) L. Liu, J.E. Stelmach, S.R. Natarjan, M.H. Chen, S.B. Singh,
C.D. Schwartz, C.E. Fitzgerald, S.J. O
Keefe, D.M. Zaller, D.M.
Schmatz, J.B. Doherty, Bioorg. Med. Chem. Lett. 13 (2003)
3979;
(b) S.W. Kaldor, V.J. Kalish, J.F. Davies II, B.V. Shetty, J.E.
Fritz, K. Appelt, J.A. Burgess, K.M. Campanale, N.Y. Chir-
gadze, D.K. Clawson, B.A. Dressman, S.D. Hatch, D.A. Khalil,
M.B. Kosa, P.P. Lubbenhusen, M.A. Muesing, A.K. Patick,
S.H. Reich, K.S. Su, J.H. Tatlock, J. Med. Chem. 40 (1997)
3979.
[5] (a) G. Liu, J.R. Huth, E.T. Olejniczak, R. Mendoza, P. DeVires,
S. Leitza, E.B. Reilly, G.F. Okasinski, S.W. Fesik, T.W. von
Geldern, J. Med. Chem. 44 (2001) 1202;
(b) S.F. Nielsen, E.Ø. Nielsen, G.M. Olsen, T. Liljefors, D. Peters,
J. Med. Chem. 43 (2000) 2217.
[6] (a) G.W. Parshall, S.D. Ittel, Homogeneous Catalysis, second ed.,
Wiley, New York, 1992;
(b) L.S. Hegedus, in: E.W. Abel, F.G.A. Stone, G. Wilkinson
(Eds.), Comprehensive Organometallic Chemistry II, vol. 12,
Pergamon, Oxford, UK, 1995;
(c) B. Cornils, W.A. Herrmann (Eds.), Applied Homogeneous
Catalysis with Organometallic Compounds, vols. 1–3, second ed.,
Wiley-VCH, Germany, 2002;
(d) M. Beller, C. Bolm (Eds.), Transition Metals for Organic
Synthesis, vols. 1–2, Wiley-VCH, New York, 1998;
(e) L. Brandsma, S.F. Vasilevsky, H.D. Verkruijsse (Eds.),
Application of Transition metal Catalysts in Organic Synthesis,
Springer, New York, 1998.
[7] J.M. Berg, R.H. Holm, in: T.G. Spiro (Ed.), Metal Ions in
Biology, vol. 4, Wiley, New York, 1982.
[8] (a) R.J. Angelici, Acc. Chem. Res. 21 (1988) 387;
(b) C. Bianchini, A. Meli, in: B. Cornils, W.A. Herrmann (Eds.),
Applied Homogenous Catalysis with Organometallic Com-
pounds, vol. 2, Wiley-VCH, 2002.
[9] (a) L.L. Hegedus, R.W. McCabe, in: Catalyst Poisoning, Marcel
Dekker, New York, 1984;
(b) A.T. Hutton, in: G. Wilkinson, R.D. Guillard, J.A. McClev-
erty (Eds.), Comprehensive Coordination Chemistry, vol. 5,
Pergamon, Oxford, U.K., 1984.
[10] (a) T. Weber, R. Prins, R.A. van Santen (Eds.), Transition Metal
Sulphides, Kluwer Academic Publishers, Dordrecht, 1998;
(b) E.I. Stiefel, K. Matsumoto (Eds.), Transition Metal Sulfur
Chemistry. Biological and Industrial Significance, ACS Sympo-
sium Series, vol. 653, American Chemical Society, Washington,
DC, 1996;
(c) L. Linford, H.G. ReubenheimerAdvances in Organometallic
Chemistry, vol. 32, Academic Press, San Diego, 1991;
(d) S.G. Murray, F.R. Hartley, Chem. Rev. 81 (1981) 365.
[11] (a) M. Kosugi, T. Shimizu, T. Migita, Chem. Lett. (1978) 13;
(b) H. Suzuki, H. Abe, A. Osuka, Chem. Lett. (1980) 1363;
(c) W.R. Bowman, H. Heaney, P.H.G. Smith, Tetrahedron Lett.
25 (1984) 5821;
(d) T. Yamamoto, Y. Sekine, Can. J. Chem. 62 (1984) 1544;
(e) P.G. Ciattini, E. Morera, G. Ortar, Tetrahedron Lett. 36
(1995) 4133;
(f) J.F. Hartwig, D. Barrañano, J. Am. Chem. Soc. 117 (1995)
2937;
(g) N. Zheng, J.C. McWilliams, F.J. Fleitz, J.D. Armstrong III,
R.P. Volante, J. Org. Chem. 62 (1998) 9606;
(h) C.G. Bates, R.K. Gujadhur, D. Venkataraman, Org. Lett. 4
(2002) 2803;
(i) F.Y. Kwong, S.L. Buchwald, Org. Lett. 4 (2002) 3517.
[12] (a) S. Cowdhury, S. Roy, Tetrahedron Lett. 38 (1997) 2149;
(b) T. Itoh, T. Mase, Org. Lett. 6 (2004) 4587, Using (SeR)2;
(c) T. Nishino, M. Okada, T. Kuroki, T. Watanabe, Y. Nishima,
N. Sonoda, Chem. Lett. 32 (2003) 928;
(d) C. Millois, P. Diaz, Org. Lett. 2 (2000) 1705;
(e) T. Nishino, Y. Nishiyama, N. Sonoda, Chem. Lett. 32 (2003)
918;
(f) T. Nishino, M. Okada, T. Kuroki, T. Watanabe, Y. Nishiy-
ama, N. Sonoda, J. Org. Chem. 67 (2002) 8696.
[13] (a) D. Morales-Morales, R. Redón, Y. Zheng, J.R. Dilworth,
Inorg. Chim. Acta. 328 (2002) 39;
(b) D. Morales-Morales, C. Grause, K. Kasaoka, R. Redón, R.E.
Cramer, C.M. Jensen, Inorg. Chim. Acta. 300-302 (2000) 958;
(c) D. Morales-Morales, R. Redón, C. Yung, C.M. Jensen, Chem.
Commun. (2000) 1619;
(d) D. Morales-Morales, R. Redón, Z. Wang, D.W. Lee, C. Yung,
K. Magnuson, C.M. Jensen, Can. J. Chem. 79 (2001) 823;
(e) D. Morales-Morales, R.E. Cramer, C.M. Jensen, J. Organo-
met. Chem. 654 (2002) 44;
(f) X. Gu, W. Chen, D. Morales-Morales, C.M. Jensen, J. Mol.
Catal. A. 189 (2002) 119;
(g) D.W. Lee, C.M. Jensen, D. Morales-Morales, Organometal-
lics. 22 (2003) 4744;
(h) D. Morales-Morales, R. Redón, C. Yung, C.M. Jensen, Inorg.
Chim. Acta. 357 (2004) 2953;
(i) C. Herrera-Álvarez, V. Gómez-Benı́tez, R. Redón, J.J. Garcı́a,
S. Hernández-Ortega, R.A. Toscano, D. Morales-Morales, J.
Organomet. Chem. 689 (2004) 2464;
(j) J-G. Fierro-Arias, R. Redón, J.J. Garcı́a, S. Hernández-Ortega,
R.A. Toscano, D. Morales-Morales, J. Mol. Cat. A. 233 (2005)
17.
[14] O. Baldovino-Pantaleón, D. Morales-Morales, J. Fluorine Chem.
(submitted for publication).
[15] General procedure for the synthesis of the complexes
[NiCl2{C5H3N-2,6-(CHNArf)2}]. All complexes were synthesized
by the following method illustrated for the synthesis of
[NiCl2{C5H3N-2,6-(CHNC6H3-2,3-F2)2}] (1).
Synthesis of [NiCl2 {C5H3N-2,6-(CHNC6H3-2,3-F2)2}] (1). 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 Æ 6H2O (0.078 g, 0.33 mmol) in absolute meth-
anol (10 mL). The resulting green solution was stirred at room
temperature for 2 h. After this, an orange suspension is noted and
the solvent evaporated in vacuo. The product was purified by
recrystallization from MeOH. The resulting precipitate was
filtered washed with hexane (3 · 5 mL) and dried under vacuum.
Crystals suitable for single crystal X-ray diffraction studies were
obtained from a dichloromethane/methanol (4:1) solution. An
orange solid (142 mg) was obtained in 88% yield. Mp: 240 C
(decomp). FT-IR (KBr): mmax 1587, 1490 (C@N), cm 1. Elem.
Anal. Calc. for [C19H11Cl2F4N3Ni] (486.92): C, 46.87; H, 2.28;
found: C, 46.87; H, 2.39. MS-FAB+ [M Cl]+ = 450 (100%),
[M 2Cl]+ = 415 (68%) m/z.
Synthesis of [NiCl2{C5H3N-2,6-(CHNC6H3-2,5-F2)2} (2).
{C5H3N-2,6-(CHNC6H3-2,5-F2)2} (120 mg, 0.33 mmol) and
NiCl2 Æ 6H2O (0.078 g, 0.33 mmol) afforded a microcrystalline
yellow solid (159 mg) in 98% yield. Mp: 260 C (decomp). FT-IR
(KBr): mmax 1595, 1498 (C@N), cm 1. Elem. Anal. Calc. for
[C19H11Cl2F4N3Ni] (486.92): C, 46.87; H, 2.28; found: C, 46.87;
H, 2.26. MS-FAB+ [M Cl]+ = 450 (61%), [M 2Cl]+ = 415
(39%) m/z.
 O. Baldovino-Pantaleón et al. / Inorganic Chemistry Communications 8 (2005) 955–959
Synthesis of [NiCl2{C5H3N-2,6-(CHNC6)H3-3,4-F22} (3).
{C5H3N-2,6-(CHNC6H3-3,4-F2)2} (0.12 g, 0.33 mmol) and
NiCl2 Æ 6H2O (0.078 g, 0.33 mmol) afforded a microcrystalline
yellow-orange solid (146 mg) in 90% yield. Mp: 290 C (decomp).
FT-IR (KBr): mmax 1610, 1514 (C@N,) cm 1. Elem. Anal. Calc. for
[C19H11Cl2F4N3Ni] (486.92): C, 46.87; H, 2.28; found: C, 46.86; H,
2.29. MS-FAB+ [M Cl]+ = 450 (63%), [M 2Cl]+ = 415 (49%)
m/z.
Synthesis of [NiCl2 {C5H3N-2,6-(CHNC6H3-3,5-F2)2}] (4).
{C5H3N-2,6-(CHNC6H3-3,5-F2)2} (0.12 g, 0.33 mmol) and
NiCl2 Æ 6H2O (0.078 g, 0.33 mmol) afforded a red solid (160 mg)
in 99% yield. Mp: 330 C (decomp). FT-IR (KBr): mmax, 1598
(C@N,) cm 1. Elem. Anal. Calc. for [C19H11Cl2F4N3Ni] (486.92):
C, 46.87; H, 2.28; found: C, 46.88; H, 2.30. MS-FAB+
[M Cl]+ = 450 (100%), [M 2Cl]+ = 415 (38%) m/z.
Synthesis of [NiCl2 {C5H3N-2,6-(CHNC6H2-2,3,4-F3)2}] (5).
{C5H3N-2,6-(CHNC6H2-2,3,4-F3)2} (0.130 g, 0.33 mmol) and
NiCl2 Æ 6H2O (0.078 g, 0.33 mmol) afforded a red solid (167 mg)
in 96% yield. Mp: 350 C (decomp). FT-IR (KBr): mmax 1628, 1511
(C@N) cm 1. Elem. Anal. Calc. for [C19H9Cl2F6N3Ni] (522.90):
C, 43.64; H, 1.73; found: C, 43.65; H, 1.75. MS-FAB+
[M Cl]+ = 486 (100%), [M 2Cl]+ = 451(77%) m/z.
Synthesis of [NiCl2 {C5H3N-2,6-(CHNC6H2-2,3,6-F3)2}] (6).
{C5H3N-2,6-(CHNC6H2-2,3,6-F3)2} (0.130 g, 0.33 mmol) and
NiCl2 Æ 6H2O (0.078 g, 0.33 mmol) afforded a green-yellow solid
(139 mg) in 80% yield. Mp: 195 C (decomp). FT-IR (KBr): mmax
1633, 1501 (C@N,) cm 1. Elem. Anal. Calc. for [C19H9Cl2F6N3Ni]
(522.90): C, 43.64; H, 1.73; found: C, 43.63; H, 1.74. MS-FAB+
[M Cl]+ = 486 (15%), [M 2Cl]+ = 451 (17%) m/z.
Synthesis of [NiCl2 {C5H3N-2,6-(CHNC6H2-2,4,5-F3)2}](7).
{C5H3N-2,6-(CHNC6H2-2,4,5-F3)2} (0.130 g, 0.33 mmol) and
NiCl2 Æ 6H2O (0.078 g, 0.33 mmol) afforded a yellow solid
(156 mg) in 90% yield. Mp: 280 C (decomp). FT-IR (KBr): mmax
1608, 1516 (C@N,) cm 1. Elem. Anal. Calc. for [C19H9Cl2F6N3Ni]
959
(522.90): C, 43.64; H, 1.73; found: C, 43.64; H, 1.72. MS-FAB+
[M Cl]+ = 486 (18%) m/z.
Synthesis of [NiCl2{C5H3N-2,6-(CHNC6H2-2,4,6-F3)2}] (8).
{C5H3N-2,6-(CHNC6H2-2,4,6-F3)2} (0.130 g, 0.33 mmol) and
NiCl2 Æ 6H2O (0.078 g, 0.33 mmol) afforded a yellow solid
(139 mg) in 80% yield. Mp: 250 C (decomp). FT-IR (KBr): mmax
1638, 1596 (C@N,) cm 1. Elem. Anal. Calc. for [C19H9Cl2F6N3Ni]
(522.90): C, 43.64; H, 1.73; found: C, 43.65; H, 1.75. MS-FAB+
[M Cl]+ = 486 (26%), [M 2Cl]+ = 451 (37%) m/z.
[16] Crystal data for 3: M = 486.92, C19H11Cl2F4N3Ni, monoclinic,
space group C2/c, a = 12.5212(10) Å, b = 19.9736(15) Å,
c = 8.3956(7) Å, b = 113.0030(10), V = 1932.7(3) Å3, Z = 4,
Dcalc = 1.673 g cm 3, T = 291(2) K, k (Mo Ka) = 0.71070 Å.
7690 reflections measured, 1700 unique (Rint = 0.0449).
R = 0.0341, Rw = 0.0807 (on 1700 observed reflections
[I > 1.00r(I)] and 133 variable parameters).
[17] (a) V. Gómez-Benı́tez, R. Redón, D. Morales-Morales, J. Mex.
Chem. Soc. 2 (2003) 124;
(b) D. Morales-Morales, J. Mex. Chem. Soc. 48 (2004) 338;
(c) C.M. Jensen, Chem. Commun. (1999) 2443;
(d) G. van Koten, M. Albrecht, Angew. Chem. Int. Ed. 40 (2001)
3750;
(e) M.E. van der Boom, D. Milstein, Chem. Rev. 103 (2003) 1759.
[18] General procedure for the methylthiolation of iodobenzene.
Under an atmosphere of nitrogen, a solution of 4.9 mmol of
iodobenzene, 2.45 mmol of methyl disulfide, 3.0 mg of catalyst 5
(0.0057 mmol) and 202 mg (0.924 mmol) of diethylene glycol di-n-
butylether (internal 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 in a 110 C silicon oil bath. After 4 h, the reaction
mixture was cooled to room temperature and, the organic phase
analyzed by gas chromatography (GC-MS).
[19] N. Taniguchi, J. Org. Chem. 69 (2004) 6904.