The modification of ArSCH2(3,5-Me2Pz) (Ar = phenyl or 2-pyridyl, Pz = pyrazol-1-yl) by organotin group and related reactions

Article abstract of DOI:10.1016/j.jorganchem.2010.06.006

Reaction of 1-arylthiomethyl-3,5-dimethylpyrazole [ArSCH ₂(3,5-Me₂Pz), Ar = phenyl or 2-pyridyl, Pz = pyrazol-1-yl] with Mo(CO)₆ produces complexes ArSCH₂(3,5-Me ₂Pz)Mo(CO)₄, while similar reaction with W(CO)₆ yields analogous complexes ArSCH₂(3,5-Me₂Pz)W(CO) ₄ and concomitant desulfurized complex (3,5-Me₂PzH)W(CO) ₅ in the reaction of PhSCH₂(3,5-Me₂Pz). Succedent treatment of complexes PhSCH₂(3,5-Me₂Pz)M(CO) ₄ with SnCl₄ gives heterobimetallic complexes PhSCH ₂(3,5-Me₂Pz)M(CO)₃(Cl)(SnCl₃) (M = Mo or W) in good yields. ArSCH₂(3,5-Me₂Pz) act as S,N chelating bidentate ligands through the sulfur and the pyrazolyl nitrogen atoms in the aforementioned complexes. The modification of ArSCH₂(3,5- Me₂Pz) by organotin group at the methylene group has been successfully carried out, which yields functionalized ligands Ph ₃SnCH(SAr)(3,5-Me₂Pz). Markedly different reactions are observed, upon treatment of Ph₃SnCH(SPh)(3,5-Me₂Pz) and Ph₃SnCH(SPy)(3,5-Me₂Pz) (Py = 2-pyridyl) with W(CO) ₅THF. The former yields complex Ph₃SnCH(SPh)(3,5-Me ₂Pz)W(CO)₄, as well as PhSCH₂(3,5-Me ₂Pz)W(CO)₄ with a partial loss of the organotin moiety, while no reaction takes place in the latter. In addition, reaction of Ph ₃SnCH(SPy)(3,5-Me₂Pz) with Mo(CO)₆ results in the oxidative addition reaction of the Sn-C_sp3 bond to the molybdenum(0) atom to yield novel heterometallacyclic complex CH(SPy)(3,5-Me₂Pz)Mo(CO)₃SnPh₃, in which [(2-pyridyl)thiomethyl](3,5-dimethylpyrazol-1-yl)methide acts as a tridentate κ³-[N,C,N] chelating ligand through the carbon atom, the pyrazolyl and the pyridyl nitrogen atoms, as the sulfur atom does not coordinate to the molybdenum atom anymore. Interestingly, treatment of this heterometallacyclic complex with P(OR)₃ (R = Ph or Et) gives rise to the isomerization of the C-S bond to the C-N bond, generating the thione-S coordinated complex CH(NC₄H₄C = S)(3,5-Me ₂Pz)Mo(CO)₂(P(OR)₃)SnPh₃, in which the ligand binds in a novel tridentate, monoanionic κ³-[N,C,S] chelating mode to the molybdenum atom.

Full text of DOI:10.1016/j.jorganchem.2010.06.006

Journal of Organometallic Chemistry 695 (2010) 2172e2179
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Journal of Organometallic Chemistry
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The modification of ArSCH2(3,5-Me2Pz) (Ar ¼ phenyl or 2-pyridyl,
Pz ¼ pyrazol-1-yl) by organotin group and related reactions
*
Yun-Fu Xie, Guang-Tong Zeng, Hai-Bin Song, Liang-Fu Tang
Department of Chemistry, State Key Laboratory of Elemento-Organic Chemistry, Nankai University, Tianjin 300071, 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:
Reaction of 1-arylthiomethyl-3,5-dimethylpyrazole [ArSCH2(3,5-Me2Pz), Ar ¼ phenyl or 2-pyridyl,
Pz ¼ pyrazol-1-yl] with Mo(CO)6 produces complexes ArSCH2(3,5-Me2Pz)Mo(CO)4, while similar reaction
with W(CO)6 yields analogous complexes ArSCH2(3,5-Me2Pz)W(CO)4 and concomitant desulfurized
complex (3,5-Me2PzH)W(CO)5 in the reaction of PhSCH2(3,5-Me2Pz). Succedent treatment of complexes
PhSCH2(3,5-Me2Pz)M(CO)4 with SnCl4 gives heterobimetallic complexes PhSCH2(3,5-Me2Pz)M(CO)3(Cl)
(SnCl3) (M ¼ Mo or W) in good yields. ArSCH2(3,5-Me2Pz) act as S,N chelating bidentate ligands through
the sulfur and the pyrazolyl nitrogen atoms in the aforementioned complexes. The modification of
ArSCH2(3,5-Me2Pz) by organotin group at the methylene group has been successfully carried out, which
yields functionalized ligands Ph3SnCH(SAr)(3,5-Me2Pz). Markedly different reactions are observed, upon
treatment of Ph3SnCH(SPh)(3,5-Me2Pz) and Ph3SnCH(SPy)(3,5-Me2Pz) (Py ¼ 2-pyridyl) with W(CO)5THF.
The former yields complex Ph3SnCH(SPh)(3,5-Me2Pz)W(CO)4, as well as PhSCH2(3,5-Me2Pz)W(CO)4 with
a partial loss of the organotin moiety, while no reaction takes place in the latter. In addition, reaction of
Ph3SnCH(SPy)(3,5-Me2Pz) with Mo(CO)6 results in the oxidative addition reaction of the SneCsp3 bond to
the molybdenum(0) atom to yield novel heterometallacyclic complex CH(SPy)(3,5-Me2Pz)Mo(CO)3SnPh3,
Received 7 May 2010
Received in revised form
1 June 2010
Accepted 3 June 2010
Available online 15 June 2010
Keywords:
3,5-Dimethylpyrazole
Organotin
Group 6 metal carbonyl complex
S,N chelating ligand
Oxidative addition
in which [(2-pyridyl)thiomethyl](3,5-dimethylpyrazol-1-yl)methide acts as
a tridentate k
3-[N,C,N]
chelating ligand through the carbon atom, the pyrazolyl and the pyridyl nitrogen atoms, as the sulfur
atom does not coordinate to the molybdenum atom anymore. Interestingly, treatment of this hetero-
metallacyclic complex with P(OR)3 (R ¼ Ph or Et) gives rise to the isomerization of the CeS bond to the
CeN bond, generating the thioneeS coordinated complex CH(NC4H4C ¼ S)(3,5-Me2Pz)Mo(CO)2(P(OR)3)
SnPh3, in which the ligand binds in a novel tridentate, monoanionic
molybdenum atom.
k
3-[N,C,S] chelating mode to the
Ó 2010 Elsevier B.V. All rights reserved.
1. Introduction
CH(3,5-Me2Pz)2(CO)3WSnAr3 [5], while the analogous reaction of
bis(3,5-dimethylpyrazol-1-yl)methane functionalized by organotin
halide leads to the oxidative addition of the relatively electrophilic
SneX (X represents halogen) bond to the tungsten(0) atom [4].
Interestingly, treatments of CH(3,5-Me2Pz)2(CO)3WSnAr3 with both
nucleophilic [7] and electrophilic [8] reagents bring about unusual
ring-expansion reactions. These results inspire us to explore the
analogous reactivityof other ligands with similar structural features,
and 1-phenylthiomethyl-3,5-dimethylpyrazole [9] provides an
available case. The lithiation of this ligand at the methylene group
has been successfully carried out [9], and the corresponding lithium
compound can react with various electrophiles, which makes it as
a useful synthetic intermediate. On the other hand, this ligand is
anticipated to act as a hybrid S,N chelating ligand. In this paper, we
investigate the modification of 1-phenylthiomethyl-3,5-dime-
thylpyrazole and its analog, namely 1-(2-pyridyl)thiomethyl-3,5-
dimethylpyrazole, by organotin group at the methylene group and
their related reactions with group 6 metal carbonyl complexes.
Bis(pyrazol-1-yl)methanes modified by organic functional
groups on the bridging carbon atom have drawn extensive attention
in recent years, owing to their versatile coordination chemistry
towards main group and transition metals [1e3]. Recently, we have
developed the modification of bis(pyrazol-1-yl)methanes by
organotin groups on the methine carbon atom and proved that
the reactivity of these functionalized bis(pyrazol-1-yl)methanes
markedly depends on the properties of substituents on the tin
atom [4e6]. For example, the reaction of triarylstannylbis(3,5-
dimethylpyrazol-1-yl)methane with W(CO)5THF results in the
oxidative addition reaction of the SneCsp3 bond to the tungsten(0)
atom to yield novel four-membered metallacyclic complex
* Corresponding author. Fax: þ86 22 23502458.
E-mail address: lftang@nankai.edu.cn (L.-F. Tang).
0022-328X/$ e see front matter Ó 2010 Elsevier B.V. All rights reserved.
doi:10.1016/j.jorganchem.2010.06.006

Y.-F. Xie et al. / Journal of Organometallic Chemistry 695 (2010) 2172e2179
2173
2. Results and discussion
2.1. Related reaction of 1-phenylthiomethyl-3,5-dimethylpyrazole
1-Phenylthiomethyl-3,5-dimethylpyrazole [PhSCH2(3,5-Me2Pz),
Pz ¼ pyrazol-1-yl] has been synthesized for about two decades [9],
but its coordination chemistry has drawn little attention. To gain
more convictive knowledge on its coordination ability to transition
metals and comprehensive foundations for further research, we
started our investigations with the reaction of this ligand with M
(CO)6 (M ¼ Mo or W) (Scheme 1). Reaction of PhSCH2(3,5-Me2Pz)
with Mo(CO)6 produced PhSCH2(3,5-Me2Pz)Mo(CO)4 (1), similar
reaction with W(CO)6 yielded analogous complex PhSCH2(3,5-
Me2Pz)W(CO)4 (2) and concomitant desulfurized complex
(3,5-Me2PzH)W(CO)5. Succedent reaction of complexes PhSCH2-
(3,5-Me2Pz)M(CO)4 with SnCl4 gave heterobimetallic complexes
PhSCH2(3,5-Me2Pz)M(CO)3(Cl)(SnCl3) (M ¼ Mo (3) and W (4),
respectively) in good yields.
Complexes 1e4 have been characterized by elemental analyses,
IR and NMR spectroscopy. These spectroscopic data support the
suggested structures. The IR spectra of complexes 1 and 2 show four
bands in the carbonyl stretching region, implying a typical cis-tet-
racarbonyl arrangement [10]. While three carbonyl stretching
bands are observed in the seven-coordinate complexes 3 and 4. The
structures of complexes 2 and 4 have been further confirmed by
X-ray structural analyses.
Fig. 1. The molecular structure of 2. The thermal ellipsoids are drawn at the 30% prob-
ability level. Selected bond distances (Å) and angles (ꢀ): W(1)eN(1) 2.264(4), W(1)eS(1)
2.5398(12), C(10)eS(1) 1.810(4), C(10)eN(2) 1.438(5) Å; W(1)eC(1)eO(1) 171.8(4), W
(1)eC(2)eO(2) 178.5(4), W(1)eC(3)eO(3) 178.1(4), W(1)eC(4)eO(4) 172.8(4), C(1)eW
(1)eC(4) 169.80(18), C(3)eW(1)eS(1) 173.61(14), C(3)eW(1)eN(1) 99.22(15), C(10)eS
(1)eW(1) 96.46(13), N(1)eW(1)eS(1) 77.18(8), N(2)eC(10)eS(1) 111.3(3)ꢀ.
The crystal structures of complexes 2 and 4 are presented in
Figs. 1 and 2, respectively. In these two complexes, 1-phenyl-
thiomethyl-3,5-dimethylpyrazole acts as a hybrid S,N chelating
ligand, as expected. The WeN bond distance in complex 2 is 2.264
(4) Å, similar to those found in other octahedral tungsten(0)
complexes with pyrazol-1-yl ligands, such as 2.292(6) Å in CH2(3-p-
MeOPh-5-MeSPz)2W(CO)4 [11] and 2.268(4) Å as well as 2.270(4) Å
in Me3SiCH(3,5-Me2Pz)2W(CO)4 [12]. The WeS bond distance of
2.5398(12) Å is also comparable to those reported in tungsten(0)
complexes with thioether ligands, such as 2.543(2) and 2.554(2) Å
in W(CO)4L (L ¼ 1,1,1,1-tetrakis(methylthiomethyl)methane) [13] as
well as 2.585(2) and 2.565(2) Å in (FcStBuSMe)W(CO)4 (Fc ¼ 1,10-
ferrocenyl) [14]. It is noteworthy that two cis-carbonyl groups in
this complex considerably deviate from linearity with the W(1)eC
(1)eO(1) angle of 171.8(4)ꢀ and the W(1)eC(4)eO(4) angle of 172.8
(4)ꢀ, indicating the presence of steric repulsion between the ligand
and these carbonyls. The WeN bond distance of 2.219(4) Å in
complex 4 is slightly shorter than that in complex 2, while the WeS
bond distance of 2.5702(15) Å in complex 4 is longer than the
corresponding bond distance in complex 2. These two complexes
have similar bite angle NeWeS of 76.23(11)ꢀ in complex 4 and
77.18(8)ꢀ in complex 2, respectively.
When PhSCH2(3,5-Me2Pz) was treated with butyllithium, the
methylene group was deprotonated to afford LiCH(SPh)(3,5-Me2Pz)
[9]. Treatment of this lithium compound with Ph3SnCl yielded
Ph3SnCH(SPh)(3,5-Me2Pz) (5), which was confirmed by X-ray
Fig. 2. The molecular structure of 4. The thermal ellipsoids are drawn at the 30%
probability level. Selected bond distances (Å) and angles (ꢀ): W(1)eN(1) 2.219(4), W
(1)eCl(1) 2.5409(14), W(1)eS(1) 2.5702(15), W(1)eSn(1) 2.7711(8), Sn(1)eCl(4)
2.3483(18), Sn(1)eCl(2) 2.3487(17), Sn(1)eCl(3) 2.3897(17), C(9)eS(1) 1.823(6), C(9)e
N(2) 1.461(6) Å; C(3)eW(1)eS(1) 170.80(15), N(1)eW(1)eSn(1) 150.73(10), N(1)eW
(1)eS(1) 76.23(11), Cl(2)eSn(1)eCl(3) 97.38(7), Cl(3)eSn(1)eW(1) 120.56(5), C(9)eS
(1)eW(1) 98.80(18), N(2)eC(9)eS(1) 111.7(3)ꢀ.
Scheme 1. Related reaction of 1-phenylthiomethyl-3,5-dimethylpyrazole.

2174
Y.-F. Xie et al. / Journal of Organometallic Chemistry 695 (2010) 2172e2179
diffraction. The molecular structure of ligand 5 is shown in Fig. 3,
demonstrating that the tin atom adopts a four-coordinate distorted
tetrahedral geometry. The sulfur and pyrazolyl nitrogen atoms do
not coordinate to the tin atom, possibly owing to the weak Lewis
acidity of the tin atom in tetraalkyltin. Reaction of 5 with Mo(CO)6
or W(CO)5THF in refluxing THF yielded Ph3SnCH(SPh)(3,5-Me2Pz)
M(CO)4 (M ¼ Mo (6) and W (7), respectively), with certain amount
of complex 2 in the case of tungsten. No oxidative addition product
of the SneCsp3 or SneCsp2 bond to the molybdenum(0) or tungsten
(0) atom was obtained.
Complexes 6 and 7 are air-stable in the solid state, but their
solutions, especially the solution of complex 6, are air-sensitive.
These two complexes have been characterized by spectroscopic
methods. The carbonyl stretches in their IR spectra match the
pattern for a typical cis-tetracarbonyl arrangement around the
metal atom, similar to those in complexes 1 and 2. The proton
signals assigned for pyrazole ring are considerably shifted to lower
field, compared with those in ligand 5. Four 13C NMR signals of the
carbonyls have been observed in these two complexes, implying
that four carbonyls are inequivalent possibly owing to these
substituents in the ligand preventing their free rotation in solution.
The molecular structure of complex 7 is shown in Fig. 4. To reduce
the steric repulsion between each other, the phenyl group is trans to
the triphenyltin moiety. Four carbonyls in the complex deviate from
linearity because of steric repulsion between the ligand and these
carbonyls. The WeN and WeS bond distances are 2.237(3) and
2.5236(9) Å, respectively, similar to the corresponding bond
distances in complex 2. Some angles around the Sn(1) atom (such
as the angles C(16)eSn(1)eC(23) of 119.36(13)ꢀ and C(16)eSn(1)eC
(29) of 94.78(12)ꢀ) markedly deviate from the tetrahedral geometry
of the sp3 hybridized tin atom. The deviation is more remarkable
than that in the free ligand 5 (such as the angles C(7)eSn(1)eC(19)
of 117.63(13)ꢀ and C(13)eSn(1)eC(19) of 100.82(12)ꢀ in 5) since the
chelating coordination to the tungsten atom increases the steric
congestion around the tin atom in complex 7.
Fig. 4. The molecular structure of 7. The thermal ellipsoids are drawn at the 30%
probability level. Selected bond distances (Å) and angles (ꢀ): W(1)eN(1) 2.237(3), W
(1)eS(1) 2.5236(9), Sn(1)eC(16) 2.216(3), Sn(1)eC(29) 2.126(4), C(16)eN(2) 1.455(4), C
(16)eS(1) 1.805(3) Å; W(1)eC(1)eO(1) 174.7(4), W(1)eC(2)eO(2) 177.6(4), W(1)eC
(3)eO(3) 178.2(4), W(1)eC(4)eO(4) 172.8(4), C(3)eW(1)eS(1) 174.97(11), N(1)eW
(1)eS(1) 76.87(8), N(2)eC(16)eS(1) 112.3(2), N(2)eC(16)eSn(1) 122.6(2), C(16)eSn
(1)eC(23) 119.36(13), C(16)eSn(1)eC(29) 94.78(12), C(10)eS(1)eC(16) 103.88(16), C
(10)eS(1)eW(1) 112.24(11), C(16)eS(1)eW(1) 100.55(12)ꢀ.
complex 2 in the case of tungsten suggests that the SneCsp3 bond is
still active. The oxidative additionproducts 8 are not obtained may be
as a result of their poor stability, led by the ring strain of the small
three-membered metallacycle. We suppose that similar oxidative
addition reaction can arise, if this small metallacycle is enlarged
through other coordination atoms introduced by substituting the
heteroaryl groups for the phenyl group, such as the replacement of
the phenyl group by 2-pyridyl. Thus 1-(2-pyridyl)thiomethyl-3,5-
dimethylpyrazole [PySCH2(3,5-Me2Pz)] (9) was designed and
synthesized.
Although no oxidative addition reaction takes place during the
reaction of ligand 5 with Mo(CO)6 or W(CO)5THF, the isolation of
2.2. Synthesis and related reaction of 1-(2-pyridyl)thiomethyl-3,5-
dimethylpyrazole
Ligand 9 was readily obtained by the reaction of 2-mercapto-
pyridine with 1-chloromethyl-3,5-dimethylpyrazole under basic
conditions, which is expected to act as a potential multidentate
ligand. Reaction of this ligand with Mo(CO)6 or W(CO)5THF in
refluxing THF yielded complexes PySCH2(3,5-Me2Pz)M(CO)4
(M ¼ Mo (10) and W (11), respectively) (Scheme 2). Their IR spectra
exhibit four bands for the carbonyl stretching, similar to those in
complexes 1 and 2 as well as 6 and 7. The 1H NMR spectra of these
two complexes also exhibit the expected signals of the ligand and
peak multiplicities for the pyridyl group. It is worthy of pointing out
that the protons of the methylene group of complex 11 display an
AB resonance at room temperature, which is also observed in
complex 2. These may be the results of the inversion of the
conformation of the five-membered metallacycle as well as the free
rotation of the phenyl or pyridyl group being slowed down due to
the steric repulsion among substituents. At the same time, four
carbonyl signals are observed in the 13C NMR spectra of complexes
10 and 11, like those in complexes 6 and 7.
Fig. 3. The molecular structure of 5. The thermal ellipsoids are drawn at the 30%
probability level. Selected bond distances (Å) and angles (ꢀ): Sn(1)eC(7) 2.132(4), Sn
(1)eC(19) 2.191(3), C(19)eS(1) 1.811(3), C(25)eS(1) 1.785(3), C(19)eN(1) 1.451(4) Å; C
(7)eSn(1)eC(19) 117.63(13), C(13)eSn(1)eC(19) 100.82(12), C(19)eS(1)eC(25) 100.61
(14), N(1)eC(19)eS(1) 113.4(2), S(1)eC(19)eSn(1) 112.60(15)ꢀ.
The coordination mode of ligand 9 in complexes 10 and 11 was
established by the X-ray crystal diffraction analyses of complex 10.
As shown in Fig. 5, PySCH2(3,5-Me2Pz) acts as a S,N chelating
bidentate ligand through the sulfur and pyrazolyl nitrogen atoms,

Y.-F. Xie et al. / Journal of Organometallic Chemistry 695 (2010) 2172e2179
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elevated temperature, the ligand decomposed and no isolable
complex was obtained.
Complex 13 is air-stable in the solid state, and its solution can be
manipulated in the air without notable decomposition. The proton
signal of the CH group (4.18 ppm) in the complex is markedly
shifted to higher field, compared with that in free ligand 12
(5.97 ppm), possibly owing to the relatively smaller electronega-
tivity of molybdenum than that of tin [16]. The structure of complex
13 has been confirmed by X-ray crystallography. As seen in Fig. 6,
the pyridyl nitrogen atom instead of the sulfur atom coordinates to
the molybdenum atom as mentioned previously, resulting in the
formation of novel four- and five-membered heterometallacycles.
[(2-Pyridyl)thiomethyl](3,5-dimethylpyrazol-1-yl)methide acts as
a tridentate
well as the pyrazolyl and the pyridyl nitrogen atoms. The MoeN-
bond distance of 2.258(5) Å is slightly longer than the
k
3-[N,C,N] chelating ligand through the carbon atom as
pyridyl
MoeNpyrazolyl bond distance of 2.208(5) Å, but similar to that in
complex 10 (2.263(2) Å). The structural parameters related to the
four-membered metallacycle are comparable to those in other four-
membered heterometallacyclic complexes with similar structural
features, such as CH(3,5-iPr2Pz)2W(CO)3SnPh3 [5] and CH(3,5-
Me2Pz)2W(CO)3Cl [17]. For example, the angle NeCeM in these
complexes is very close to 90ꢀ. In addition, the four-membered
heterometallacycle is nearly planar, with a mean deviation from the
plane of 0.0316 Å.
Scheme 2. Related reaction of 1-(2-pyridyl)thiomethyl-3,5-dimethylpyrazole.
and the pyridyl nitrogen atom does not coordinate to the molyb-
denum atom. The fundamental molecular framework is similar to
that in complex 2. For example, two distorted cis-carbonyls are
observed in these two complexes. Their structural parameters are
also very analogous since the covalent radii of molybdenum is close
to that of tungsten [15], such as similar MeN and MeS bond
distances as well as similar bite angle of NeMeS.
The modification of ligand 9 by organotin group at the methy-
lene group has been successfully carried out, as described above for
PhSCH2(3,5-Me2Pz). Ligand 9 could be smoothly lithiated at the
methylene group and subsequently reacted with Ph3SnCl to yield
Ph3SnCH(SPy)(3,5-Me2Pz) (12). The reactivity of ligand 12 is
significantly different from that of ligand 5. The reaction of ligand
12 with Mo(CO)6 resulted in the oxidative addition reaction of the
SneCsp3 bond to the molybdenum(0) atom to yield novel hetero-
metallacyclic complex CH(SPy)(3,5-Me2Pz)Mo(CO)3SnPh3 (13).
However, upon heating ligand 12 with W(CO)5THF in refluxing THF,
no reaction took place. When this reaction was carried out at
Complex 13 is expected to have unusual reactivity, like CH(3,5-
Me2Pz)2W(CO)3SnPh3 [7,8], owing to the polar metalecarbon bond
and ring strain in the four-membered metallacycle. Herein, we find
that the reaction of this complex with P(OR)3 is remarkably
different from the corresponding reaction of CH(3,5-Me2Pz)2W
(CO)3SnPh3 with P(OR)3 [7]. Treatment of complex 13 with P(OR)3
(R ¼ Ph or Et) results in the formation of complexes 14 and 15, in
which the four-membered metallacycle is not broken down. The
crystal structural analyses of complex 14 show that complex 13
undergoes MoeNpyridyl bond cleavage, and subsequently isomer-
izes to give the thioneeS coordinated complex (Fig. 7). The ligand
binds in a novel tridentate, monoanionic
to the molybdenum atom in this complex.
k
3-[N,C,S] chelating mode
Fig. 6. The molecular structure of 13. The thermal ellipsoids are drawn at the 30%
probability level. The uncoordinated solvent molecules have been omitted for clarity.
Selected bond distances (Å) and angles (ꢀ): Mo(1)eC(9) 2.310(6), Mo(1)eSn(1) 2.7690
(15), Mo(1)eN(1) 2.208(5), Mo(1)eN(3) 2.258(5), C(9)eS(1) 1.799(6), C(10)eS(1) 1.735
(6), C(9)eN(2) 1.471(8) Å; N(1)eMo(1)eN(3) 82.37(19), N(1)eMo(1)eC(9) 61.92(19), C
(3)eMo(1)eN(3) 166.4(2), C(3)eMo(1)eN(1) 87.5(2), C(21)eSn(1)eC(27) 103.2(2), C
(21)eSn(1)eMo(1) 117.74(15), C(9)eS(1)eC(10) 99.9(3), N(2)eC(9)eS(1) 110.3(4), N
(2)eC(9)eMo(1) 90.2(3), S(1)eC(9)eMo(1) 115.0(3), N(1)eN(2)eC(9) 110.1(5)ꢀ.
Fig. 5. The molecular structure of 10. The thermal ellipsoids are drawn at the 30%
probability level. Selected bond distances (Å) and angles (ꢀ): Mo(1)eN(3) 2.263(2), Mo
(1)eS(1) 2.5582(9), C(10)eN(2) 1.453(3), C(10)eS(1) 1.805(2) Å; Mo(1)eC(1)eO(1)
172.8(2), Mo(1)eC(2)eO(2) 178.9(2), Mo(1)eC(3)eO(3) 178.1(2), Mo(1)eC(4)eO(4)
172.3(2), C(2)eMo(1)eS(1) 173.40(7), C(2)eMo(1)eN(3) 98.31(9), N(3)eMo(1)eS(1)
76.87(6), N(2)eC(10)eS(1) 111.02(15), C(5)eS(1)eC(10) 100.33(11), C(10)eS(1)eMo(1)
96.19(8)ꢀ.

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Y.-F. Xie et al. / Journal of Organometallic Chemistry 695 (2010) 2172e2179
Scheme 3. Possible pathway of the formation of complexes 14 and 15.
14 or 15. The preference of the relatively soft molybdenum atom for
the soft sulfur atom instead of the hard nitrogen atom is possibly one
of the potential reasons of the isomerization.
In conclusion, the modification of 1-arylthiomethyl-3,5-dime-
thylpyrazole [ArSCH2(3,5-Me2Pz)] by organotin group at the methy-
lene group and their related reactions with M(CO)6 have been carried
out. ArSCH2(3,5-Me2Pz) act as S,N chelating bidentate ligands
through the sulfur and pyrazolyl nitrogen atoms in their complexes.
The reactivity of these functionalized ligands Ph3SnCH(SAr)(3,5-
Me2Pz) is different from that of Ph3SnCH(3,5-Me2Pz)2. Upon treat-
ment of the former with W(CO)5THF, no analogous oxidative addition
reaction of the SneCsp3 bond to the tungsten(0) atom, as described in
the similar reaction of the latter with W(CO)5THF [5], is observed.
However, heating Ph3SnCH(SPy)(3,5-Me2Pz) and Mo(CO)6 leads to
the oxidative addition reaction of the SneCsp3 bond to the molyb-
denum(0) atom, yielding a novel heterometallacyclic complex CH
(SPy)(3,5-Me2Pz)Mo(CO)3SnPh3, in which the sulfur atom does not
coordinate to the molybdenum atom anymore. Although some
similar structural features are observed in CH(SPy)(3,5-Me2Pz)Mo
(CO)3SnPh3 and CH(3,5-Me2Pz)2W(CO)3SnPh3, they exhibit different
reactivity. Reaction of the former with P(OR)3 gives rise to the isom-
erization of the CeS bond to the CeN bond to generate the thionee
Scoordinated complex,insteadofthePeOexchangereactionlikethat
in the latter [7].
Fig. 7. The molecular structure of 14. The thermal ellipsoids are drawn at the 30%
probability level. Selected bond distances (Å) and angles (ꢀ): Mo(1)eSn(1) 2.7432(10),
Mo(1)eN(1) 2.239(6), Mo(1)eC(8) 2.312(7), Mo(1)eP(1) 2.3891(19), Mo(1)eS(1)
2.5229(19), P(1)eO(1) 1.606(5), C(8)eN(3) 1.484(9), C(8)eN(2) 1.447(8), C(9)eS(1)
1.713(7) Å; C(10)eSn(1)eC(16) 102.1(3), C(10)eSn(1)eMo(1) 123.35(17), C(31)eMo
(1)eS(1) 164.6(2), O(1)eP(1)eO(3) 99.1(3), C(9)eS(1)eMo(1) 104.6(3), N(2)eC(8)eN
(3) 109.4(5), P(1)eMo(1)eSn(1) 137.09(5)ꢀ.
The notable change of the coordination mode is evidently
reflected by the NMR spectra of complexes 14 and 15. The proton
signal of the CH group in these two complexes (5.28 ppm in
complex 14 and 5.30 ppm in complex 15, respectively) is shifted to
lower field in comparison to the signal in complex 13. Moreover,
the shift of the 13C NMR signal of the CH group is more noticeable,
from 49.1 ppm in complex 13 to 83.1 ppm in complex 14 and
83.3 ppm in complex 15, respectively. Other marked changes are
the chemical shifts of the protons and carbons involving the pyridyl
group. A large upfield shift for the proton, related to the pyridyl
group in complex 13, is observed in complexes 14 (6.19 ppm) and 15
(6.28 ppm). At the same time, a carbon appears farther downfield
(177.8 ppm) in the 13C NMR spectra of complexes 14 and 15, and
this signal is split into a doublet by the phosphorus atom.
3. Experimental
Solvents were dried by standard methods and distilled prior to
use. All reactions were carried out under an argon atmosphere.
NMR spectra were recorded on a Bruker 400 spectrometer using
CDCl3 as solvent unless otherwise noted, and the chemical shifts
were reported in ppm with respect to reference standards (internal
SiMe4 for 1H NMR and 13C NMR spectra, external 85% H3PO4
aqueous solution for 31P NMR spectra). IR spectra were obtained
from a Nicolet 380 spectrometer as KBr discs. Elemental analyses
were carried out on an Elementar Vairo EL analyzer. 1-Phenyl-
thiomethyl-3,5-dimethylpyrazole [PhSCH2(3,5-Me2Pz)] [9] was
prepared by the published method.
2.3. Possible pathway of the formation of complexes 14 and 15
The isomerization of the CeS bond to the CeN bond has been
observed in bis [18] and tri(thioimidazolyl)methanes [19], and an
intramolecular 1,3-sigmatropic rearrangement mechanism for this
isomerization has been proposed [18]. Based on this proposal and
other known facts, a plausible pathway of the formation of complexes
14 and 15 is depicted in Scheme 3. Initially, the phosphorus ligand
replaces the pyridyl group, leading to the cleavage of the MoeNpyridyl
bond to afford a free pyridyl group. Subsequently, an intramolecular
1,3-sigmatropic rearrangement gives rise to the isomerization of the
CeS bond to the CeN bond to generate the thione intermediate.
Finally, the sulfur atom substitutes a carbonyl group to give complex
3.1. Synthesis of PhSCH2(3,5-Me2Pz)Mo(CO)4 (1)
The solution of Mo(CO)6 (0.24 g, 0.91 mmol) and PhSCH2(3,5-
Me2Pz) (0.20 g, 0.91 mmol) in THF (20 ml) was stirred and heated at

Y.-F. Xie et al. / Journal of Organometallic Chemistry 695 (2010) 2172e2179
2177
reflux for 6 h. After cooling to room temperature, the solvent was
removed in vacuo, and the residue was purified by column chro-
matography on silica using ethyl acetate/hexane (V:V ¼ 1:10) as
eluent. The green-yellow eluate was concentrated to dryness under
a reduced pressure, and the residue was recrystallized from CH2Cl2/
hexane to give green-yellow crystals of 1. Yield: 0.24 g (62%). 1H
mixture was added a solution of Ph3SnCl (3.86 g, 10 mmol) in THF
(25 ml). The reaction mixture was stirred at ꢁ70 ꢀC for 1 h, allowed to
reach room temperature slowly and stirred for additional 1 h. The
solventwasremovedinvacuo, andtheresiduewasrecrystallizedfrom
hexane to give white crystals of 5. Yield: 4.54 g (80%).1H NMR:
d 1.69,
2.21 (s, s, 3H, 3H, CH3), 5.70 (s, br, 2H, CH and H4 of pyrazole),
7.30e7.41, 7.69e7.72 (m, m, 14H, 6H, SnC6H5 and SC6H5) ppm. 13C
NMR:
d 2.10, 2.50 (s, s, 3H, 3H, CH3), 5.03 (s, br, 2H, CH2), 5.99 (s, 1H,
H4 of pyrazole), 7.09e7.12, 7.29e7.39 (m, m, 2H, 3H, C6H5) ppm. 13
C
NMR: d
11.0, 13.4 (CH3), 58.0 (CH), 106.3 (C4 of pyrazole), 128.4, 128.6,
NMR:
d
12.3, 16.5 (CH3), 58.4 (CH2), 108.0 (C4 of pyrazole), 129.9,
128.9, 129.4, 129.5, 136.6, 137.4, 139.0, 139.5, 147.3 (SnC6H5, SC6H5 as
well as C3 and C5 of pyrazole) ppm. Anal. Calc. for C30H28N2SSn: C,
63.51; H, 4.97; N, 4.94. Found: C, 63.50; H, 5.33; N, 5.10%.
130.8, 131.2, 132.8 (C6H5), 142.1, 153.8 (C3 and C5 of pyrazole), 219.6,
220.3 (CO) ppm. IR: nCO ¼ 2020.4 (s), 1897.2 (sh), 1875.2 (vs), 1823.7
(vs) cmꢁ1. Anal. Calc. for C16H14MoN2O4S: C, 45.08; H, 3.31; N, 6.57.
Found: C, 44.78; H, 3.68; N, 6.55%.
3.5. Reaction of 5 with Mo(CO)6
3.2. Synthesis of PhSCH2(3,5-Me2Pz)W(CO)4 (2)
The solution of Mo(CO)6 (0.16 g, 0.60 mmol) and 5 (0.34 g,
0.60 mmol) dissolved inTHF (40 ml) was heated at reflux for 5 h. After
cooling to room temperature, the solvent was removed under
reduced pressure, and the residue was purified by column chroma-
tography on silica using CH2Cl2/hexane (V:V ¼ 1:1) as eluent. The
green-yellow eluate was concentrated to dryness under reduced
pressure to give a green-yellow solid of Ph3SnCH(SPh)(3,5-Me2Pz)Mo
The solution of W(CO)6 (0.32 g, 0.91 mmol) and PhSCH2(3,5-
Me2Pz) (0.20 g, 0.91 mmol) in dioxane (40 ml) was stirred and
heated at reflux for 5 h. After cooling to room temperature, the
solvent was removed in vacuo, and the residue was purified by
column chromatography on silica using ethyl acetate/CH2Cl2/
hexane (V:V:V ¼ 2:5:20) as eluent to yield two products. The first
green-yellow band was confirmed as known complex (3,5-
Me2PzH)W(CO)5 (29 mg, 7.6%) according to its spectroscopic data.
(CO)4 (6). Yield: 0.26 g (56%). 1H NMR:
5.67 (s, 1H, CH), 5.81 (s, 1H, H4 of pyrazole), 6.98e7.01, 7.18e7.19,
d 1.82,2.33(s, s, 3H, 3H, CH3),
7.26e7.33 (m, m, m, 2H, 3H,15H, SnC6H5 and SC6H5).13C NMR:
d 12.6,
1H NMR:
d
2.31 (s, 6H, CH3), 5.93 (s, 1H, H4 of pyrazole), 9.35 (s, br,
16.8 (CH3), 59.2 (CH), 108.2 (C4 of pyrazole), 127.6, 129.1, 129.4, 129.7,
130.2, 135.9, 137.0, 140.0, 141.2, 153.0 (SnC6H5, SC6H5 as well as C3 and
C5 of pyrazole), 204.9, 206.5, 219.5, 220.1 (CO). IR: nCO ¼ 2018.0 (s),
1905.3 (vs), 1880.7 (vs), 1842.9 (vs) cmꢁ1. Anal. Calc. for C34H28Mo-
N2O4SSn: C, 52.67; H, 3.64; N, 3.61. Found: C, 52.71; H, 3.84; N, 3.69%.
1H, NH) ppm. IR: nNH ¼ 3386.2 (m), nCO ¼ 2074.7 (w), 1947.0 (s),
1919.1 (vs), 1832.5 (vs) cmꢁ1. The second green-yellow band was
confirmed as compound 2 (0.11 g, 24%). 1H NMR:
d 2.16, 2.53 (s, s,
3H, 3H, CH3), 5.02, 5.18 (d, J ¼ 11.4 Hz, d, J ¼ 11.4 Hz, 1H, 1H, CH2),
6.02 (s, 1H, H4 of pyrazole), 7.08e7.10, 7.31e7.42 (m, m, 2H, 3H,
C6H5) ppm. 13C NMR:
d
12.4, 17.2 (CH3), 58.4 (CH2), 107.8 (C4 of
3.6. Reaction of 5 with W(CO)5THF
pyrazole), 129.8, 130.8, 131.3, 132.7 (C6H5), 141.7, 154.1 (C3 and C5 of
pyrazole), 210.2, 210.8 (CO) ppm. IR: nCO ¼ 2013.9 (s), 1890.4 (sh),
1867.9 (vs), 1817.8 (vs) cmꢁ1. Anal. Calc. for C16H14N2O4SW: C, 37.37;
H, 2.74; N, 5.45. Found: C, 37.39; H, 2.75; N, 5.54%.
Compound 5 (0.17 g, 0.30 mmol) was added to a solution of W
(CO)5THF inTHF, prepared in situ by the irradiation of a solution of W
(CO)6 (0.11 g, 0.3 mmol) in THF (40 ml) for 8 h, and the mixture was
stirred and heated at reflux for 4 h. The solvent was removed in
vacuo, and the residue was purified by column chromatography on
silica using ethyl acetate/hexane (V:V ¼ 1:4) as eluent to yield two
products. The first green-yellow band was confirmed as Ph3SnCH
3.3. Reaction of 1 and 2 with SnCl4
SnCl4 (0.4 mmol) was added by syringe to a stirred solution of 1
or 2 (0.4 mmol) in 20 ml of CH2Cl2. After continuously stirring at
room temperature for 2 h, the solution was concentrated to dryness
under a reduced pressure, and the residue was recrystallized from
CH2Cl2/hexane to give orange-red crystals of 3 or 4.
(SPh)(3,5-Me2Pz)W(CO)4 (7) (28 mg, 11%). 1H NMR:
d
1.94, 2.45 (s, s,
2
3H, 3H, CH3), 5.80 (s, JSneH ¼ 17.8 Hz, 1H, CH), 5.91 (s, 1H, H4 of
pyrazole), 7.04e7.08, 7.28e7.32, 7.36e7.41 (m, m, m, 2H, 4H, 14H,
SnC6H5 and SC6H5) ppm. 13C NMR:
d 13.0,17.8 (CH3), 60.6 (CH),108.2
(C4 of pyrazole), 127.8, 129.7, 129.8, 130.1, 130.2, 135.8, 137.0, 139.9,
141.1, 153.6 (SnC6H5, SC6H5 as well as C3 and C5 of pyrazole), 202.1,
203.0, 210.3, 210.6 (CO) ppm. IR: nCO ¼ 2017.1 (s), 1902.9 (vs), 1875.5
(vs), 1824.6 (vs) cmꢁ1. Anal. Calc. for C34H28N2O4SSnW: C, 47.31; H,
3.27; N, 3.25. Found: C, 47.05; H, 3.60; N, 3.24%. The second green-
yellow band was confirmed as compound 2 (9.7 mg, 6.3%) according
to its spectroscopic data.
3.3.1. PhSCH2(3,5-Me2Pz)Mo(CO)3(Cl)SnCl3 (3)
This compound was obtained by the reaction of 1 with SnCl4.
Yield: 91%. 1H NMR (DMSO-d6):
d 1.97, 2.07 (s, s, 3H, 3H, CH3), 5.48
(s, 2H, CH2), 5.81 (s, 1H, H4 of pyrazole), 7.31e7.35, 7.40e7.43 (m, m,
3H, 2H, C6H5) ppm. IR: nCO ¼ 2026.2 (vs), 1962.5 (vs), 1933.3
(vs) cmꢁ1. Anal. Calc. for C15H14Cl4MoN2O3SSn: C, 27.35; H, 2.14; N,
4.25. Found: C, 27.11; H, 2.15; N, 4.29%.
3.7. Synthesis of PySCH2(3,5-Me2Pz) (Py ¼ 2-pyridyl) (9)
3.3.2. PhSCH2(3,5-Me2Pz)W(CO)3(Cl)SnCl3 (4)
This compound was obtained by the reaction of 2 with SnCl4.
To a stirred solution of EtONa (5.10 g, 75 mmol) in ethanol
(75 ml) at 0 ꢀC was added 2-mercaptopyridine (4.17 g, 37.5 mmol).
The reaction mixture was continuously stirred for 30 min, and then
1-chloromethyl-3,5-dimethylpyrazole hydrochloride (6.34 g,
35 mmol) was added. Subsequently, the reaction mixture was
stirred at ambient temperature for additional 3 h. The solvent was
removed in vacuo, and water (75 ml) was added. The water phase
was extracted with CH2Cl2 (3 ꢂ 50 ml). The organic layers were
combined and dried over anhydrous MgSO4. After removing the
solvent, the residue was recrystallized from ethyl acetate/hexane to
Yield: 90%. 1H NMR (DMSO-d6):
d 1.97, 2.07 (s, s, 3H, 3H, CH3), 5.47
(s, 2H, CH2), 5.81 (s, 1H, H4 of pyrazole), 7.30e7.36, 7.40e7.43 (m, m,
3H, 2H, C6H5) ppm. IR: nCO ¼ 2019.0 (s), 1945.6 (s), 1923.9 (vs) cmꢁ1
.
Anal. Calc. for C15H14Cl4N2O3SSnW: C, 24.13; H, 1.89; N, 3.75. Found:
C, 23.66; H, 2.32; N, 3.41%.
3.4. Synthesis of Ph3SnCH(SPh)(3,5-Me2Pz) (5)
A hexane solution of n-BuLi (2.5 M, 4.0 ml,10 mmol) was added to
a solution of PhSCH2(3,5-Me2Pz) (2.18 g, 10 mmol) in THF (75 ml) at
ꢁ70 ꢀC, and the mixture was stirred for 1 h at that temperature. To the
give yellow solids of 9 (3.37 g, 44%). 1H NMR:
3H, CH3), 5.75 (s, 1H, H4 of pyrazole), 5.85 (s, 2H, CH2), 6.99e7.02,
d 2.19, 2.26 (s, s, 3H,

2178
Y.-F. Xie et al. / Journal of Organometallic Chemistry 695 (2010) 2172e2179
7.19, 7.46e7.50, 8.45 (m, d, J ¼ 4.8 Hz, m, d, J ¼ 8.0 Hz,1H,1H,1H,1H,
9. This compound was recrystallized from ethyl acetate to yield
C5H4N) ppm. 13C NMR:
d
11.2, 13.6 (CH3), 47.6 (CH2), 105.9 (C4 of
yellow crystals of 12. Yield: 51%. 1H NMR:
d 2.19, 2.29 (s, s, 3H, 3H,
pyrazole), 120.3, 122.9, 136.5, 139.9, 148.8, 149.2, 156.4 (C5H4N, C3
and C5 of pyrazole) ppm. Anal. Calc. for C11H13N3S: C, 60.24; H, 5.97;
N, 19.16. Found: C, 60.10; H, 6.05; N, 19.30%.
CH3), 5.79 (s, 1H, H4 of pyrazole), 5.97 (s, 2JSneH ¼ 27.7 Hz, 1H, CH),
6.86e6.90, 7.11, 7.41e7.44, 7.85 (m, d, J ¼ 8.0 Hz, m, d, J ¼ 4.3 Hz, 1H,
1H, 1H, 1H, C5H4N), 7.32e7.34, 7.57e7.76 (m, m, 9H, 6H,
SnC6H5) ppm. 13C NMR:
d
11.7, 13.3 (CH3), 51.2 (CH), 107.1 (C4 of
pyrazole), 120.1, 122.9, 127.9, 128.1, 136.8, 136.9, 139.4, 143.8, 146.1,
147.9, 156.0 (C5H4N, SnC6H5 as well as C3 and C5 of pyrazole) ppm.
Anal. Calc. for C29H27N3SSn: C, 61.29; H, 4.79; N, 7.39. Found: C,
61.12; H, 4.87; N, 7.55%.
3.8. Synthesis of PySCH2(3,5-Me2Pz)Mo(CO)4 (10)
This complex was obtained by the reaction of Mo(CO)6 and 9 as
described above for complex 6. The reaction time was 4 h. Yield:
46%. 1H NMR:
d
2.32, 2.49 (s, s, 3H, 3H, CH3), 5.88 (s, br, 3H, H4 of
pyrazole and CH2), 7.15e7.19, 7.56e7.59, 7.70e7.75, 8.33e8.35 (m,
m, m, m, 1H, 1H, 1H, 1H, C5H4N) ppm. 13C NMR:
d
12.2, 16.1 (CH3),
3.11. Synthesis of PySCH(3,5-Me2Pz)Mo(CO)3SnPh3 (13)
50.1 (CH2), 107.3 (C4 of pyrazole), 122.7, 124.2, 137.9, 142.2, 148.4,
148.5, 155.2 (C5H4N, C3 and C5 of pyrazole), 201.0, 205.5, 219.2,
220.3 (CO) ppm. IR: nCO ¼ 2023.6 (s), 1917.9 (vs), 1885.6 (vs), 1840.2
(vs) cmꢁ1. Anal. Calc. for C15H13MoN3O4S: C, 42.16; H, 3.07; N, 9.83.
Found: C, 41.72; H, 3.42; N, 10.04%.
This compound was similarly obtained as above-mentioned
for compound 1 by the reaction of Mo(CO)6 with compound 12.
The eluent was CH2Cl2/hexane (V:V ¼ 1:1). Yield: 71%. 1H NMR:
d
1.94, 2.27 (s, s, 3H, 3H, CH3), 4.18 (s, 1H, CH), 5.76 (s, 1H, H4 of
pyrazole), 7.00e7.04, 7.23e7.26, 7.28e7.34, 9.24 (m, m, m, d,
J ¼ 5.1 Hz, 1H, 1H, 1H, 1H, C5H4N), 7.28e7.34, 7.49e7.66 (m, m, 9H,
3.9. Synthesis of PySCH2(3,5-Me2Pz)W(CO)4 (11)
6H, SnC6H5) ppm. 13C NMR:
d
9.5, 12.2 (CH3), 49.1 (CH), 104.7 (C4
This complex was obtained by the reaction of 9 and W(CO)5THF
as described above for complex 7. Complex 11 was purified by
column chromatography on silica using CH2Cl2/hexane (V:V ¼ 2:1)
of pyrazole), 119.7, 122.5, 128.1, 128.3, 136.9, 137.1, 141.3, 143.9,
147.8, 153.3, 170.0 (C5H4N, SnC6H5 as well as C3 and C5 of
pyrazole) ppm. No signal of carbonyl carbons was observed
possibly due to the low signal intensity and the limited solubility
of 13. IR: nCO ¼ 1974.4 (vs), 1888.9 (vs), 1859.4 (vs) cmꢁ1. Anal.
Calc. for C32H27MoN3O3SSn: C, 51.36; H, 3.64; N, 5.62. Found: C,
51.86; H, 3.85; N, 5.57%.
as eluent. Yield: 32%. 1H NMR (acetone-d6):
d 2.33, 2.59 (s, s, 3H, 3H,
CH3), 5.22 (d, J ¼ 13.0 Hz, 1H, CH2), 6.08 (s, 1H, H4 of pyrazole), 6.66
(d, J ¼ 13.0 Hz, 1H, CH2), 7.35 (ddd, J ¼ 7.5, 4.9, 1.0 Hz, 1H, C5H4N),
7.65 (dt, J ¼ 8.1, 0.9 Hz, 1H, C5H4N), 7.96 (ddd, J ¼ 8.0, 7.6, 1.8 Hz, 1H,
C5H4N), 8.46 (ddd, J ¼ 4.9, 1.8, 0.9 Hz, 1H, C5H4N) ppm. 13C NMR
(acetone-d6):
d
11.7, 16.2 (CH3), 51.4 (CH2), 107.1 (C4 of pyrazole),
123.4, 123.9, 138.5, 142.3, 149.1, 152.7, 155.0 (C5H4N, C3 and C5 of
pyrazole), 201.1, 202.7, 210.1, 210.8 (CO) ppm. IR: nCO ¼ 2017.0 (vs),
3.12. Reaction of 13 with P(OR)3 (R ¼ Ph or Et)
1909.7 (vs), 1877.9 (vs), 1833.9 (vs) cmꢁ1
. Anal. Calc. for
The mixture of compound 13 (0.4 mmol) and P(OR)3 (4 mmol)
was stirred and heated at 80 ꢀC for 4 h. After cooling to room
temperature, the reaction mixture was washed with hexane to
remove the excess of P(OR)3, and the residue was purified by
column chromatography on silica using CH2Cl2/hexane as eluent.
The eluate was concentrated to dryness under a reduced pressure,
and the residue was recrystallized from CH2Cl2/hexane or ethyl
acetate/hexane to give red crystals.
C15H13N3O4SW: C, 34.97; H, 2.54; N, 8.16. Found: C, 34.92; H, 2.49;
N, 8.38%.
3.10. Synthesis of Ph3SnCH(SPy)(3,5-Me2Pz) (12)
This compound was similarly obtained as above-mentioned for
compound 5, while PhSCH2(3,5-Me2Pz) was replaced by compound
Table 1
Crystal data and refinement parameters for compounds 2, 4, 5, 7 and 10.
Compound
2
4
5
7
10
Formula
C16H14N2O4SW
514.20
C15H14Cl4N2O3SSnW
746.68
C30H28N2SSn
567.29
C34H28N2O4SSnW
863.18
C15H13MoN3O4S
427.28
Formula weight
Crystal size (mm)
T (K)
0.16 ꢂ 0.14 ꢂ 0.10
0.20 ꢂ 0.16 ꢂ 0.12
0.22 ꢂ 0.20 ꢂ 0.16
0.22 ꢂ 0.08 ꢂ 0.06
0.18 ꢂ 0.16 ꢂ 0.10
294(2)
294(2)
294(2)
113(2)
113(2)
l
(Mo K
a
) (Å)
0.71073
Monoclinic
P21/n
11.6448(19)
13.695(2)
11.6458(19)
90
107.56(1)
90
1770.5(5)
4
1.929
984
6.663
2.17e26.38
3622 (0.0329)
2963
218
1.042
0.71073
Monoclinic
P21/c
8.343(3)
16.964(6)
16.455(5)
90
98.278(6)
90
2304.8(13)
4
2.152
1400
6.642
1.73e25.02
4050 (0.0399)
3276
246
1.083
0.71073
Monoclinic
P21/c
15.623(3)
10.1353(17)
17.681(3)
90
104.794(3)
90
2706.7(8)
4
1.392
1152
1.041
1.35e26.44
5538 (0.0519)
3289
309
1.003
0.71070
Monoclinic
P21/c
17.350(3)
9.7523(14)
19.370(3)
90
100.517(2)
90
3222.5(8)
4
1.779
1672
4.446
2.14e27.88
7680 (0.0675)
6739
391
1.037
0.71073
Triclinic
ꢀ
Pı
Crystal system
Space group
a (Å)
b (Å)
c (Å)
a
b
g
8.4385(17)
8.4704(17)
12.750(3)
96.64(3)
102.01(3)
105.78(3)
843.3(3)
2
1.683
428
0.925
1.66e25.02
2950 (0.0313)
2584
219
1.118
(ꢀ)
(ꢀ)
(ꢀ)
V (Å)3
Z
Dc (g cmꢁ3
F(000)
)
m
(mmꢁ1
Range (ꢀ)
)
q
No. of unique reflections (Rint
)
No. of observed reflections (I > 2
No. of parameters
GOF
s(I))
Residuals R, Rw
0.0258, 0.0595
0.0267, 0.0533
0.0375, 0.0584
0.0305, 0.0689
0.0239, 0.0606

Y.-F. Xie et al. / Journal of Organometallic Chemistry 695 (2010) 2172e2179
2179
Table 2
Crystal data and refinement parameters for compounds 13 and 14.
3.13. Crystal structure determinations
Crystals of 2, 4, 7, 10, 13 and 14 suitable for X-ray analyses were
obtained by slow diffusion of hexane into their CH2Cl2 solutions at
ꢁ18 ꢀC. While crystals of 5 suitable for X-ray analyses were
obtained by slowly cooling its hot hexane solution. Intensity data
were collected on a Bruker SMART CCD diffractometer for 2, 4 and 5
as well as Rigaku Saturn CCD detector for 7, 10, 13 and 14, respec-
tively. Semi-empirical absorption corrections were applied using
the SADABS program [20] for 2, 4 and 5 as well as using the Crys-
talclear program [21] for 7, 10, 13 and 14. The crystal of 14 was
twinned and the reflection data were measured for the two twin
domains, scaled and combined together using Twin solve in the
Crystalclear program [21]. Overlapping reflections could not be
satisfactorily measured and were discarded, leading to a data
completeness of 90.2%. The structures were solved by direct
methods and difference Fourier map using SHELXS of the SHELXTL
package and refined with SHELXL [22] by full-matrix least-squares
on F2. All non-hydrogen atoms were refined anisotropically. A
summary of the fundamental crystal data for 2, 4, 5, 7, 10, 13 and 14
is listed in Tables 1 and 2, respectively.
Compound
13.0.25CH2Cl2
32.25H27.5Cl0.5MoN3O3SSn
769.49
14
Formula
C
C49H42MoN3O5PSSn
1030.52
0.26
113(2)
0.71073
Formula weight
Crystal size (mm)
T (K)
0.20 ꢂ 0.16 ꢂ 0.12
ꢂ 0.18 ꢂ 0.14
113(2)
l
(Mo K
a
) (Å)
0.71073
Monoclinic
C2/c
29.539(6)
15.229(3)
18.250(4)
90
127.28(3)
90
6532(2)
8
1.565
3060
1.289
1.74e25.02
5751 (0.0393)
Crystal system
Space group
a (Å)
b (Å)
c (Å)
Triclinic
ꢀ
Pı
9.3560(19)
15.014(3)
16.949(3)
69.33(3)
89.63(3)
81.71(3)
2201.8(8)
2
1.554
1040
0.987
4.79e26.00
18607 (0.0428)
a
b
g
(ꢀ)
(ꢀ)
(ꢀ)
V (Å)3
Z
Dc (g cmꢁ3
F(000)
)
m
(mmꢁ1
Range (ꢀ)
)
q
No. of unique
reflections (Rint
No. of observed
)
5114
18473
reflections (I > 2
No. of parameters
GOF
s(I))
416
1.113
555
1.176
Acknowledgements
Residuals R, Rw
0.0498, 0.1147
0.0839, 0.2126
This work is supported by the National Natural Science Foun-
dation of China (Nos. 20672059 and 20721062).
3.12.1. Synthesis of CH(NC4H4C]S)(3,5-Me2Pz)Mo(CO)2(P(OPh)3)
SnPh3 (14)
Appendix A. Supplementary material
This compound was obtained by the reaction of 13 with P
(OPh)3. The reaction mixture was purified by column chromatog-
raphy using CH2Cl2/hexane (V:V ¼ 1:2) as eluent. Crystallization
from CH2Cl2/hexane afforded red crystals of 14. Yield: 39%. 1H
CCDC numbers 773775e773781 for 2, 4, 5, 7,10,13 and 14 contain
the supplementary crystallographic data for this paper. These data
can be obtained free of charge from The Cambridge Crystallographic
Data Centre via www.ccdc.cam.ac.uk/data_request/cif.
NMR:
d
1.60, 2.23 (s, s, 3H, 3H, CH3), 5.28 (d, 3JPH ¼ 2.8 Hz, 1H, CH),
5.65 (s, 1H, H4 of pyrazole), 6.19, 6.84 (t, J ¼ 6.6 Hz, d, J ¼ 6.5 Hz,
1H, 1H, C5H4NS), 6.83e7.17, 7.35e7.46 (m, m, 24H, 8H, C5H4NS,
References
SnC6H5 and OC6H5) ppm. 13C NMR:
d 9.8, 12.6 (CH3), 83.1 (d,
[1] A. Otero, J. Fernández-Baeza, A. Lara-Sánchez, J. Tejeda, L.F. Sánchez-Barba,
Eur. J. Inorg. Chem. (2008) 5309e5326.
[2] C. Pettinari, R. Pettinari, Coord. Chem. Rev. 249 (2005) 663e691.
[3] A. Otero, J. Fernández-Baeza, A. Antiñolo, J. Tejeda, A. Lara-Sánchez, Dalton
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[4] Z.-K. Wen, Y.-F. Xie, S.-B. Zhao, R.-Y. Tan, L.-F. Tang, J. Organomet. Chem. 693
(2008) 1359e1366.
[5] L.-F. Tang, S.-B. Zhao, W.-L. Jia, Z. Yang, D.-T. Song, J.-T. Wang, Organometallics
22 (2003) 3290e3298.
JPC ¼ 48.9 Hz, CH), 106.3 (C4 of pyrazole), 114.5, 121.4, 121.5, 124.2,
127.6, 127.8, 129.3, 132.3, 134.6, 136.9, 141.4, 144.9, 149.1 (C5H4N,
SnC6H5, OC6H5 as well as C3 and C5 of pyrazole), 151.9 (d,
JPC ¼ 11.6 Hz, OC6H5), 177.8 (d, JPC ¼ 10.5 Hz, C]S), 228.9 (d,
JPC ¼ 32.9 Hz, CO), 229.8 (d, JPC ¼ 29.3 Hz, CO) ppm. 31P NMR:
d
157.4 ppm. IR: nCO ¼ 1896.0 (vs), 1824.7 (vs) cmꢁ1. Anal. Calc. for
C49H42MoN3O5PSSn: C, 57.11; H, 4.11; N, 4.08. Found: C, 56.78; H,
4.37; N, 4.41%.
[6] Z.-K. Wen, Z. Yang, H.-B. Song, L.-F. Tang, Chin. J. Chem. 27 (2009) 993e998.
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[9] A.R. Katritzky, J.N. Lam, Can. J. Chem. 67 (1989) 1144e1147.
[10] L.E. Orgel, Inorg. Chem. 1 (1962) 25e29.
3.12.2. Synthesis of CH(NC4H4C]S)(3,5-Me2Pz)Mo(CO)2(P(OEt)3)
SnPh3 (15)
This compound was obtained by the reaction of 13 with P(OEt)3.
The reaction mixture was purified by column chromatography
using CH2Cl2/hexane (V:V ¼ 1:1) as eluent. Crystallization from
ethyl acetate/hexane afforded red crystals of 15. Yield: 45%. 1H
[11] L.-F. Tang, W.-L. Jia, Z.-H. Wang, J.-T. Wang, H.-G. Wang, J. Organomet. Chem.
649 (2002) 152e160.
[12] L.-F. Tang, W.-L. Jia, X.-M. Zhao, P. Yang, J.-T. Wang, J. Organomet. Chem. 658
(2002) 198e203.
[13] W. Levason, L.P. Ollivere, G. Reid, N. Tsoureas, M. Webster, J. Organomet.
Chem. 694 (2009) 2299e2308.
[14] V.C. Gibson, N.J. Long, R.J. Long, A.J.P. White, C.K. Williams, D.J. Williams,
E. Grigiotti, P. Zanello, Organometallics 23 (2004) 957e967.
[15] N.L. Allinger, X. Zhou, J. Bergsma, J. Mol. Struct. (THEOCHEM) 312 (1994)
69e83.
[16] D.C. Ghosh, T. Chakraborty, B. Mandal, Theor. Chem. Acc. 124 (2009) 295e301.
[17] Y.-F. Xie, Z.-K. Wen, R.-Y. Tan, J. Hong, S.-B. Zhao, L.-F. Tang, Organometallics
27 (2008) 5684e5690.
[18] R.M. Silva, M.D. Smith, J.R. Gardinier, J. Org. Chem. 70 (2005) 8755e8763.
[19] C. Gwengo, R.M. Silva, M.D. Smith, S.V. Lindeman, J.R. Gardinier, Inorg. Chim.
Acta 362 (2009) 4127e4136.
[20] G.M. Sheldrick, SADABS, Program for Empirical Absorption Correction of Area
Detector Data. University of Göttingen, Germany, 1996.
[21] Crystal Structure 3.7.0 and Crystalclear 1.36: Crystal Structure Analysis
Package. Rigaku and Rigaku/MSC, TX, 2000e2005.
[22] G.M. Sheldrick, SHELXS97 and SHELXL97. University of Göttingen, Germany,
1997.
NMR:
d
1.20 (t, J ¼ 7.0 Hz, 9H, CH2CH3), 1.62, 2.29 (s, s, 3H, 3H, CH3),
3.91 (q, J ¼ 7.0 Hz, 6H, CH2CH3), 5.30 (d, 3JPH ¼ 3.6 Hz, 1H, CH), 5.67
(s, 1H, H4 of pyrazole), 6.28, 6.96, 7.08e7.20, 7.59 (t, J ¼ 6.4 Hz, d,
J ¼ 6.4 Hz, m, d, J ¼ 8.4 Hz, 1H, 1H, 1H, 1H, C5H4NS), 7.08e7.20,
7.41e7.53 (m, m, 9H, 6H, C6H5) ppm. 13C NMR:
d 9.8, 12.5 (CH3), 16.1
(d, JPC ¼ 6.3 Hz, CH2CH3), 60.7 (d, JPC ¼ 4.4 Hz, CH2CH3), 83.3 (d,
JPC ¼ 46.8 Hz, CH), 106.1 (C4 of pyrazole), 114.6, 127.6, 127.7, 132.3,
134.6, 136.9, 141.3, 141.6, 145.1, 149.1 (C5H4N, C6H5 as well as C3 and
C5 of pyrazole), 177.8 (d, JPC ¼ 11.4 Hz, C]S), 231.0 (d, JPC ¼ 28.8 Hz,
CO), 232.7 (d, JPC ¼ 32.5 Hz, CO) ppm. 31P NMR:
d 171.0 ppm. IR:
nCO ¼ 1883.4 (vs), 1807.6 (vs) cmꢁ1. Anal. Calc. for C37H42Mo-
N3O5PSSn$0.5CH3CO2C2H5: C, 50.34; H, 4.98; N, 4.52. Found: C,
49.98; H, 5.40; N, 5.00%.