New pentacoordinate bicyclodiazastannsulfide formed between the functionalized cyclopentadienyl ring and tin

Article abstract of DOI:10.1016/j.jorganchem.2006.05.010

New pentacoordinate bicyclodiazastannsulfide fused cyclopentadienyl M-Sn (M = Mo or W) bonded organometallic heterocycle {μ-[C₅H₄(CH₃)C{double bond, long}N{single bond}N{double bond, long}C(S)Ar]M(CO)₃SnCl₂

Full text of DOI:10.1016/j.jorganchem.2006.05.010

Journal of Organometallic Chemistry 691 (2006) 3633–3639
www.elsevier.com/locate/jorganchem
New pentacoordinate bicyclodiazastannsulfide formed between
the functionalized cyclopentadienyl ring and tin
a
a
b
a,
*
Shan-Shan Chen , Yan-Ye Dou , Miao Du , Liang-Fu Tang
a
Department of Chemistry, State Key Laboratory of Elemento-Organic Chemistry, Nankai University, Tianjin 300071, PR China
b
College of Chemistry and Life, Tianjin Normal University, Tianjin 300074, PR China
Received 14 April 2006; accepted 9 May 2006
Available online 19 May 2006
Abstract
New pentacoordinate bicyclodiazastannsulfide fused cyclopentadienyl M–Sn (M = Mo or W) bonded organometallic heterocycle {l-
[C5H4(CH3)C@NAN@C(S)Ar]M(CO)3SnCl2} has been obtained by the condensation reaction of CH3COC5H4M(CO)3SnCl3 with
arylthiocarboxyhydrazide (ArCSNHNH2, Ar = 2-furanyl, 2-thienyl, 2- or 4-hydroxyphenyl) in mild conditions. While the similar
reaction of CH3COC5H4M(CO)3SnCl3 with ArCONHNH2 (Ar = 2- or 4-hydroxyphenyl) only gives non-cyclic compounds
[C5H4(CH3)C@NANHC(O)Ar]M(CO)3SnCl3, in which the tin atom remains tetracoordinate. In bicyclodiazastannsulfide the tin atom
prefers to adopt pentacoordinate geometry, while in the corresponding bicyclodiazastannoxide the tin atom is hexacoordinate. In addi-
tion, phenylhydrazine, 2- or 4-hydroxyphenylcarboxyhydrazide is used to react with CH3COC5H4M(CO)3SnCl3, only tetracoordinate
non-cyclic tin compound is obtained.
ꢀ 2006 Elsevier B.V. All rights reserved.
Keywords: Cyclopentadienyl; Tin; Group 6 carboxyl metal compound; Thicarboxydrazide; Heterocycle
1. Introduction
Encouraged by the fascinating results we obtained on
binuclear tin complexes before, we recently became inter-
ested in studying the transition metal–tin bonded heterodi-
metallic complexes owing to their unusual structural
feature and reactivity [25–27]. The previous work of our
group showed that the reaction of functionalized acetylcy-
clopentadienyl M–Sn bonded heterodimetallic complexes
with phenylhydrazine formed a normal hydrazone, in
which the tin atom is tetracoordinate, while their analo-
gous reaction with aroylhydrazine yielded a novel bridging
dinuclear bicyclodiazastannoxide [28,29], in which the tin
atom, instead of assuming general pentacoordinate geome-
try in known bicyclodiazastannoxide analogues [30,31],
prefers to be hexacoordinate through absorbing the chlori-
dion or solvent molecules. It seems that it is difficult to
obtain the pentacoordinate tin in these cyclopentadienyl
M–Sn bonded heterocycles. Provided the knowledge that
the sulfur atom has high affinity for many metals, we found
it very intriguing to know if the sulfur atom substituting
for the oxygen atom in aroylhydrazine can stabilize the
The synthesis and reactivity of heterodimetallic com-
plexes with a directed polar metal–metal bond continues
to be an active research area in organometallic chemistry
due to their unusual structures, reactions and potential cat-
alytic activities [1–12]. Among these complexes, M–Sn
bonded complexes have drawn special attentions and been
extensively investigated owing to their applications in
many catalytic processes, which often display good selec-
tivity compared to the mononuclear complexes possibly
for the sake of the cooperation effect of two metals.
Recently, many achievements have been gained in MASn
bonded complexes, especially Mo–Sn or W–Sn bonded
complexes [13–24].
*
Corresponding author. Fax: +86 22 23502458.
E-mail address: lftang@nankai.edu.cn (L.-F. Tang).
0022-328X/$ - see front matter ꢀ 2006 Elsevier B.V. All rights reserved.
doi:10.1016/j.jorganchem.2006.05.010

3634
S.-S. Chen et al. / Journal of Organometallic Chemistry 691 (2006) 3633–3639
pentacoordinate tin in these cyclopentadienyl M–Sn bonded
heterocycles. In this paper we present the results of this
study. As we predicted, the reaction of CH3COC5H4-
M(CO)3SnCl3 (M = Mo and W) with arylthiocarboxyhyd-
razide provides pentacoordinate bicyclodiazastannsulfide.
2. Results and discussion
2.1. Reaction of CH3COC5H4M(CO)3SnCl3 with
arylthiocarboxyhydrazide
The reaction of CH3COC5H4M(CO)3SnCl3 (M = Mo or
W) with arylthiocarboxyhydrazide at room temperature
yields bicyclodiazastannsulfides 1–6 (Scheme 1). These
complexes have low solubility in common organic solvents,
moderate solubility in strongly polar solvents such as ace-
tone, DMF and DMSO at room temperature. The com-
plexes have been characterized by element analyses, IR as
Fig. 1. The molecular structure of complex 2. The thermal ellipsoids are
drawn at the 30% probability level. The uncoordinated solvent acetone
˚
molecule has been omitted for clarity. Selected bond distances (A) and
angles (ꢁ): W(1)–Sn(1), 2.7419(5), Sn(1)–Cl(1) 2.361(1), Sn(1)–Cl(2),
2.455(1), Sn(1)–N(1) 2.417(4), Sn(1)–S(1) 2.443(1), N(1)–C(9) 1.281(6),
˚
N(2)–C(10) 1.298(6), N(1)–N(2) 1.397(5), S(1)–C(10) 1.752(5) A; N(1)–
Sn(1)–Cl(2) 159.64(10), Cl(1)–Sn(1)–N(1) 90.75(10), S(1)–Sn(1)–W(1)
136.97(4), C(9)–N(1)–N(2) 116.3(4), C(9)–N(1)–Sn(1), 122.3(3), N(2)–
N(1)–Sn(1) 120.8(3), C(10)–N(2)–N(1) 111.8(4), N(2)–C(10)–S(1) 127.6(4),
C(10)–S(1)–Sn(1) 101.20(16), N(1)–C(9)–C(18) 126.2(5), C(9)–N(1)–N(2)–
C(10) 153.5(4), N(2)–C(10)–C(11)–O(4) À6.4(7), C(4)–C(8)–C(9)–N(1)
À56.4(7)ꢁ.
1
well as H NMR spectra. No characteristic mNH peak is
observed in their IR spectra. The peak due to O–H stretch-
ing has been found at 3352.8 cmÀ1 in 5 and 3326.9 cmÀ1 in
6, respectively. The mC@N peaks appear around 1638–
1604 cmÀ1. The metal carbonyl stretching bands have also
1
been observed in the region of 2037–1917 cmÀ1. Their H
NMR spectra demonstrate the structures by exhibiting
the expected proton signals, such as two sets of Cp ring res-
onances, corresponding to the monosubstituted cyclopen-
tadienyl group. Owing to low solubility, only 13C NMR
spectra of complexes 4 and 5 can be observed in satisfac-
tory quality, which indicate two sets of signals of the imino
carbon atoms as well as three signals of metal carbonyl car-
bon atoms. In addition, the 119Sn NMR signal of 4 in
CD3SOCD3 occurs at À347.5 ppm.
The structures of 2, 3 and 5 have been confirmed further
by X-ray single crystal diffraction analyses. Their structures
are presented in Figs. 1–3, respectively. Although heteroa-
toms of the aryl groups in these three complexes do not
coordinate to the tin atom of adjacent molecules, unlike
in analogous bicyclodiazastannoxide fused cyclopentadie-
nyl M–Sn bonded heterocycle [28,29], the tin atom in com-
plexes 2, 3 and 5 is pentacoordinate, and has a distorted
trigonal bipyramidal coordination with one chlorine atom
and one nitrogen atom occupying the axial positions. The
axial angle of \Cl–Sn–N is very analogous in these com-
plexes (159.6(1)ꢁ for 2, 160.6(1)ꢁ for 3 and 160.66(5)ꢁ for
5, respectively). Other geometric features of complexes 2,
3 and 5 are also markedly different from those of their bicy-
clodiazastannoxide analogues. For example, five-mem-
Fig. 2. The molecular structure of complex 3. The thermal ellipsoids are
drawn at the 30% probability level. Selected bond distances (A) and angles
(ꢁ): Mo(1)–Sn(1) 2.7300(7), Sn(1)–Cl(1) 2.365(1), Sn(1)–Cl(2) 2.446(1),
˚
Sn(1)–N(1) 2.387(4), Sn(1)–S(1) 2.448(1), S(1)–C(11) 1.760(6), N(1)–C(9)
˚
1.281(8), N(1)–N(2) 1.391(6), N(2)–C(11) 1.286(8) A; N(1)–Sn(1)–Cl(2)
160.6(1), Cl(1)–Sn(1)–N(1) 87.1(1), S(1)–Sn(1)–Mo(1) 134.67(5), C(9)–
N(1)–N(2) 118.0(4), C(9)–N(1)–Sn(1) 122.6(4), N(1)–C(9)–C(10) 125.1(5),
C(11)–N(2)–N(1) 113.1(5), N(2)–C(11)–S(1) 127.4(5), C(4)–C(8)–C(9)–
N(1) 65.9(7), C(9)–N(1)–N(2)–C(11) À159.5(5), N(2)–C(11)–C(12)–S(2)
1.4(8)ꢁ.
bered ring of Sn–N–N–C–S remarkably deviates from the
coplanarity, with mean deviation from the plane of
˚
˚
˚
0.1340 A in 2, 0.1422 A in 3 and 0.1425 A in 5, respectively.
In addition, the AC@NAN@CA moiety in these three
complexes is also uncoplanar. The mean deviation from
˚
˚
˚
the plane is 0.1338 A in 2, 0.1023 A in 3 and 0.1126 A in
5, respectively. The torsion angle of \C–N–N–C
(153.5(4)ꢁ in 2, À159.5(5)ꢁ in 3 and À157.6(2)ꢁ in 5, respec-
Scheme 1. Ar = 2-furanyl, M = Mo (1), W (2); Ar = 2-thienyl, M = Mo
(3), W (4); Ar = p-hydroxylphenyl, M = Mo (5), W (6).

S.-S. Chen et al. / Journal of Organometallic Chemistry 691 (2006) 3633–3639
3635
such as in l-[C5H4(CH3)C@NAN@C(O)C6H5]W(CO)3-
˚
SnCl2(EtOH) (complex A, 2.7767(9) A) [28], l-[C5H4-
(CH3)C@NAN@C(O)C4H3O]W(CO)3SnCl2(H2O) (complex
˚
B, 2.8134(9) A) [29], and l-{[C5H4(CH3)C@NA
N@C(O)]2C6H4}{W(CO)3SnCl2(DMSO)}2 (complex C,
˚
2.8118(7) A) [29]. Furthermore, the Mo–Sn bond distances
˚
˚
in complexes 3 and 5 are 2.7300(7) A and 2.7365(3) A,
respectively, also shorter than that in corresponding bicy-
clodiazastannoxide analogues, such as {l-[C5H4(CH3)C@
˚
NAN@C(O)PyH]M(CO)3SnCl3} (complex D, 2.8338(8) A)
[28]. On the other hand, the Sn–N bond distance in these
˚
˚
three complexes (2.417(4) A in 2, 2.387(4) A in 3 and
˚
Fig. 3. The molecular structure of complex 5. The thermal ellipsoids are
drawn at the 30% probability level. The solvent uncoordinated acetone
2.390(2) A in 5, respectively) is longer than that in the
related bicyclodiazastannoxides, such as 2.259(6) A in com-
plex B, 2.231(2) A in complex D.
˚
˚
molecule has been omitted for clarity. Selected bond distances (A) and
˚
angles (ꢁ): Mo(1)–Sn(1) 2.7365(3), Sn(1)–Cl(1) 2.4319(7), Sn(1)–Cl(2)
2.3797(8), Sn(1)–N(1) 2.390(2), Sn(1)–S(1) 2.4322(7), S(1)–C(11) 1.754(3),
O(4)–C(15) 1.369(3), N(1)–C(9) 1.287(3), N(1)–N(2) 1.383(3), N(2)–C(11)
2.2. Reaction of CH3COC5H4M(CO)3SnCl3 with o- or
p-hydroxyphenylcarboxyhydrazide
˚
1.298(3) A; Cl(2)–Sn(1)–Cl(1) 96.25(3), N(1)–Sn(1)–Cl(1) 160.66(5), S(1)–
Sn(1)–Mo(1) 135.93(2), C(9)–N(1)–N(2) 117.4(2), C(9)–N(1)–Sn(1)
123.11(17), N(2)–N(1)–Sn(1) 119.52(15), C(11)–N(2)–N(1) 113.3(2),
C(11)–S(1)–Sn(1) 100.69(9), N(2)–C(11)–S(1) 126.4(2), N(1)–C(9)–C(10)
124.8(2), C(9)–N(1)–N(2)–C(11) À157.6(2), N(2)–C(11)–C(12)–C(13)
À17.7(4), C(4)–C(8)–C(9)–N(1) 68.8(4)ꢁ.
It is known that the hydroxyl group in phenol, a power-
ful electron-donating group, can coordinate to the tin atom
in many mononuclear bicyclodiazastannoxides [30–33].
The observation that the phenolic oxygen atom in complex
5 does not coordinate to the tin atom and the knowledge
that the tin atom in bicyclodiazastannoxide usually dis-
plays hexacoordinate through absorbing complexing sol-
vent molecules encouraged us to explore whether the
phenolic oxygen atom can coordinate to the tin atom in
the dinuclear bicyclodiazastannoxides. At the same time,
to further confirm the existence of pentacoordinate tin in
bicyclodiazastannsulfide as well as the hexacoordinate tin
in bicyclodiazastannoxide, the reaction of p-hydroxyphenyl
tively) has also indicated that the AC@NAN@CA moiety
has poor coplanarity.
It is also noted that the coordination number of tin in
complexes 2, 3, 5 and the corresponding bicyclodiazastann-
oxides markedly affects their geometric parameters. Some
key bond distances, such as M–Sn, Sn–N, Sn–O, Sn–S
and Sn–Cl bond distances, are listed in Table 1. It can be
˚
seen that the W–Sn bond distance (2.7419(5) A) in 2 is
shorter than those in bicyclodiazastannoxide analogues,
Table 1
Comparison of some key bond distances (A) in bicyclodiazastannsulfides and bicyclodiazastannoxides
˚
Compound
M–Sn
Sn–Cl
Sn–N
Sn–S
Sn–O
Reference
This work
l-[C5H4(CH3)C@N–N@C(S)C4H3O]W(CO)3SnCl2 (2)
2.7419(5)
2.361(1)
2.455(1)
2.365(1)
2.446(1)
2.4319(7)
2.3797(8)
2.445(3)
2.454(4)
2.404(1)
2.459(2)
2.487(2)
2.423(2)
2.563(1)
2.512(1)
2.442(1)
2.349(2)
2.346(3)
2.353(2)
2.325(2)
2.348(2)
2.352(2)
2.417(4)
2.443(1)
l-[C5H4(CH3)C@N–N@C(S)C4H3S]Mo(CO)3SnCl2 (3)
2.7300(7)
2.7365(3)
2.7767(9)
2.8134(9)
2.8118(7)
2.8338(8)
2.387(4)
2.390(2)
2.237(9)
2.259(6)
2.263(6)
2.231(2)
2.448(1)
This work
This work
[28]
l-[C5H4(CH3)C@NAN@C(S)(C6H4OH-p)]Mo(CO)3SnCl2 (5)
l-[C5H4(CH3)C@NAN@C(O)C6H5]W(CO)3SnCl2(EtOH) (A)
l-[C5H4(CH3)C@NAN@C(O)C4H3O]W(CO)3SnCl2(H2O) (B)
l-{[C5H4(CH3)C@NAN@C(O)]2C6H4}{W(CO)3SnCl2(DMSO)}2 (C)
l-[C5H4(CH3)C@NAN@C(O)PyH]Mo(CO)3SnCl3 (D)
2.4322(7)
2.10(1)
2.126(4)
2.144(5)
2.166(2)
[29]
[29]
[29]
[C5H4(CH3)C@NANHC(O)(C6H4OH-p)]W(CO)3SnCl3 (10)
[C5H4(CH3)C@NANHC(O)(C6H3(NO2)2)]Mo(CO)3SnCl3 (E)
[C5H5Fe(CO)2]2[(o-NH2)C6H4C(O)@NAN@CHC6H4O]Sn
2.7138(9)
2.7040(7)
This work
[28]
2.5421(8)
2.5242(7)
2.247(4)
2.149(5)
2.198(4)
[31]

3636
S.-S. Chen et al. / Journal of Organometallic Chemistry 691 (2006) 3633–3639
carboxyhydrazide or salicylhydrazide with CH3COC5H4M-
(CO)3SnCl3 is carried out. However, upon treatment of
these two reaction reagents under similar reaction condi-
tions with ArCSNHNH2 only yields nonbridged complexes
7–10 (Scheme 2), in which the benzoylhydrazone does not
enolize the –NHCO– moiety to the AN@C(OH)A moiety.
Neither the imino nitrogen atom, nor carbonyl oxygen
atom or the phenolic oxygen atom does not coordinate
to the tin atom.
These complexes also have low solubility in common
organic solvents, moderate solubility in strongly polar
solvents such as acetone, DMF and DMSO at room tem-
perature. Their IR spectra confirm the tetracoordinate
tin complexes having a AC@NANHC@OA moiety. The
characteristic mNH peak is observed in the region
3186–3289 cmÀ1. The mC@N peaks appear around 1605–
1615 cmÀ1, similar with those in complexes 1–6. In addi-
tion, a mC@O absorption band between 1633–1648 cmÀ1 is
observed in these four complexes. The 13C NMR spectra
of complexes 8 and 10 can be clearly observed, which dis-
play one signal of the carbonyl carbon atom (168.4 ppm
in 8 and 166.9 ppm in 10, respectively) as well as one signal
of the imino carbon atom (159.5 ppm in 8 and 160.6 ppm
in 10, respectively).
The structure of complex 10 has also been confirmed by
X-ray single crystal diffraction analyses. As seen in Fig. 4,
the tin atom is tetracoordinate with a distorted tetrahedral
geometry, similar with that in [C5H4(CH3)C @NANHC-
(O)(C6H3(NO2)2)]Mo(CO)3SnCl3 (complex E) [28], and
the SnCl3 group is away from the aroylhydrazone moiety.
The cooperation effects of several factors maybe result in
the formation of the non-cyclic tetracoordinate tin complex
rather than a bridging penta- or hexacoordinate tin com-
plex. With such a weaker donor of the oxygen atom com-
pared with the sulfur atom, the electron-donating hydroxyl
group of phenol weakening the enolizability of the
–NHCO– moiety to the AN@C(OH)A moiety. In addition,
the large strain maybe exists in the corresponding bicyclo-
diazastannoxide, if formed.
Fig. 4. The molecular structure of complex 10. The thermal ellipsoids are
drawn at the 30% probability level. The solvent uncoordinated acetone
˚
molecule has been omitted for clarity. Selected bond distances (A) and
angles (ꢁ): W(1)–Sn(1) 2.7138(9), Sn(1)–Cl(2) 2.346(3), Sn(1)–Cl(1)
2.349(2), Sn(1)–Cl(3) 2.353(2), N(1)–C(9) 1.275(9), N(1)–N(2) 1.377(7),
˚
N(2)–C(11) 1.385(9), O(4)–C(11) 1.221(8), O(5)–C(15) 1.364(8) A; Cl(2)–
Sn(1)–Cl(1) 98.76(10); Cl(1)–Sn(1)–Cl(3) 100.45(10), C(9)–N(1)–N(2)
117.4(6), N(1)–N(2)–C(11) 118.2(6), O(4)–C(11)–N(2) 120.6(6), C(9)–
N(1)–N(2)–C(11) 177.8(6), N(1)–N(2)–C(11)–O(4) À1.3(10), O(4)–C(11)–
C(12)–C(13) 169.4(8), C(4)–C(8)–C(9)–N(1) À3.3(11)ꢁ.
tin atom weakening the bonding between the Sn–Cl as well
as the Sn–M.
Combined with previous work, it seems that the tin
atom prefers to be pentacoordinate in these heterobime-
tallic bicyclodiazastannsulfides; while in corresponding
bicyclodiazastannoxide analogues, it is usually hexacoor-
dinate. However, when salicylhadrazide, p-hydroxy-
phenylcarboxyhydrazide and phenylhydrazine are used
to react with CH3COC5H4M(CO)3SnCl3, only non-cyclic
tetracoordinate tin complexes are obtained. Furthermore,
the structural feature of the tin center in these heterobi-
metallic complexes significantly depends on the coordina-
tion number of the tin atom.
3. Experimental
Solvents were dried by the standard methods prior to
use. All reactions were carried out under an argon atmo-
sphere using standard Schlenk and Cannula techniques.
NMR spectra were obtained with a Mercury 300BB or
Bruker AV300 spectrometer, and the chemical shifts were
reported in ppm with respect to the reference. IR spectra
data were obtained from a Bio-Rad FTS 135 spectrometer
using KBr discs. Element analyses were carried out on a
Perkin–Elmer 2400 C analyzer. CH3COC5H4M(CO)3SnCl3
(M = Mo or W) [28] and arylthiocarboxyhydrazide [34]
were prepared by the published methods.
Compared with the pentacoordinate tin complex 2 and
the hexacoordinate tin complexes A, B and C, the tetraco-
ordinate tin complex 10 has shorter W–Sn bond distance
˚
(2.7138(9) A) (see Table 1). The Sn–Cl bond distances in
complex 10 are similar to those in the tetracoordinate tin
complex E, but shorter than those in penta- and hexacoor-
dinate tin complexes. These short bond distances obviously
arise from the increment of the coordination number of the
3.1. Preparation of complex 1
2-Furanthiocarboxyhydrazide (21 mg, 0.15 mmol) was
added to the solution of CH3COC5H4Mo(CO)3SnCl3
(76.9 mg, 0.15 mmol) in 10 ml absolute ethanol. The reac-
tion mixture was stirred continuously for 2 h at room tem-
perature, during which a yellow precipitate was formed
gradually. The solvent was concentrated to ca. 2 ml under
a reduced pressure, and the precipitate was filtered off,
Scheme 2. Ar = o-hydroxylphenyl, M = Mo (7), W (8); Ar = p-hydroxyl-
phenyl, M = Mo (9), W (10).

S.-S. Chen et al. / Journal of Organometallic Chemistry 691 (2006) 3633–3639
3637
washed with cold absolute ethanol and recrystallized from
acetone/hexane to yield yellow crystals of 1. Yield: 81%. 1H
NMR (DMSO-d6): d 8.13, 7.49, 6.85 (s, d, m, 1H, 1H, 1H,
C4H3O), 6.24, 6.05 (s, s, 2H, 2H, C5H4), 2.67 (s, 3H, CH3).
was 3 h. After similar workup, yellow crystals of 5 were
obtained. Yield: 84%. 1H NMR (DMSO-d6): d 10.4 (s,
1H, OH), 7.99, 6.89 (d, d, 2H, 2H, C6H4), 6.20, 5.98 (s, s,
2H, 2H, C5H4), 2.61 (s, 3H, CH3). 13C NMR (DMSO-
d6): d 21.4 (CH3), 89.2, 94.7, 99.3 (C5H4), 115.4, 122.0,
126.6, 129.9 (C6H4), 161.5, 162.5 (C@N), 206.6, 223.5,
227.8 (CO). IR: mOH = 3352.8 (br); mCO = 2029.2 (vs),
1936.7 (br, vs); mC@N = 1619.4 (m), 1616.5 (m) cmÀ1. Anal.
Calc. for C20H18Cl2MoN2O5SSn: C, 35.09; H, 2.63; N,
4.09. Found: C, 35.65; H, 2.86; N, 3.59%.
IR:
m
mCO = 2031.6 (vs), 1981.3 (vs), 1935.3 (vs);
C@N = 1607.7 (m) cmÀ1. Anal. Calc. for C18H16Cl2Mo-
N2O5SSn: C, 32.83; H, 2.43; N, 4.26. Found: C, 32.67;
H, 2.92; N, 3.95%.
3.2. Preparation of complex 2
This complex was obtained similarly using 2-fur-
anthiocarboxyhydrazide to react with CH3COC5H4W-
(CO)3SnCl3 as described above for 1. After similar
3.6. Preparation of complex 6
This complex was obtained similarly using 4-hydroxy-
benzothiocarboxyhydrazide to react with CH3COC5H4
W(CO)3SnCl3 as described above for 1. The reaction time
was 3 h. After similar workup, red crystals of 6 were
obtained. Yield: 79%. 1H NMR (CD3COCD3): d 8.09,
6.94 (d, d, 2H, 2H, C6H4), 6.46, 6.11 (t, t, 2H, 2H,
1
workup, red crystals of 2 were obtained. Yield: 85%. H
NMR (DMSO-d6): d 8.05, 7.42, 6.78 (s, d, m, 1H, 1H,
1H, C4H3O), 6.34, 6.07 (s, s, 2H, 2H, C5H4), 2.63 (s,
3H, CH3). IR: mCO = 2024.8 (vs), 1967.6 (vs), 1923.3
(vs); mC@N = 1608.1 (m) cmÀ1. Anal. Calc. for C18H16-
Cl2N2O5SSnW: C, 28.95; H, 2.14; N, 3.75. Found: C,
28.72; H, 2.45; N, 3.68%.
C5H4), 2.68 (s, 3H, CH3). IR:
m
OH = 3326.9 (br);
C@N = 1604.9
. Anal. Calc. for C20H18Cl2N2O5SSnW: C,
m
CO = 2024.0 (vs), 1927.0 (br, vs);
m
(m) cmÀ1
3.3. Preparation of complex 3
31.09; H, 2.33; N, 3.63. Found: C, 31.28; H, 2.62; N, 3.70%.
This complex was obtained similarly using 2-thio-
phenethiocarboxyhydrazide to react with CH3COC5H4-
Mo(CO)3SnCl3 as described above for 1. The reaction time
was 3 h. After similar workup, yellow crystals of 3 were
3.7. Preparation of complex 7
Salicylhydrazide (22.8 mg, 0.15 mmol) was added to
the solution of CH3COC5H4Mo(CO)3SnCl3 (76.9 mg,
0.15 mmol) in 10 ml absolute ethanol. The reaction mixture
was stirred and refluxed continuously for 3 h to obtain a
yellow solution. The solvent was removed under a reduced
pressure and the residual solid was recrystallized from ace-
tone/hexane to yield yellow crystals of 7 (76.9 mg, 74%). 1H
NMR (DMSO-d6): d 12.07 (s, 1H, OH), 7.98, 7.50, 7.00 (d,
m, m, 1H, 1H, 2H, C6H4), 5.86, 5.78 (s, s, 2H, 2H, C5H4),
2.57 (s, 3H, CH3). IR: mOH = 3425.6 (br); mNH = 3286.5 (w),
1
obtained. Yield: 84%. H NMR (DMSO-d6): d 7.95, 7.25
(m, m, 2H, 1H, C4H3S), 6.16, 5.96 (s, s, 2H, 2H, C5H4),
2.61 (s, 3H, CH3). IR: mCO = 2036.3 (vs), 1984.4 (vs),
1920.0 (vs); mC@N = 1637.9 (m) cmÀ1. Anal. Calc. for
C15H10Cl2MoN2O3S2Sn: C, 29.22; H, 1.62; N, 4.55.
Found: C, 28.76; H, 2.01; N, 4.45%.
3.4. Preparation of complex 4
m
m
CO = 2061.8 (vs), 1989.4 (s), 1943.4 (vs), 1930.1 (vs);
This complex was obtained similarly using 2-thio-
phenethiocarboxyhydrazide to react with CH3COC5H4-
W(CO)3SnCl3 as described above for 1. The reaction time
was 3 h. After similar workup, red crystals of 4 were
obtained. Yield: 82%. 1H NMR (CD3COCD3): d 7.86,
7.72, 7.14 (d, d, m, 1H, 1H, 1H, C4H3S), 6.35, 6.01 (t, t,
2H, 2H, C5H4), 2.53 (s, 3H, CH3). 13C NMR
(CD3COCD3): d 22.4 (CH3), 88.5, 94.2, 94.9 (C5H4),
128.7, 131.9, 132.9, 140.4 (C4H3S), 162.5, 166.9 (C@N),
206.9, 216.9, 223.6 (CO). 119Sn NMR (DMSO-d6):
d À 347.5. IR: mCO = 2029.2 (vs), 1970.6 (vs), 1917.8 (vs);
C@O = 1633.6 (m); mC@N = 1615.1 (m) cmÀ1. Anal. Calc.
for C20H19Cl3MoN2O6Sn: C, 34.07; H, 2.70; N, 3.97.
Found: C, 33.66; H, 2.71; N, 3.89%.
3.8. Preparation of complex 8
This complex was obtained similarly using salicylhyd-
razide (22.8 mg, 0.15 mmol) to react with CH3COC5H4W-
(CO)3SnCl3 (90 mg, 0.15 mmol) as described above for 7.
After similar workup, yellow crystals of 8 were obtained.
1
Yield: 79%. H NMR (DMSO-d6): d 12.22 (br, 1H, OH),
m
C@N = 1609.7 (m) cmÀ1. Anal. Calc. for C15H10Cl2-
8.05, 7.56, 7.06 (d, m, m, 1H, 1H, 2H, C6H4), 6.11, 5.96
(s, s, 2H, 2H, C5H4), 2.65 (s, 3H, CH3). 13C NMR
(DMSO-d6): d 19.6 (CH3), 85.0, 93.9, 94.0 (C5H4), 117.1,
119.1, 125.9, 129.3, 133.9, 134.4 (C6H4), 159.5 (C@N),
N2O3S2SnW: C, 25.57; H, 1.42; N, 3.98. Found: C, 25.80;
H, 1.74; N, 3.78%.
3.5. Preparation of complex 5
168.4 (C@O), 212.9 (CO). IR:
m
OH = 3423.8 (br);
m
NH = 3287.6 (m); mCO = 2049.7 (vs), 1981.7 (s), 1949.4
This complex was obtained similarly using 4-hydroxy-
benzothiocarboxyhydrazide to react with CH3COC5H4-
Mo(CO)3SnCl3 as described above for 1. The reaction time
(sh), 1937.4 (vs);
m
C@O = 1647.2 (s);
mC@N = 1610
(m) cmÀ1. Anal. Calc. for C20H19Cl3N2O6SnW: C, 30.28;
H, 2.40; N, 3.53. Found: C, 30.51; H, 2.79; N, 3.97%.

3638
S.-S. Chen et al. / Journal of Organometallic Chemistry 691 (2006) 3633–3639
Table 2
Crystal data and refinement parameters for complexes 2, 3, 5 and 10
Compound
2 Æ CH3COCH3
3
5 Æ CH3COCH3
10 Æ CH3COCH3
Formula
C18H16Cl2N2O5SSnW
745.83
0.24 · 0.16 · 0.12
Monoclinic
P21/n
C15H10Cl2MoN2O3S2Sn
615.90
0.24 · 0.14 · 0.10
Orthorhombic
Pna21
C20H18Cl2MoN2O5SSn
683.95
0.22 · 0.12 · 0.10
Monoclinic
C20H19Cl3N2O6SnW
792.26
0.22 · 0.14 · 0.12
Monoclinic
P21/n
Formula weight
Crystal size(mm)
Crystal system
Space group
P21/c
Cell parameters
˚
a (A)
9.0838(14)
20.514(3)
12.548(2)
96.881(2)
2321.3(6)
4
19.498(3)
10.6125(15)
9.8148(14)
90.0
2030.9(5)
4
10.2796(8)
16.7830(12)
14.3355(11)
91.5510(10)
2472.3(3)
4
12.941(4)
15.431(5)
14.067(5)
113.456(4)
2576.9(14)
4
˚
b (A)
˚
c (A)
b (ꢁ)
3
˚
V (A)
Z
T (K)
293(2)
2.134
3.82–50.06
1408
0.71073
6.379
293(2)
2.014
4.18–50.04
1184
0.71073
2.333
293(2)
1.838
3.74–50.06
1336
0.71073
1.851
293(2)
1.803
3.62–50.06
1356
0.71073
1.803
Calcd. density (g cmÀ3
2h Range (ꢁ)
F(000)
)
˚
k (Mo Ka) (A)
l (mmÀ1
)
No. of reflections measured
No. of reflections observed [Rint
No. of parameters
12520
4099 [0.0306]
274
10208
3447 [0.0291]
236
13310
4364 [0.0191]
293
13759
4546 [0.0390]
301
]
Residuals R, Rw [I > 2r(I)]
GOF
0.0261, 0.0538
1.040
0.0272, 0.0638
1.072
0.0207, 0.0485
1.028
0.0373, 0.0949
1.021
3.9. Preparation of complex 9
the acetone solution of these complexes at À18 ꢁC. Crystals
of complexes 2, 5 and 10 crystallize with one molecular
acetone, respectively. Intensity data were collected on a
Bruker SMART CCD diffractometer with graphite-mono-
This complex was obtained similarly using 4-hydroxyl-
phenylhydrazide to react with CH3COC5H4Mo(CO)3SnCl3
as described above for 7. After similar workup, yellow crys-
tals of 9 were obtained. Yield: 78%. 1H NMR (DMSO-d6):
d 8.00, 6.88 (d, d, 2H, 2H, C6H4), 5.77, 5.72 (s, s, 2H, 2H,
˚
chromated Mo Ka radiation (k = 0.71073 A) using the x/
2h scan technique, and a semi-empirical absorption correc-
tion was applied for all complexes. The structures were
solved by direct methods and refined by full-matrix least-
squares on F2. The absolute structure parameter for 3
was 0.00(3). All non-hydrogen atoms were refined aniso-
tropically. A summary of the fundamental crystal data
for 2, 3, 5 and 10 is listed in Table 2.
C5H4), 2.56 (s, 3H, CH3). IR: mOH = 3380.5 (br); mNH
3186.2 (w), mCO = 2051.1 (vs), 1929.1 (s), 1962.7 (vs);
C@O = 1645.4 (m); mC@N = 1605.4 (m) cmÀ1. Anal. Calc.
=
m
for C20H19Cl3MoN2O6Sn: C, 34.07; H, 2.70; N, 3.97.
Found: C, 34.52; H, 2.35; N, 4.35%.
3.10. Preparation of complex 10
Acknowledgements
This complex was obtained similarly using 4-hydrox-
ylphenylhydrazide to react with CH3COC5H4W-
(CO)3SnCl3 as described above for 7. After similar workup,
This work is supported by the National Natural Science
Foundation of China (Nos. 20472037 and 20421202) and
the Ministry of Education of China (NCET-04-0227).
1
red crystals of 10 were obtained. Yield: 82%. H NMR
(DMSO-d6): d 8.07, 6.96 (d, d, 2H, 2H, C6H4), 6.03, 5.91
(s, s, 2H, 2H, C5H4), 2.57 (s, 3H, CH3). 13C NMR
(DMSO-d6): d 19.2 (CH3), 84.8, 93.7, 95.0 (C5H4), 115.1,
119.1, 123.5, 129.8 (C6H4), 160.6 (C@N), 166.9 (C@O),
213.0 (CO). IR: mOH = 3426.3 (br); mNH = 3288.5 (m);
Appendix A. Supplementary information
Crystallographic data (CIF files) for the structures of
complexes 2, 3, 5 and 10 have been deposited with the
Cambridge Crystallographic Data Centre, CCDC No.
600530 for 2, CCDC no.600527 for 3, 600528 for 5, and
CCDC no. 600529 for 10. Copies of this information
may be obtained free of charge from CCDC, 12 Union
Road, Cambridge, CB2, 1EZ, UK, fax: +44 1223 336
033; e-mail: deposit@ccdc.cam.ac.uk or www: http://
www.ccdc.cam.ac.uk). Supplementary data associated with
this article can be found, in the online version, at
doi:10.1016/j.jorganchem.2006.05.010.
m
CO = 2044.7 (vs), 1979.0 (s), 1951.7 (vs); mC@O = 1645.5
(m); Anal. Calc. for
m
C@N = 1605.6 (m) cmÀ1
.
C20H19Cl3N2O6SnW: C, 30.28; H, 2.40; N, 3.53. Found:
C, 30.46; H, 2.63; N, 3.95%.
3.11. X-ray crystallography
Crystals of complexes 2, 3, 5 and 10 suitable for X-ray
analysis were obtained by slow diffusion of hexane into

S.-S. Chen et al. / Journal of Organometallic Chemistry 691 (2006) 3633–3639
3639
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