Reactivity of diorganotin(IV) dichlorides towards N, P, and O donor ligands: Crystal structure of [SnMe2Cl2(phendione)]

Article abstract of DOI:10.1007/s00706-012-0733-5

The reactions of diorganotin(IV) dichlorides SnR2Cl2 (R = Me, n-Bu) with a series of ligands having N, P, or O donor atoms have been investigated. The reaction of SnR2Cl2 (R = Me, n-Bu) with the bidentate chelating pyridyl ligands of phendione (1,10-phenanthroline-5,6- dione) and ndppz (11-nitrodipyrido[3,2-a: 20,30-c]phenazine) affords new hexa-coordinated 1:1 adducts with general formula SnR2Cl2L (R = Me, n-Bu; L = phendione, ndppz). On the other hand, SnMe2Cl2 reacted with xantphos [9,9-dimethyl-4,5-bis(diphenylphosphino)xanthene] to yield the hexa-coordinated 1:2 adduct [SnMe2Cl2 (xantphos)2] in the solid state. However, it dissociates in solution to give the penta-coordinated 1:1 complex [SnMe2 Cl2(xantphos)]. Notably, the analogous n-Bu derivative does not react, even under forcing conditions. Finally, the tin(IV) compounds SnR2Cl2 (R = Me, n-Bu) react with dppap [2-(diphenylphosphinoamino)pyridine] to give the penta-coordinated 1:1 adducts [SnR2Cl2(dppap)] (R = Me, n-Bu). The resulting complexes have been characterized by nuclear magnetic resonance (NMR) spectroscopy and elemental analysis. The X-ray crystal structure determination of [SnMe2Cl2(phendione)] reveals that the compound crystallized with two independent molecules in the asymmetric unit with a trans-[SnMe2] configuration. Springer-Verlag 2012.

Full text of DOI:10.1007/s00706-012-0733-5

Monatsh Chem
DOI 10.1007/s00706-012-0733-5
ORIGINAL PAPER
Reactivity of diorganotin(IV) dichlorides towards N, P, and O
donor ligands: crystal structure of [SnMe2Cl2(phendione)]
•
B. Z. Momeni R. Kia S. Ghanbarzadeh
•
Received: 9 August 2011 / Accepted: 6 February 2012
Ó Springer-Verlag 2012
Abstract The reactions of diorganotin(IV) dichlorides
SnR2Cl2 (R = Me, n-Bu) with a series of ligands having N,
P, or O donor atoms have been investigated. The reaction
of SnR2Cl2 (R = Me, n-Bu) with the bidentate chelating
pyridyl ligands of phendione (1,10-phenanthroline-5,6-
dione) and ndppz (11-nitrodipyrido[3,2-a:20,30-c]phena-
zine) affords new hexa-coordinated 1:1 adducts with
general formula SnR2Cl2L (R = Me, n-Bu; L = phendi-
one, ndppz). On the other hand, SnMe2Cl2 reacted with
crystallized with two independent molecules in the asym-
metric unit with a trans-[SnMe2] configuration.
Keywords Organotin ꢀ Coordination ꢀ Pyridyl ꢀ
NMR ꢀ Crystal structure
Introduction
xantphos
[9,9-dimethyl-4,5-bis(diphenylphosphino)xan-
Pyridyl derivatives of tin(IV) compounds play an important
role in developing the coordination and organometallic
chemistry of tin [1–4]. It is well known that there is a relation
between the antitumor activity of organotin(IV) adducts
containing N donor ligands and Sn–N bond length [5, 6].
These versatile ligands adopt various modes of coordination
to form 1:1 or 1:2 adducts, affording penta- or hexa-coor-
dinated complexes of tin(IV) [7]. The common geometries
for organotin(IV) compounds are a trigonal bipyramidal or
an octahedral geometry [8]. Notably, the unusual seven-
coordinated dimethyltin(IV) dichloride adduct in a pentag-
onal bipyramidal geometry has been isolated with a
tridentate pyridyl heterocycle [2,4,6-tris(2-pyridyl)-1,3,5-
triazine] [9]. The geometries of organotin(IV) adducts are
affected by the nature of the organic group (R), halide or
pseudohalide, and donor ligand [10]. Many organotin(IV)
adducts dissociate in solution, and the behavior in solution is
dependent upon the nature of the organotin(IV) compound
and solvent [2, 11]. As part of our interest in the investigation
of the coordination chemistry of tin, particularly that of or-
ganotin compounds, we prepared some diorganotin(IV)
adducts including two bidentate pyridyl ligands: 1,10-phen-
anthroline-5,6-dione (phendione) and 11-nitrodipyrido-
[2,3-a:20,30-c]phenazine (ndppz). It has been shown that
phendione can interact with the metal centers through qui-
nonoid or diiminic functionality [12]. On the other hand, the
thene] to yield the hexa-coordinated 1:2 adduct [SnMe2Cl2
(xantphos)2] in the solid state. However, it dissociates in
solution to give the penta-coordinated 1:1 complex [SnMe2
Cl2(xantphos)]. Notably, the analogous n-Bu derivative
does not react, even under forcing conditions. Finally, the
tin(IV) compounds SnR2Cl2 (R = Me, n-Bu) react with
dppap [2-(diphenylphosphinoamino)pyridine] to give the
penta-coordinated 1:1 adducts [SnR2Cl2(dppap)] (R = Me,
n-Bu). The resulting complexes have been characterized by
nuclear magnetic resonance (NMR) spectroscopy and ele-
mental analysis. The X-ray crystal structure determination
of [SnMe2Cl2(phendione)] reveals that the compound
B. Z. Momeni (&) ꢀ S. Ghanbarzadeh
Department of Chemistry, K.N. Toosi University of Technology,
P.O. Box 16315-1618, 15418 Tehran, Iran
e-mail: momeni@kntu.ac.ir
R. Kia
X-ray Crystallography Lab, Plasma Physics Research Center,
Science and Research Branch, Islamic Azad University,
Tehran, Iran
R. Kia
Department of Chemistry, Science and Research Branch,
Islamic Azad University, Tehran, Iran
123

B. Z. Momeni et al.
Scheme 1
2
2
3
1
3
4
1
14
N
13
10
5
8
1
8a
9a
4a
N
O
O
4N
6
9
7
6
12
2
3
4
3
5
10
O
N
5N
N
NO2
11
10a
N
5
4
4'
3'
2
9
8
NHPPh2
6
PPh2
xantphos
1'
PPh2
7
2'
phendione
dppap
ndppz
presence of two types of basic centers P and O atoms in 4,5-
bis(diphenylphosphino)-9,9-dimethylxanthene (xantphos)
or P and N atoms in 2-(diphenylphosphinoamino)pyridine
(dppap) makes them the ideal ligands to study the differ-
ent coordinating abilities of two sets of donor atoms
(Scheme 1). Interestingly, both of these phosphinohetero-
arenes can act as monodentate or bidentate ligands. We used
these types of ligands to obtain more information about the
relative reactivities of organotin(IV) complexes towards N,
P, or O donor ligands.
Scheme 2
NMR spectrum of complex 1 displayed a signal at
d = -184 ppm. It has been reported that d values range
from ?200 to -60 ppm for four-coordinated, from -90 to
-190 ppm for five-coordinated, and from -210 to
-400 ppm for six-coordinated tin complexes in solution
[16]. Thus, the signal at -184 ppm is in the range of those
reported for the penta-coordinated diorganotin(IV) com-
plexes. The signal at d = -184 ppm confirms that the
complex 1 is not stable in solution and dissociates to some
extent to afford the penta-coordinated tin(IV) complex. The
chemical shift of 1 is significantly more upfield to the starting
complex SnMe2Cl2 (d = 137.2 ppm in CDCl3) [17],
resulting from the coordination of an N atom to the tin center.
On the other hand, the reaction of dibutyltin(IV)
dichloride with phendione resulted in the formation of the
Results and discussion
NMR studies
Reactions of diorganotin(IV) dichlorides (SnR2Cl2,
R = Me, n-Bu) with the bidentate pyridyl ligand phendi-
one resulted in formation of hexa-coordinated 1:1
complexes [SnR2Cl2(phendione)] [R = Me (1), n-Bu (2)]
as shown in Scheme 2. The products were characterized
1
unambiguously by H and 119Sn NMR spectroscopy and
elemental analysis.
The 1H NMR of the complex [SnMe2Cl2(phendione)] (1)
1
complex [SnBu2Cl2(phendione)] (2) (Scheme 2). The H
NMR spectrum of complex 2 in CDCl3 contains a triplet at
2
in CDCl3 shows a signal at d = 1.2 ppm with J(119Sn–
2
H) = 77.6 Hz and J(117Sn–H) = 74.4 Hz (Fig. 1), differ-
3
d = 0.87 ppm with J(HH) = 7.4 Hz due to the methyl
groups of the butyl ligands as shown in Fig. 1. The
ent from that of the starting complexSnMe2Cl2, which shows
2J(119Sn–H) = 68.6 Hz and 2J(117Sn–H) = 65.7 Hz in
CDCl3 [13]. The magnitude of the coupling constant of the
methyl protons with 119Sn is a useful guide for determination
of the geometry of the tin atom. This coupling constant is in
the range of the penta-coordinated dimethyltin(IV) com-
plexes [14, 15]. These data suggest that the interaction
between SnMe2Cl2 and phendione is not maintained in
solution and the complex undergoes partial dissociation to
afford the penta-coordinated tin(IV) complex.
CH2CH3 resonance appears as a multiplet at d = 1.32 ppm
with J(HH) = 7.2 Hz, while the protons of SnCH2 and
3
SnCH2CH2 groups of the butyl ligands appear as a broad
multiplet at d = 1.58–1.80 ppm. Therefore, the tin satel-
lites could not be resolved. The 119Sn NMR spectrum of
complex 2 in acetone-d6 shows a signal at d = -194 ppm
which clearly indicates the presence of a hexa-coordinated
adduct of dibutyltin(IV) in solution.
The complex [SnMe2Cl2(ndppz)] (3) was prepared by
reaction of SnMe2Cl2 with ndppz, as shown in Scheme 2. It
The complex 1 was insoluble in most of the common
organic solvents such as acetone, dichloromethane, dichlo-
roethane, and tetrachloroethane to provide a satisfactory
119Sn NMR spectrum. Therefore, the 119Sn NMR spectrum
of complex 1 was recorded in acetone-d6 in the presence of
small amounts of dimethyl sulfoxide (DMSO)-d6. The 119Sn
1
was readily characterized by its H NMR spectrum, which
contained a signal at d = 1.19 ppm with J(119Sn–H) =
2
105.2 Hz and J(117Sn–H) = 101.2 Hz in CDCl3. These
2
coupling constants are in the range of the other hexa-
coordinate dimethyltin(IV) complexes [2, 18]. Moreover,
123

Reactivity of diorganotin(IV) dichlorides
Fig. 1 1H NMR spectra of
a [SnMe2Cl2(phendione)] (1)
and b [SnBu2Cl2(phendione)]
(2) in CDCl3
H3
(a)
H1
H2
SnCH3
2J(119Sn-H)
2J(117Sn-H)
H3
(b)
H2
H1
CH3
SnCH2 and SnCH2CH2
CH2CH
reaction of SnBu2Cl2 with ndppz affords the hexa-coordi-
nated complex [SnBu2Cl2(ndppz)] (4). The formation of a
1:1 adduct has been supported by elemental analysis.
Of particular note, the reaction of SnMe2Cl2 with
xantphos resulted in formation of complex [SnMe2Cl2
(xantphos)2] (5) in the solid state; however, it dissociates in
solution to give the complex [SnMe2Cl2(xantphos)] (6)
(Scheme 3).
70.7 Hz. This coupling constant is in the range of the other
penta-coordinated dimethyltin(IV) complexes [14, 15]. On
the other hand, the 31P NMR of complex 6 in CDCl3 shows a
signal at d = -16.8 ppm which is very close to that observed
for xantphos [19]. The elemental analysis results show that
there is a 1:2 Sn:xantphos molar ratio which indicates the
formation of a hexa-coordinated organotin(IV) adduct in
the solid state, i.e., [SnMe2Cl2(xantphos-j O)2] (5). On the
basis of these data, we suggest that SnMe2Cl2 is ligated by
xantphos with two coordinated oxygen atoms, giving the
1
The H NMR of complex [SnMe2Cl2(xantphos)] (6) in
CDCl3 showsasignalatd = 1.2 ppm with2J(119/117Sn–H) =
Scheme 3
xantphos
SnMe2Cl2
[SnMe2Cl2(xantphos- O)2]
5 (solid state)
[SnMe2Cl2(xantphos- O)]
6 (solution)
123

B. Z. Momeni et al.
complex (5) in the solid state. However, it dissociates in
solution, resulting in the formation of the penta-coordinated
complex [SnMe2Cl2(xantphos-j O)] (6). This indicates that
thesamestructureisnotretainedinthetwophases. Incontrast,
in the case of reaction of Sn(n-Bu)2Cl2 with xantphos, isola-
tion of 1:1 or 1:2 dibutyltin dichloride adducts was not
successful. Moreover, growth of single crystals from reaction
of [SnBu2Cl2] with xantphos in CH2Cl2/hexane indicated the
presence of the starting materials, consistent with the litera-
ture [19]. It can be seen that the simple substitution of the Me
to n-Bu groups prevents the formation of a dibutyltin(IV)-
xantphos adduct. The most significant conclusion of the
reaction of diorganotin(IV) dichloride with xantphos is the
formation of 1:1 or 1:2 adduct (acid to base), due to the less
bulky methylgroupsonthe diorganotin(IV)dichloride. Itmay
be possible that excessive steric repulsion between the bulky
phenyl substituents on the phosphorus atoms and butyl units
inhibits the formation of 1:1 or 1:2 adducts in the reaction of
SnBu2Cl2 with xantphos.
It can be seen that the formation of penta- or hexa-
coordinate species is influenced by both the nature of the
ligand and the nature of diorganotin compound. In sum-
mary, the basicities towards diorganotin dichlorides vary as
expected: N-pyridyl [ O [ P donor ligands.
Description and discussion of the crystal structure of 1
The molecular structure of [SnMe2Cl2(phendione)] (1) is
shown in Fig. 2. Selected bond distances and angles are
also given in Table 1. Two independent molecules of
compound 1 form the asymmetric unit, labeled (1) and (2).
The crystal structure of 1 shows that the tin atom exists in
an octahedral geometry as revealed by the C(1)–Sn–C(2)
angles which deviate insignificantly from linearity
[171.6(3)° to 175.2(4)°]. The chlorine atoms are cis to each
other, while the methyl groups are trans. This is consistent
with the other diorganotin dihalide adducts containing
bidentate ligands which have cis halogens [25, 26]. Phen-
dione acts in a bidentate manner, as expected through both of
the nitrogen atoms adopting cis conformation. Interestingly,
there is one structure with planar phendione with O(4)–
C(22)–C(23)–O(3) torsion angle of -0.8(10)° and another
one with a slightly distorted phendione ligand resulting from
the nonaromaticity of the central quinoid ring with O(2)–
C(8)–C(9)–O(1) torsion angle of 10.6(15)°. The Sn–C bond
distances are not equal [for example, Sn(1)–C(14) =
In addition, we have investigated the reaction of dior-
ganotin dichlorides with dppap. This ligand exhibits a
number of coordination modes which have been exten-
sively studied [20–22]. Dimethyltin(IV) dichloride and
dibutyltin(IV) dichloride reacted with dppap to give the
complexes [SnR2Cl2(dppap)] [R = Me (7), Bu (8)] in
solution (Scheme 4).
The nature of 1:1 adducts for 7 and 8 in the solid state
was verified by elemental analysis results. The 1H NMR of
complex 7 in CDCl3 shows a signal at d = 1.2 ppm with
2J(119/117Sn–H) = 72.3 Hz, indicating the presence of the
penta-coordinated adduct [SnMe2Cl2(dppap)] (7) in solu-
tion. Moreover, the coupling between methyl hydrogens
and 31P nuclei could not be observed, largely due to the N
ligating atom of pyridyl. It was known that the phosphine
oxides are much more reactive towards tin(IV) compounds
relative to phosphine ligands. There are relatively few
examples of tin(IV)-phosphine adducts having P donor
atoms. In most of the cases, the resulting coordination
compounds were isolated by using oxidized P donors [23,
24]. In view of the fact that the interaction between tin(IV)
compounds and P donor ligands is not well recognized and
the absence of the coupling between hydrogen and phos-
phorus nuclei, we propose that interaction between
SnR2Cl2 takes place via the N-pyridyl atom. Unfortunately,
the complexes 3–8 were too insoluble, even in DMSO, to
provide 13C or 119Sn NMR spectra.
˚
˚
2.097(7) A and Sn(1)–C(13) = 2.123(7) A]. The Sn–Cl
bonds are also inequivalent [for example, Sn(1)–Cl(1) =
˚
2.4739(19) and Sn(1)–Cl(2) = 2.506(2) A]. The bond
lengths of the two Sn–N bonds are different with Sn(1)–N(2)
˚
[2.469(5) A] and Sn(2)–N(3) [2.453(5) A] being longer than
˚
˚
˚
Sn(1)–N(1) [2.436(5) A] and Sn(2)–N(4) [2.401(6) A],
respectively, which is due to the packing of the crystal. The
N1–Sn(1)–N2 and N3–Sn(2)–N4 bite angles are 67.34(17)°
and 68.11(18)°, respectively, which are consistent with those
observed for other chelating diimine ligands [2]. The crystal
structure of [SnMe2Cl2(phendione)] reported here may be
compared to that of [SnPh2Cl2(phendione)] [27]. The in-
equivalent Sn–N and Sn–Cl bond distances have also been
observed in the crystal structure of [SnPh2Cl2(phendi-
one)]ꢀ2Me2CO; however, the phenyl groups are in cis sites.
The interesting features of the crystal structure are short
intermolecular C–HꢀꢀꢀCl contacts (Table 2) which link
neighboring molecules together into chains along the a-
axis, which seems to be effective in the stabilization of the
crystal packing (Fig. 3).
SnR2Cl2 + dppap
[SnR2Cl2(dppap)]
Experimental
R = Me (7)
R = Bu (8)
Dichloromethane was distilled from P2O5, and diethyl ether
was distilled from sodium/benzophenone ketyl. Acetone
Scheme 4
123

Reactivity of diorganotin(IV) dichlorides
Fig. 2 The molecular structure
of complex 1, showing 30%
probability displacement
ellipsoids and the atomic
numberings. H atoms are
omitted for clarity. The open
bond shows the minor
component of the disordered Cl
atom
˚
Table 1 Selected bond distances (A) and bond angles (°) for com-
plex 1
Table 2 Hydrogen bond data
˚
˚
D–HꢀꢀꢀA
HꢀꢀꢀA/A
DꢀꢀꢀA/A
D–HꢀꢀꢀA/°
Sn(1)–C(14)
Sn(1)–C(13)
Sn(1)–N(1)
Sn(1)–N(2)
Sn(1)–Cl(1)
Sn(1)–Cl(2)
O(1)–C(9)
2.097(7)
2.123(7)
2.436(5)
2.469(5)
C(13)–Sn(1)–Cl(2)
N(1)–Sn(1)–Cl(2)
N(2)–Sn(1)–Cl(2)
Cl(1)–Sn(1)–Cl(2)
90.1(2)
C(1)–H(1A)ꢀꢀꢀCl(1)
C(2)–H(2A)ꢀꢀꢀO(4)a
C(17)–H(17A)ꢀꢀꢀO(1)b
C(25)–H(25A)ꢀꢀꢀO(1)c
C(28)–H(28C)ꢀꢀꢀCl(2)
2.80
2.44
2.48
2.52
2.83
3.475(8)
3.351(8)
3.39(1)
130
168
168
142
160
165.49(13)
98.19(14)
102.61(8)
175.2(4)
89.9(3)
3.31(1)
2.4739(19) C(28)–Sn(2)–C(27)
3.744(9)
2.506(2)
1.196(9)
1.211(8)
2.111(9)
2.123(8)
2.401(6)
2.453(5)
C(28)–Sn(2)–N(4)
C(27)–Sn(2)–N(4)
C(28)–Sn(2)–N(3)
C(27)–Sn(2)–N(3)
N(4)–Sn(2)–N(3)
89.8(3)
Symmetry codes: a1 - x, 1 - y, 1 – z; bx, 3/2 - y, 1/2 ? z; cx,
-1 ? y, z
O(2)–C(8)
89.2(3)
Sn(2)–C(28)
Sn(2)–C(27)
Sn(2)–N(4)
Sn(2)–N(3)
Sn(2)–Cl(3A)
Sn(2)–Cl(3B)
Sn(2)–Cl(4)
86.3(3)
68.11(18)
Aldrich. Phendione, ndppz, and dppap were prepared
according to the literature [12, 20, 28]. All solvents and
reagents were used without further purification. NMR spectra
were recorded using a Bruker Avance DRX 500 spectrometer.
Data are reported relative to the residual protonated solvent
signal (1H), SnMe4 (119Sn), or 85% H3PO4 (31P). All chemical
shifts and coupling constants are reported in ppm and Hz,
respectively. Elemental analyses were performed on a
PerkinElmer 2400 II elemental analyzer.
C(28)–Sn(2)–Cl(3A) 89.4(7)
C(27)–Sn(2)–Cl(3A) 95.4(7)
2.5094(10) N(4)–Sn(2)–Cl(3A)
2.5100(10) N(3)–Sn(2)–Cl(3A)
92.2(5)
160.2(5)
2.557(2)
C(28)–Sn(2)–Cl(3B) 99.4(6)
C(27)–Sn(2)–Cl(3B) 85.3(6)
C(14)–Sn(1)–C(13) 171.6(3)
C(14)–Sn(1)–N(1) 86.4(2)
C(13)–Sn(1)–N(1) 89.4(2)
C(14)–Sn(1)–N(2) 87.2(3)
C(13)–Sn(1)–N(2) 84.5(3)
N(4)–Sn(2)–Cl(3B)
N(3)–Sn(2)–Cl(3B)
84.7(5)
151.6(5)
X-ray diffraction measurements were made on a STOE
IPDS 2T diffractometer with graphite monochromated Mo
Ka radiation. The yellow block crystal was mounted on a
glass fiber and used for data collection. Data collection and
reduction were performed by X-AREA 1.52 [29] program.
The multiscan absorption correction was performed by
MULABS routine [30]. The structure was solved by direct
methods using SHELXS97 and subsequent difference
Fourier map and then refined by a full-matrix least-squares
on F2 by SHELXL97 in SHELXTL package [31]. Non-
hydrogen atoms were refined anisotropically. All of the H
atoms were positioned geometrically and constrained to
ride on their parent atoms with Uiso(H) = 1.2 or 1.5
Ueq(C). One of the chlorine atoms (Cl3) was disordered in
Cl(3A)–Sn(2)–Cl(3B) 12.5(6)
C(28)–Sn(2)–Cl(4)
67.34(17) C(27)–Sn(2)–Cl(4)
89.5(3)
N(1)–Sn(1)–N(2)
89.3(3)
C(14)–Sn(1)–Cl(1) 96.6(2)
C(13)–Sn(1)–Cl(1) 90.8(2)
N(4)–Sn(2)–Cl(4)
N(3)–Sn(2)–Cl(4)
161.40(15)
93.28(14)
106.4(5)
113.7(5)
N(1)–Sn(1)–Cl(1)
N(2)–Sn(1)–Cl(1)
91.89(12) Cl(3A)–Sn(2)–Cl(4)
158.68(14) Cl(3B)–Sn(2)–Cl(4)
C(14)–Sn(1)–Cl(2) 92.2(2)
Symmetry transformations used to generate equivalent atoms: #1 -
x ? 1/2, y, z
and the other reagents were used without further purifica-
tion. Dimethyltin dichloride and dibutyltin dichloride were
purchased from Merck, and xantphos was purchased from
123

B. Z. Momeni et al.
Fig. 3 The crystal packing of
complex 1, viewed down the
c-axis, showing linking of the
neighboring molecules through
intermolecular C–HꢀꢀꢀO
interactions along the a-axis. H
atoms except those involving
the interactions are omitted for
clarity. Intermolecular
interactions are shown as
dashed lines
Dibutyldichloro(1,10-phenanthroline-5,6-dione-j2-
two positions as Cl3A and Cl3B with refined site occu-
pancy ratio of 0.71(5)/0.29(5). All refinements were
performed using the SHELXTL crystallographic software
package. All calculations were done using PLATON [32].
A summary of the crystal data, experimental details, and
refinement parameters is given in Table 3. CCDC 787513
contains the supplementary crystallographic data for this
paper. These data can be obtained free of charge via
http://www.ccdc.cam.ac.uk/conts/retrieving.html, or from
the Cambridge Crystallographic Data Centre, 12 Union
Road, Cambridge CB2 1EZ, UK; fax: ?44-1223-336033;
or e-mail: deposit@ccdc.cam.ac.uk.
N,N0)tin(IV) (2, C20H24Cl2N2O2Sn)
Following the same procedure as for the preparation of 1, a
solution of 100 mg phendione (0.48 mmol) in 10 cm3
dichloromethane was added to a solution of 146 mg Sn(n-
Bu)2Cl2 (0.48 mmol) in 10 cm3 dichloromethane. The
solution was stirred for 24 h. The resultant yellow solution
was evaporated to yield a yellow solid which was filtered
off. The solid was washed with diethyl ether and air dried.
Yield: 85%; m.p.: 101–102 °C; 1H NMR (CDCl3):
d = 0.87 (t, 6H, 3J(HH) = 7.4 Hz, CH3), 1.32 (m, 4H,
3J(HH) = 7.2 Hz, CH2CH3), 1.58–1.80 (m, 8H, SnCH2
and SnCH2CH2), 7.71 (dd, 2H, 3J(HH) = 7.8 Hz,
4J(HH) = 4.8 Hz, H2), 8.60 (d, 2H, 3J(HH) = 7.8 Hz,
Dichlorodimethyl(1,10-phenanthroline-5,6-dione-j2-
N,N0)tin(IV) (1, C14H12Cl2N2O2Sn)
3
H3), 9.28 (d, 2H, J(HH) = 4.4 Hz, H1) ppm; 119Sn NMR
A solution of 100 mg phendione (0.48 mmol) in 10 cm3
dichloromethane was added to a solution of 105 mg
SnMe2Cl2 (0.48 mmol) in 6 cm3 dichloromethane to afford
a yellow solid. The product was then filtered off, washed
with diethyl ether, and air dried. Crystals suitable for X-ray
structure determination were grown from an acetone/
hexane solution. Yield: 89%; m.p.: 190 °C (dec); 1H
(acetone-d6): d = -194 ppm.
Dichlorodimethyl(11-nitrodipyrido[3,2-a:20,30-c]phena-
zine-j2-N,N0)tin(IV) (3, C20H15Cl2N5O2Sn)
A solution of 100 mg ndppz (0.31 mmol) in 20 cm3
dichloromethane was added to a solution of 67 mg
SnMe2Cl2 (0.31 mmol) in 6 cm3 dichloromethane. The
resultant solution was stirred for 24 h. The solvent was
evaporated to give a brown solid. The solid was filtered off,
washed with diethyl ether, and air dried. Yield: 82%; m.p.:
266 °C; 1H NMR (CDCl3): d = 1.20 (s, 6H, 2J(119Sn–
H) = 105.2 Hz, 2J(117Sn–H) = 101.2 Hz, Sn–Me), 8.19 (m,
2
NMR (CDCl3): d = 1.20 (s, 6H, J(119Sn–H) = 77.6 Hz,
3
2J(117Sn–H) = 74.4 Hz, Sn–Me), 7.68 (dd, 2H, J(HH) =
7.8 Hz, 4J(HH) = 4.8 Hz, H2), 8.59 (dd, 2H, 3J(HH) =
7.8 Hz, 4J(HH) = 1.8 Hz, H3), 9.26 (dd, 2H, 3J(HH) = 4.7
Hz, 4J(HH) = 1.6 Hz, H1) ppm; 119Sn NMR (acetone-
d6/DMSO-d6): d = -184 ppm.
3
3
2H, J(HH) = 5.3 Hz, H2,7), 8.63 (d, 1H, J(HH) = 9.2 Hz,
123

Reactivity of diorganotin(IV) dichlorides
Dichlorodimethylbis[9,9-dimethyl-4,5-bis(diphenylphos-
phino)xanthene-j-O]tin(IV) (5, C79H70Cl2O2P4Sn)
Table 3 Experimental details, crystal data, and refinement param-
eters for complex 1
A solution of 100 mg xantphos (0.17 mmol) in 30 cm3
dichloromethane was added to a solution of 38 mg
SnMe2Cl2 (0.17 mmol) in 6 cm3 dichloromethane. The
solution was stirred for 10 h. The resultant colorless
solution was evaporated to dryness to afford a white solid.
The product was then filtered off, washed with n-hexane,
and air dried. Yield: 72%; m.p.: 206–208 °C (dec).
Empirical formula
Formula weight/g mol-1
Temperature/K
C14H12Cl2N2O2Sn
429.85
293 (2)
˚
Wavelength/A
0.71073
Crystal system
Space group
Z
Monoclinic
P21/c
8
1
NMR data for [SnMe2Cl2(xantphos-j O)] (6): H NMR
˚
a/A
14.7050 (10)
15.3702 (14)
14.4135 (9)
94.652 (5)
3,247.0 (4)
1.759
(CDCl3): d = 1.21 (s, 6H, 2J(119/117Sn–H) = 70.7 Hz, Sn–
Me), 1.66 (m, 6H, CH3), 6.56 (d, 2H, J(HH) = 6.2 Hz,
˚
b/A
3
˚
c/A
3
H1,8), 6.96 (t, 2H, J(HH) = 7.6 Hz, H2,7), 7.19–7.27 (m,
b/°
Volume/A
3
phenyl groups), 7.40 (d, 2H, J(HH) = 7.2 Hz, H3,6) ppm;
3
˚
31P NMR (CDCl3): d = -16.8 ppm.
D
calc/g cm-3
Absorption coefficient/mm-1 1.907
Dichlorodimethyl[2-(diphenylphosphinoamino)
pyridine-j-N]tin(IV) dichoromethane hemisolvate
(7, C19H21Cl2N2PSnꢀ0.5CH2Cl2)
F (000)
1,680
h range/°
Index ranges
1.92–25.50
A solution of 100 mg dppap (0.36 mmol) in 20 cm3
dichloromethane was added to a solution of 79 mg
SnMe2Cl2 (0.36 mmol) in 6 cm3 dichloromethane to give
a white solid. The product was then filtered off, washed
with n-hexane, and air dried. Yield: 86%; m.p.:
350–352 °C (dec); 1H NMR (CDCl3): d = 1.26 (s, 6H,
2J(119/117Sn–H) = 72.3 Hz, Sn–Me), 6.81 (t, 1H,
3J(HH) = 6.6 Hz, H5), 7.06 (d, 1H, 3J(HH) = 8.8 Hz,
H3), 7.41 (m, 1H, H4), 7.52 (m, 1H, H6), 7.74 (d, 1H,
2J(31P–H) = 5.8 Hz, NH), 7.75–7.81 (m, phenyl groups)
ppm.
-17 B h B 17, -18 B k B 17,
-16 B l B 17
Reflections collected
12,181
Independent reflections [Rint
Observed reflections
]
5,462/0.056
3,552 [I [ 2r(I)]
0.772/1.000
Full-matrix least-squares on F2
Max./min. transmission
Refinement method
Data/restraints/parameters
Goodness of fit (GOF)
Final R indices [I [ 2r(I)]
R indices (all data)
5,462/8/381
0.916
R1 = 0.0477, wR2 = 0.0933
R1 = 0.0872, wR2 = 0.1033
1.157, -1.512
Largest differences in peak,
-3
˚
Dibutyldichloro[2-(diphenylphosphinoamino)pyridine-j-
N]tin(IV) (8, C25H33Cl2N2PSn)
hole/e A
Following the same procedure as for the preparation of 7, a
solution of 100 mg dppap (0.36 mmol) in 20 cm3 dichlo-
romethane was added to a solution of 109 mg Sn(n-
Bu)2Cl2 (0.36 mmol) in 10 cm3 dichloromethane to afford
a white solid. The solid was then filtered off, washed with
n-hexane, and air dried. Yield: 80%; m.p.: 328 °C (dec);
1H NMR (CDCl3): d = 0.87 (t, 6H, 3J(HH) = 7.0 Hz,
CH3), 1.32 (m, 4H, J(HH) = 5.3 Hz, CH2CH3), 1.75 (br,
3
8H, SnCH2, SnCH2CH2), 6.74 (t, 2H, J(HH) = 6.5 Hz,
H5), 7.19 (d, 1H, 3J(HH) = 8.7 Hz, H3), 7.38 (m, 1H,
H4), 7.44 (d, 1H, 3J(HH) = 6.4 Hz, H6), 7.67 (d, 1H,
2J(31P–H) = 6.0 Hz, NH), 7.71–7.79 (br m, phenyl groups)
ppm.
H13), 8.79 (dd, 1H, 3J(HH) = 9.2 Hz, 4J(HH) = 2.3 Hz, H12),
9.38 (d, 1H, 4J(HH) = 2.4 Hz, H10), 9.88 (m, 2H,
3J(HH) = 3.6 Hz, H1,8), 9.95 (dd, 2H, 3J(HH) = 8.0 Hz,
4J(HH) = 1.8 Hz, H3,6) ppm.
Dibutyldichloro(11-nitrodipyrido[3,2-a:20,30-c]phenazine-
j2-N,N’)tin(IV) (4, C26H27Cl2N5O2Sn)
3
Following the same procedure for the preparation of 2, a
solution of 100 mg ndppz (0.31 mmol) was reacted with
93 mg Sn(n-Bu)2Cl2 (0.31 mmol) to afford a brown solid.
The solid was recrystallized from CH2Cl2/diethyl ether.
1
Yield: 73%; m.p.: 188 °C; H NMR (CDCl3): d = 0.69 (t,
6H, 3J(HH) = 7.3 Hz, CH3), 1.12 (m, 4H, 3J(HH) =
7.4 Hz, CH2CH3), 1.48 (m, 4H, 3J(HH) = 8.0 Hz,
SnCH2CH2), 1.64 (m, 4H, 3J(HH) = 7.2 Hz, SnCH2),
8.16 (m, 2H, 3J(HH) = 4.8 Hz, H2,7), 8.62 (d, 1H,
Acknowledgments We thank the Science Research Council of K.N.
Toosi University of Technology for financial support.
3
3J(HH) = 9.2 Hz, H13), 8.77 (dd, 1H, J(HH) = 9.2 Hz,
References
4J(HH) = 2.2 Hz, H12), 9.36 (d, 1H, 4J(HH) = 2.0 Hz,
3
H10), 9.81 (br, 2H, H1,8), 9.93 (m, 2H, J(HH) = 6.3 Hz,
1. Davies NA, Dillon KB, Harris RK, Hewitson GF, Toms L (1994)
Polyhedron 13:19
H3,6) ppm.
123

B. Z. Momeni et al.
2. Momeni BZ, Shahbazi S, Khavasi HR (2010) Polyhedron
29:1393
3. Momeni BZ, Rominger F, Hosseini SS (2009) Acta Crystallogr
Sect E 65:m690
4. Buntine MA, Hall VJ, Kosovel FJ, Tiekink ERT (1998) J Phys
Chem A 102:2472
5. Crowe AJ, Smith PJ, Atassi G (1984) Inorg Chim Acta 93:179
6. Crowe AJ, Smith PJ, Cardin CJ, Parge HE, Smith FE (1984)
Cancer Lett 24:45
17. McGrady MM, Tobias RS (1965) J Am Chem Soc 87:1909
18. Bardi R, Piazzesi A, Ettorre R, Plazzogna G (1984) J Organomet
Chem 270:171
19. Hillebrand S, Bruckmann J, Kru¨ger C, Haenel MW (1995) Tet-
rahedron Lett 36:75
20. Aucott SM, Slawin AMZ, Woollins JD (2000) J Chem Soc
Dalton Trans 2559
21. Aucott SM, Slawin AMZ, Woollins JD (1997) Phosphorus. Sulfur
Silicon Relat Elem 124:473
7. Van Den Berghe E, Van Der Kelen GP (1968) J Organomet
Chem 11:479
8. Yoder CH, Mokrynka D, Coley SM, Otter JC, Haines RE,
Grushow A, Ansel LJ, Hovick JW, Mikus J, Shermak MA,
Spencer JN (1987) Organometallics 6:1679
9. Lo KM, Das VGK, Ng SW (1999) Acta Crystallogr Sect C 55:1058
10. Cunningham D, Landers EM, McArdle P, Chonchubhair NN
(2000) J Organomet Chem 612:53
11. Pettinari C, Pellei M, Marchetti F, Santini C, Miliani M (1998)
Polyhedron 17:561
22. Ainscough EW, Peterson LK (1970) Inorg Chem 9:2699
23. Pettinari C, Marchetti F, Cingolani A, Pettinari R, Drozdov A,
Troyanov S (2001) Inorg Chim Acta 312:125
24. Yoder CH, Otter JC, Grushow A, Ganunis TF, Enders BG, Zafar
AI, Spencer JN (1990) J Organomet Chem 385:33
25. Das VGK, Chee-Keong Y, Smith PJ (1987) J Organomet Chem
327:311
26. Crowe AJ, Smith PJ (1982) J Organomet Chem 224:223
27. de Alencastro RB, Bomfim JAS, Filgueiras CAL, Howie RA,
Wardell JL (2005) Appl Organomet Chem 19:479
28. Choi C-S, Mutai T, Arita S, Araki K (2000) J Chem Soc Perkin
Trans 2:243
12. Calderazzo F, Marchetti F, Pampaloni G, Passarelli V (1999) J
Chem Soc Dalton Trans 4389
13. Garoufis A, Koutsodimou A, Raptopoulou CP, Simopoulos A,
Katsaros N (1999) Polyhedron 18:3005
14. Casella G, Ferrante F, Saielli G (2008) Inorg Chem 47:4796
15. Lockhart TP, Manders WF (1986) Inorg Chem 25:892
29. Stoe F, Cie X (2009) X-AREA: program for the acquisition and
analysis of data, V 1.52. Stoe & Cie GmbH, Darmstadt
30. Blessing RH (1995) Acta Crystallogr Sect A 51:33
31. Sheldrick GK (2008) Acta Crystallogr Sect A 64:112
32. Spek AL (2009) Acta Crystallogr Sect D 65:148
ˇ ´ ´ˇ
16. Holecek J, Nadvornık M, Handlır K, Lycka A (1986) J Organo-
met Chem 315:299
´
ˇ
123