Stabilizing, non-covalent interactions in the solid state structure of novel aryltin hydrides and halogenides

Article abstract of DOI:10.1139/cjc-2013-0503

A group of novel aryltin chlorides, bromides and hydrides (Ar _nSnY_4-n) (Ar = o-tolyl, 2,6-xylyl, 1-naphthyl, 2-naphthyl, p-n-butylphenyl; Y = Cl, Br, H) have been synthesized and structurally characterized via X-ray diffraction.These compounds display noncovalent intermolecular interactions in the form of edge to face, π-π stacking and C-H···π interactions resulting in discrete arrangements in the solid state.The strength of these interactions and their effect on resulting structural parameters, as well as the consequence of the aromatic substituent on the type of interactions present, will be highlighted and discussed.

Full text of DOI:10.1139/cjc-2013-0503

556
ARTICLE
Stabilizing, non-covalent interactions in the solid state
structure of novel aryltin hydrides and halogenides
Cathrin Zeppek, Roland C. Fischer, Ana Torvisco, and Frank Uhlig
Abstract: A group of novel aryltin chlorides, bromides and hydrides (ArnSnY4-n) (Ar = o-tolyl, 2,6-xylyl, 1-naphthyl, 2-naphthyl,
p-n-butylphenyl; Y = Cl, Br, H) have been synthesized and structurally characterized via X-ray diffraction. These compounds
display noncovalent intermolecular interactions in the form of edge to face, ␲–␲ stacking and C–H···␲ interactions resulting in
discrete arrangements in the solid state. The strength of these interactions and their effect on resulting structural parameters,
as well as the consequence of the aromatic substituent on the type of interactions present, will be highlighted and discussed.
Key words: aryltin halides, aryltin hydrides, crystal packing motifs, intermolecular interactions, ␲–␲ stacking.
Résumé : De nouveaux chlorures, bromures et hydrures d’arylétain (ArnSnY4-n) (où Ar = o-tolyl, 2,6-xylyl, 1-naphthyl, 2-naphthyl
ou p-n-butylphenyl, et Y = Cl, Br ou H) ont été synthétisés et leur structure été déterminée par cristallographie aux rayons X. Ces
composées présentent des interactions intermoléculaires non covalentes de type bord-face, empilement ␲ et C–H···␲, qui
conduisent a` des arrangements distincts a` l’état solide. La force de ces interactions, leur effet sur les caractéristiques structurelles
qui en résultent et l’impact du substituant aromatique sur les types d’interaction présents, seront exposés et étudiés. [Traduit par
la Rédaction]
Mots-clés : halogénure d’arylétain, hydrure d’arylétain, motifs d’un empilement cristallin, interactions intermoléculaires, em-
pilement ␲.
their presence and ultimately their effect on aryltin species have
never been studied.
Introduction
The synthesis and detailed characterization of various tetraaryl
In an effort to expand the existing library of compounds and
stannanes (Ar4Sn) exhibiting aliphatic substituents on the aro-
study the underlying factors leading to solid state structures, we
matic ring via a Grignard reaction pathway has been well estab-
present a series of novel tetraaryl stannanes (1–3) and aryltin
lished.1–2 These compounds serve as starting materials for the
generation of aryltin halogenides (ArnSnX4-n), which themselves
act as major precursors for the formation of highly oxygen and
temperature labile aryltin hydrides (ArnSnH4-n). Hence, the major-
halogenides (4–7) with aryl substituents ranging in steric demand
from o-tolyl to naphthyl. In addition, a novel aryltin monohydride
species 2,6-xylyl3SnH (8) is presented. The types of noncovalent
interactions present in these systems will be highlighted and com-
ity of reported crystallographically studied aryl substituted tin
pared to previously reported compounds. In addition, the nature
species have been tetraaryl stannanes3–9 and aryltin monochlo-
of the aromatic substituent and its direct effects on the type of
rides10–19 and dichlorides.20–27 However, solid state examples of
electrostatic interaction that arises in these structures will be
trichlorides are limited, and the only aryltin hydride species to
have been characterized crystallographically is Mes2SnH2 (Mes =
2,4,6-trimethylphenyl).28 Very recently, we reported the synthe-
discussed.
Results and discussion
sis, detailed characterization, and DFT studies of novel aryltin
chloride and hydride species.2 Their potential use as starting ma-
terials for polyarylstannanes provided the motivation to establish
the generation of aryltin trihydrides displaying a hitherto more or
less neglected compound class of organotins. On the way towards
these crucial starting materials, we were able to generate a large
variety of aromatic tin compounds as well as elucidating their
solid state structure via single crystal X-ray crystallography. While
not previously mentioned in literature, tetraaryl stannanes, aryltin
chlorides, bromides, and hydrides exhibit noncovalent interac-
tions in the solid state, stemming from the aromatic substituents.
The role of aromatic noncovalent interactions in the stabilization
of compounds in solid state and their importance in chemical and
biological processes have been well documented.29–33 However,
Synthesis
For the generation of aryltin halogenides and hydrides (4–9),
the corresponding tetraaryl stannane (1–3) was synthesized first
and then used for all further conversions (Scheme 1). In each case,
the commercially available arylbromide was converted into the
Grignard reagent in THF or Et2O, respectively, and subsequently
treated with SnCl4 to generate the corresponding tetraaryl stan-
nane (Ar4Sn).1 The synthesis of tetraaryl stannanes as well as their
use as precursors in the generation of aryltin halogenides and
hydrides have been well established.1–2 In the case of the sterically
demanding 2,6-xylyl aryl residue, the formation of 2,6-xylyl4Sn
was not observed, and 2,6-xylyl3SnBr (4) was isolated. This halogen
interchange has also been described for the preparation of sterically
Received 31 October 2013. Accepted 26 January 2014.
C. Zeppek, R.C. Fischer, A. Torvisco, and F. Uhlig. TU Graz, 6330 Institut für Anorganische Chemie, 8010 Graz, Stremayrgasse 9/IV, Austria.
Corresponding author: Ana Torvisco (e-mail: ana.torviscogomez@tugraz.at).
This article is part of a Special Issue commemorating the 14th International Conference on the Coordination and Organometallic Chemistry of Germanium, Tin, and Lead
(ICCOC-GTL 2013) held in Baddeck, NS, July 2013.
Can. J. Chem. 92: 556–564 (2014) dx.doi.org/10.1139/cjc-2013-0503
Published at www.nrcresearchpress.com/cjc on 4 February 2014.

Zeppek et al.
557
Scheme 1. General synthetic scheme towards tetraaryl stannanes and aryltin derivatives.
encumbered species of mesityl tin compounds.34 Isolation of
the different aryltin species as well as optimization of the re-
action conditions to get a single product were not necessary, be-
cause the mixtures were treated with excess SnCl4 to generate the
desired aryltin trichlorides (5–7), according to the Kozeshkov
equilibrium.35–38
To obtain the aryltin hydride species (Ar3SnH 8, ArSnH3 9), the
respective aryltin monobromide and trichloride were subjected to
a hydrogenation reaction in Et2O with an excess of LiAlH4 (lithium
aluminum hydride) as described in literature.39 Compounds 2,6-
Xylyl3SnH (8) and p-n-butylphenylSnH3 (9) were generated at 0 and
–30 °C, respectively, and isolated by gently removing the solvent
under reduced pressure. Afterwards, liquid aryltin hydrides were
distilled at room temperature (RT) using a turbomolecular pump,
and solid hydrides were recrystallized. The thermal instability of
organotin hydrides, as well as the affinity towards oxygen, is re-
ported to increase with replacement of each organic group by a
hydrogen atom.40 As a result, p-n-butylphenylSnH3 (9) is a very
unstable liquid, sensitive towards high temperature and oxygen
and is stored at –80 °C under inert conditions like other reported
tin trihydrides.2,41
noncovalent interactions in the solid state through the aromatic
substituents. These stabilizing interactions are described and
compared to those present in previously reported species. In ad-
dition, interactions for model aromatic systems (benzene, tolu-
ene, naphthalene) are included for comparison.
Tetraaryl stannanes (1–3)
Compounds 1-naphthyl4Sn (1), 2-naphthyl4Sn (2), and p-n-
butylphenyl4Sn (3) are comparable to previously reported tetraaryl
stannanes (Table 2). Each Sn atom is in a near tetrahedral environ-
ment with C-Sn-C angles ranging from 107°–114°. With respect to
averaged Sn–C bonds, these fall within a narrow range of 2.13–
2.15 Å and are not affected by the degree of bulkiness caused
by the organic substituent on Sn. In most cases and as seen for
phenyl4Sn,3 tetraaryl stannanes crystallize in high symmetry
space groups, mainly tetragonal, and display highly ordered pack-
ing motifs. These consist of columns of symmetry related mole-
cules. This packing motif is also seen in 2-naphthyl4Sn (2) (Fig. 2),
which crystallizes in the I-4 space group. For this compound, each
of these columns consists of interlocking neighbouring molecules
by edge to face interactions (2.50 Å) through the naphthyl sub-
stituents (Table 2). These values fall within range for edge to face
interactions found in biological and organic systems (2.4–3.1 Å).29–30
While not reported in literature, slightly longer interactions on
average are observed for phenyl4Sn (2.95 Å). In the case of
1-naphthyl4Sn (1), which crystallizes in the monoclinic space
group P21/n, discrete column formation is not observed in agree-
ment with the lower symmetry. This results in the molecules
orienting themselves to maximize interactions between neigh-
bouring molecules, and numerous edge to face interactions
ranging from 2.53–2.95 Å are observed. 1-Naphthyl4Sn (1) and 2-
naphthyl4Sn (2) compare well with the herringbone packing
structure of naphthalene, which also exhibits edge to face inter-
actions (2.81 Å).43
Introduction of n-butyl groups in the para position of the phen-
yl substituent in p-n-butylphenyl4Sn (3) results in crystallization in
the low symmetry space group P-1. This is due to the higher degree
of rotation of the n-butyl groups, compared to the t-butyl groups of
p-t-butylphenyl4Sn,9 which is tetragonal (P42/n). In addition to the
presence of edge to face interactions (2.96 Å) in compound 3,
C–H···␲ interactions are observed between the methylene hy-
drogens of the butyl substituents and the phenyl groups of neigh-
bouring molecules (2.91 Å) (Table 2). However, despite the potential
for the t-butyl group in p-t-butylphenyl4Sn for C–H···␲ interactions,
only an edge to face interaction (2.98 Å) is observed between the
phenyl substituents of neighbouring molecules.
119Sn NMR Spectroscopy
Table 1 summarizes 119Sn NMR shifts of all included compounds
(1–9) measured in C6D6 as well as published shifts of substituted
triaryltin bromides and phenylnSnY4-n (Y = Cl, Br, H) species for
comparison. For the aryltin chloride species (ArnSnCl4-n), an in-
crease in number of chlorines results in a lower shielding of the
119Sn nucleus, thus in a high field shift in 119Sn NMR, which has
recently been extensively studied.2 In this manner, the listed
shifts fall in an expected range according to the number of
halogens or hydrogens bonded to the tin. 119Sn shifts of the pre-
sented tetraaryl stannanes lie between –118 to –122 ppm, whereas
aryltin chlorides are high field shifted (–58 to –64 ppm). Triaryltin
bromides show an increased high field shift in comparison to
their corresponding chlorides, as seen for Ph3SnCl (–45 ppm,
CDCl3) and Ph3SnBr (–60 ppm, CDCl3).42 In addition, aryl moieties
exhibiting methyl substitution in both ortho positions of the ar-
omatic ring bonded to the Sn lead to high field shift increases in
comparison to the nonsubstituted phenyl derivative (phenylnSnY4-n).
This effect has been described in detail for the 2,6-xylyl and mesi-
tyl residue and is explained by hyperconjugation, which causes
the Sn atom to exhibit a slightly higher electron density.2 The
compound 2,6-xylyl3SnBr (4) shows the lowest shift for all re-
ported triaryltin bromides.
Crystallographic studies
The presence of aromatic secondary interactions and their im-
portance as stabilizing factors for these aryltin derivatives in the
solid state has been rarely discussed or simply overlooked. Specif-
ically, interactions attributed to the aromatic substituents includ-
ing ␲–␲ stacking, edge to face, or C–H···␲ interactions have been
neglected. Figure 1 summarizes the types of aromatic noncovalent
interactions and acceptable ranges found in biological and or-
ganic systems.29–31 All novel aryltin compounds presented display
Aryltin hydrides and bromides (4, 8)
While compounds 1 and 2 show a propensity towards edge to
face interactions due to the nature of the naphthyl moiety, addi-
tion of methyl groups on the aryl substituent of Sn should lead to
C–H···␲ interactions being preferred in packing motifs. This is
indeed the case for 2,6-xylyl3SnBr (4) and 2,6-xylyl3SnH (8), where
the molecules in the solid state arrange themselves to maximize
these interactions (Table 3). It should be noted that Aryl3SnCl
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558
Can. J. Chem. Vol. 92, 2014
Table 1. 119Sn NMR shifts (C6D6) of all included compounds.
119Sn NMR
shift (ppm)
119Sn NMR
shift (ppm)
Compound
Compound
Aryl4Sn
ArylSnCl3
phenylSnCl3
2
phenyl4Sn2
−127
−119
−118
−122
−61
−61
−64
−58
1-naphthyl4Sn (1)
2-naphthyl4Sn (2)
p-n-butylphenyl4Sn (3)
Aryl3SnBr
o-tolylSnCl3 (5)
2-naphthylSnCl3 (6)
p-n-butylphenylSnCl3 (7)
Aryl3SnH
phenyl3SnBr1
o-tolyl3SnBr1
−60a
−54a
−57a
−52a
−132
−121a
phenyl3SnH2
2,6-xylyl3SnH (8)
ArylSnH3
−163
−287
m-tolyl3SnBr1
p-tolyl3SnBr42
2,6-xylyl3SnBr (4)
mesityl3SnBr1
2
phenylSnH3
p-n-butylphenylSnH3 (9)
−345
−345
ameasured in CDCl3.
Fig. 1. Orientations of aromatic noncovalent interactions and
accepted ranges.29–31
an elongated Sn–Br bond in 2,6-xylyl3SnBr (4) and mesityl3SnBr
(2.547(1) Å), compared to phenyl3SnBr (2.495(2) Å). While 2,6-
xylyl3SnBr (4) does not exhibit any edge to face interactions
within acceptable ranges, the lack of methyl groups in Ph3SnBr
allows for very close contacts (2.63–3.14 Å).
Synthetic applications for triorgano tin hydrides (R3SnH) are a
well investigated field in organometallic and organic synthesis,
especially in mediating radical additions, rearrangement and
elimination reactions.47 Furthermore in the last decade, organo-
tin dihydrides (R2SnH2) have been explored as precursors in the
formation of polymeric materials exhibiting a linear backbone
of covalently bonded tin atoms.28,48–49 However, the solid state
structures of organotin hydrides have not been well studied.
While alkyl tin hydrides are liquid, the only solid state examples
of aryltin hydrides known to date have been isolated by our work-
ing group and include mesityl2SnH2,28 phenyl3SnH,44 and 2,6-
xylyl3SnH (8) (Table 3). As mentioned above, presence of methyl
groups at the 2- and 6-position of the aryl substituent results in a
slight increase of the average Sn–C bond length in 2,6-xylyl3SnH
(2.159(5) Å) and mesityl2SnH2 (2.154(9) Å), compared to phenyl3SnH
(2.141(4) Å). In the case of 2,6-xylyl3SnH, Sn–H was not reliably
located in the difference map, which is a common problem with
light atoms (hydrogen) located next to heavy atoms because of
their poor scattering abilities. For mesityl2SnH2,28 which is a di-
hydride, Sn–H bonds are on average 1.669(2) Å. In phenyl3SnH,44
the hydrogen at the tin atom was located in the difference map
exhibiting the first experimental Sn–H bond length for a monos-
tannane (1.13(5) Å).
Table 2. List of Sn−C bond lengths and noncovalent interactions for
selected tetraaryl stannanes and model aromatic systems.
Space
Sn−C (Å) Edge to
group (avg.)
face (Å)
C−H···␲ (Å)
phenyl4Sn3
o-tolyl4Sn4
P-421c
P-421c
I41/a
I-4
P-421c
P-1
2.139(5)
2.86−3.14
—
3.13
2.78
—
3.07
3.21
2.96
2.98
2.53−2.95
2.50−3.15
2.84
2.78
2.81
—
3.36
—
3.22
3.39
2.95−3.39
3.24
2.91
—
—
—
—
2.61
—
2.152(5)
2.150(3)
2.147(6)
2.134(5)
2.139(2)
2.129(4)
2.137(2)
2.138(5)
2.154(6)
2.145(7)
—
m-tolyl4Sn5
p-tolyl4Sn6
3,5-xylyl4Sn7
2,4-xylyl4Sn8
p-ethylphenyl4Sn9
C2/c
p-n-butylphenyl4Sn (3) P-1
p-t-butylphenyl4Sn9
1-naphthyl4Sn (1)
2-naphthyl4Sn (2)
benzene33
P42/n
P21/n
I-4
Pbca
P21/c
P21/a
Nevertheless, packed structures of 8 (Fig. 4) reveal staggered
chains of alternating edge to face (2.87 Å) and C–H···␲ interactions
(2.70–2.81 Å). The lack of these methyl substituents on phenyl3SnH
results exclusively in the presence of edge to face interactions,
however, an additional Sn–H···␲ interaction, 3.092(3) Å, is ob-
served.44 In mesityl2SnH2, only C–H···␲ interactions ranging from
2.70 and 2.75 Å are observed.
toluene33
—
—
naphthalene43
species are better studied and therefore not included in these
discussions.10–13,15 As shown in Fig. 3, molecules of compound
2,6-xylyl3SnBr (4) are arranged in a staggered formation creating
chains propagated through C–H···␲ interactions (2.78 Å) from a
methyl group and a neighbouring 2,6-xylyl substituent. These in-
teractions are well within range for reported C–H···␲ interactions
(2.3–3.4 Å).29 These latter are also visible in the solid state packing
motif for toluene,33 which in addition to edge to face interactions
(2.78 Å), exhibits closer C–H···␲ interactions from the methyl
group (2.61 Å) (Table 2). While no Sn–Br interactions were seen
between neighbouring molecules, the closest distances being well
over 8 Å, C–H···Br interactions were observed (3.03–3.10 Å) be-
tween chains. Compared to phenyl3SnBr (2.114(8) Å), a slight in-
crease in the average Sn–C bond lengths is seen for 2,6-xylyl3SnBr
(4) (2.164(8) Å) and mesityl3SnBr (2.169(5) Å), consistent with in-
creased steric bulk around the Sn center due to the methyl groups
at the 2- and 6-positions of the aryl substituent (Table 3). This
increased steric bulk around the Sn center is also manifested by
Aryltin trichlorides (5, 6)
Until a recent contribution from this working group,2 only two
examples of structurally characterized aryl trichloro stannanes
had been reported in literature (Table 4).50–51 The compounds
(2,6-Mes)PhSnCl3 (Mes = (2,4,6-Me)Ph) and Ph*SnCl3 (Ph* = (2,6-
Trip)Ph, Trip = (2,4,6-iPr)Ph) employ sterically hindered substitu-
ents containing methylated aryl moieties on the phenyl substituents
and only exhibit C–H···␲ interactions (Table 4). More recent exam-
ples include methyl-substituted phenyl and naphthyl derivatives.
In the case of 1-naphthylSnCl32and 2-naphthylSnCl3 (6), large de-
viations from Sn–C or Sn–Cl bond lengths are not observed.
However, the naphthyl derivatives display much different crystal
packing motifs than for the aforementioned bulkier substituents.
In both 1-naphthylSnCl3 and 2-naphthylSnCl3 (6) (Fig. 5), the
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Zeppek et al.
559
Fig. 2. Crystal packing diagram for 2-naphthyl4Sn (2). Edge to face interactions are highlighted by dashed bonds. All non-carbon atoms shown
as 30% shaded ellipsoids. Hydrogen atoms not involved in intermolecular interactions removed for clarity.
Table 3. List of Sn−C bond lengths and noncovalent interactions for selected aryl tin hydrides and bromides.
Space
group
Sn−C (Å)
(avg)
Sn−X (Å)
(avg)
Edge to
face (Å)
C−H···␲ (Å)
C−H···Br (Å)
Sn−H···␲ (Å)
phenyl3SnH44
P21/c
P-1
C2/c
P21/c
P21/c
P-1
2.141(4)
2.159(5)
2.154(9)
2.114(8)
2.164(8)
2.169(5)
1.13(5)
—
1.669(2)
2.495(2)
2.547(3)
2.547(1)
2.78
2.87
—
2.63−3.14
—
—
—
—
—
3.092(3)
2,6-xylyl3SnH (8)
2.70−2.81
2.70−2.75
—
2.78
3.01
—
—
—
—
—
28
mesityl2SnH2
phenyl3SnBr45
2,6-xylyl3SnBr (4)
mesityl3SnBr46
3.03
3.03−3.10
2.96
3.17
Fig. 3. Crystal packing diagram for 2,6-xylyl3SnBr (4). C–H···␲ interactions are highlighted by dashed bonds. All non-carbon atoms shown as
30% shaded ellipsoids. Hydrogen atoms not involved in intermolecular interactions removed for clarity.
naphthyl substituents show a large propensity towards ␲–␲ stack-
ing. In each case, molecules arrange to maximize these interac-
tions, creating infinite layers of parallel stacked naphthalene
derivatives with a specific distance between the ring centers (d).
They are also found to be parallel-displaced to each other with a
certain offset (R). This is in stark contrast to the previously men-
tioned herringbone structure present for naphthalene, which is
dominated by edge to face interactions and corresponds more to
larger polycyclic aromatic molecules, such as coronene, kekulene,
or graphite.29,52 1-NaphthylSnCl3 and 2-naphthylSnCl3 (6) show
similar interplanar distances of 3.56 and 3.54 respectively. These
findings are in accordance with a reported range of 3.4–3.6 Å for
benzene29 or 3.35 Å in graphite.52 2-NaphthylSnCl3 (6) shows a
slightly larger displacement (R) of 1.76 Å. Offset distances for other
benzyl systems are found in the range 1.6–1.8 Å.29 In addition to
␲–␲ stacking, C–H···Cl interactions were observed between lay-
ers for both compounds (Table 4). If the number of naphthyl
substituents is increased as seen in 1-naphthyl2SnCl2 (Fig. 6) and 2-
naphthyl2SnCl2 (6), ␲–␲ stacking in the solid state is maintained,
however, infinite linear chains are formed between neighbouring
molecules.2 1-Naphthyl2SnCl2 shows an interplanar distance (d) of
3.60 Å, while 2-naphthyl2SnCl2 is packed slightly tighter with a
distance of 3.40 Å.
Also exhibiting close ␲–␲ stacking interactions (d = 3.46, R =
1.65 Å) in the solid state is o-tolylSnCl3 (5), which is a low temper-
ature melting solid (4 °C), and subsequently obtaining a suitable
solid state structure proved challenging (Table 4). Crystal packing
diagrams of o-tolylSnCl3 (5) display neighbouring molecules posi-
tioned to maximize C–H···␲ interactions from methyl groups
(2.89 Å), while allowing ␲–␲ stacking interactions (Fig. 7). If methyl
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560
Can. J. Chem. Vol. 92, 2014
Fig. 4. Crystal packing diagram for 2,6-xylyl3SnH (8). Edge to face and C–H···␲ interactions are highlighted by dashed bonds. All non-carbon
atoms shown as 30% shaded ellipsoids. Hydrogen atoms not involved in intermolecular interactions removed for clarity.
Table 4. List of Sn−C bond lengths and noncovalent interactions for aryltin tri- and dichlorides.
Parallel
displaced (Å)
Space
group
Sn−C (Å)
(avg)
Sn−Cl (Å)
(avg)
Edge to
face (Å)
d
R
C−H···␲ (Å)
C−H···Cl (Å)
o-tolylSnCl3 (5)
2,6-xylylSnCl3
P-1
2.109(4)
2.123(2)
2.128(6)
2.155(5)
2.114(11)
2.097(3)
2.118(2)
2.106(8)
2.132(2)
2.332(1)
2.332(1)
2.315(2)
2.324(3)
2.306(7)
2.359(1)
2.354(19)
3.46
—
—
1.65
—
—
—
—
3.04
—
—
—
—
—
2.89
2.74
2.90
3.15
—
—
—
—
2.95
2.91
2.79
—
2.90
2.86
3.12
2.91
2
Pbcn
P21/c
P-1
P21/c
Pnma
P2/n
P21/n
50
(2,6-Mes)PhSnCl3
51
phenyl*SnCl3
—
—
2
1-naphthylSnCl3
2-naphthylSnCl3 (6)
1-naphthyl2SnCl2
2-naphthyl2SnCl2
3.56
3.54
3.60
3.40
1.63
1.76
1.42
1.67
2
2
Note: Mes = (2,4,6-Me)Ph; phenyl* = (2,6-Trip)Ph, Trip = (2,4,6-iPr)Ph.
Fig. 5. Crystal packing diagram for 2-naphthylSnCl3 (6). ␲–␲ stacking and C–H···Cl interactions are highlighted by dashed bonds. All non-
carbon atoms shown as 30% shaded ellipsoids. Hydrogen atoms not involved in intermolecular interactions removed for clarity.
substitution is increased as seen for 2,6-xylylSnCl3, only C–H···␲ in-
teractions are present(2.74 Å).2 It should be noted that o-tolylSnCl3
Conclusions
A series of novel organotin species containing methyl or n-butyl
displays the shortest Sn–Cl bond (2.132(2) Å) due to the lower steric
hindrance afforded to the Sn atom by the o-tolyl substituent, com-
pared to 2,6-xylylSnCl3 (2.123(2) Å).
substituted phenyl and naphthyl residues have been synthesized
and fully characterized by NMR spectroscopy and X-ray crystallog-
raphy. In addition, the presence and nature of noncovalent inter-
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Zeppek et al.
561
Fig. 6. Crystal packing diagram for 1-naphthyl2SnCl2.2 ␲–␲ stacking interactions are highlighted by dashed bonds. All non-carbon atoms
shown as 30% shaded ellipsoids. Hydrogen atoms not involved in intermolecular interactions removed for clarity.
Fig. 7. Crystal packing diagram for o-tolylSnCl3 (5). C–H···␲ and ␲–␲
stacking interactions are highlighted by dashed bonds. All non-
Experimental
carbon atoms shown as 30% shaded ellipsoids. Hydrogen atoms not
involved in intermolecular interactions removed for clarity.
Materials and methods
All reactions, unless otherwise stated, were carried out using
standard Schlenk line techniques under nitrogen atmosphere. All
dried and deoxygenated solvents were obtained from a solvent
drying system (Innovative Technology Inc). SnCl4 anhydrous (98%
v/v) was purchased at Alfa Aesar, distilled and stored under ni-
trogen. C6D6 was distilled over sodium and stored under nitrogen.
All other chemicals from commercial sources (arylbromides and
Ph3SnCl) were utilized without further purification. All starting
compounds, tetraaryl stannanes (Ar4Sn) (1–3), were obtained ac-
cording to published procedures; however, the work up proce-
dure for p-butylphenyl4Sn (3) was modified.2,53 2,6-Xylyl3SnBr (4)
was generated as the main product in the attempted synthesis of
the corresponding tetraaryl stannane, as already mentioned in
literature.34 All aryltin trichlorides (5–7) were synthesized follow-
ing the literature procedure via a Kozeshkov redistribution reac-
tion.35,37–38 Aryltin monohydride and trihydride were generated
according to the preparation method of Finholt, Bond, and
Schlesinger in Et2O using lithium aluminum hydride (LiAlH4) as
reducing agent.39 For already published compounds, only 1H, 13C,
and 119Sn NMR are provided. Elemental analysis was performed
with an Elementar Vario EL III. Melting point measurements were
carried out by three-fold determination with a Stuart Scientific
SMP 10 (up to 300 °C).
actions in the solid state of the presented compounds was studied
and compared to those existing but never mentioned and simply
overlooked in literature. Three different types of aromatic, non-
covalent interactions could be detected, including the most prom-
inent edge to face interaction, a parallel displaced ␲–␲ stacking as
well as a C–H···␲ interaction of methyl groups to the neighbouring
ring system. Edge to face interactions are found in the solid state
structure of all presented organotins, mostly in the presence of
additional interactions bringing about typical packing motifs.
However, the discussed tetraarylstannanes 1-naphthyl4Sn (1) and
2-naphthyl4Sn (2) exclusively display edge to face interactions as
stabilizing elements in the solid state. Substitution with aliphatic
chains to the aromatic ring, as seen for p-n-butylphenyl4Sn (3),
results in both edge to face intermolecular and C–H···␲ interac-
tions. 2-NaphthylSnCl3 (6) and similar naphthyl tin mono- and
dichlorides arrange themselves in the solid state to accommodate
␲–␲ stacking interactions through the naphthyl substituents
of neighbouring molecules. Onefold and twofold methyl substitu-
tion in the ortho positions of the phenyl ring, in the case of
o-tolylSnCl3 (5) and 2,6-xylylSnCl3, give rise to the coexistence of
␲–␲ stacking interactions through the aromatic rings as well as
C–H···␲ interactions through the methyl groups and the aromatic
rings of neighbouring substituents as stabilizing factors. Fi-
nally, the solid state structures of the novel tin monohydride
2,6-xylyl3SnH (8) and monobromide 2,6-xylyl3SnBr (4) presented,
exhibit both edge to face intermolecular as well as C–H···␲ inter-
actions.
NMR spectroscopy
1H (300.22 MHz), 13C (75.5 MHz), and 119Sn (111.92 MHz) NMR
spectra were recorded on a Mercury 300 MHz spectrometer from
Varian at 25 °C. Chemical shifts are given in parts per million
(ppm) relative to TMS (␦ = 0 ppm) regarding 13C and 1H and relative
to SnMe4 in the case of 119Sn. Coupling constants (J) are reported in
Hertz (Hz). All NMRs were taken in C6D6. Reactions were moni-
tored via 119Sn NMR using a D2O capillary as external lock signal.
For complete peak assignment, multinuclear NMR experiments
were also carried out (H,H-COSY and C,H-HETCOR) as well as shift
comparisons to already known and similar compounds in litera-
ture were made.2,54–55
Crystal structure determination
All crystals suitable for single crystal X-ray diffractometry were
removed from a Schlenk flask and immediately covered with a
layer of silicone oil. Due to the low melting point of 4 °C for
o-tolylSnCl3 (7), the compound was recrystallized neat in the
fridge and placed in silicon oil cooled down with dry ice. A single
crystal was selected, mounted on a glass rod on a copper pin, and
placed in the cold N2 stream provided by an Oxford Cryosystems
cryometer. XRD data collection was performed for compounds
1–6 and 8 on a Bruker Apex II diffractometer, with use of Mo K␣
radiation (␭ = 0.71073 Å) and a CCD area detector. Empirical ab-
sorption corrections were applied using SADABS.56 The structures
Published by NRC Research Press

562
Can. J. Chem. Vol. 92, 2014
Table 5. Crystallographic data and details of measurements for compounds 1–6 and 8.
Compound
1
2
3
4
5
6
8
Formula
Fw (g mol−1
a (Å)
b (Å)
c (Å)
C40H28Sn
627.31
11.0020(3)
12.3126(4)
21.3522(6)
90
90.789(1)
90
2892.16(15)
4
C40H28Sn
627.31
19.0493(17)
19.0493(17)
7.8388(8)
90
90
90
2844.5(6)
4
C40H52Sn
651.50
C24H27BrSn
514.05
7.9774(3)
18.6305(6)
14.5078(4)
90
94.680(1)
90
2149.00(12)
4
C7H7Cl3Sn
316.17
C10H7Cl3Sn
352.20
9.1965(3)
7.0776(2)
18.0394(5)
90
90
90
1174.17(6)
4
C24H28Sn
435.15
)
10.2809(3)
13.5926(4)
26.0182(8)
92.532(2)
96.022(2)
97.922(2)
3574.97(19)
4
7.1993(8)
8.6524(10)
17.4519(19)
76.418(3)
78.788(3)
81.902(4)
1031.4(2)
4
6.9415(4)
11.9714(7)
12.8316(8)
108.672(2)
91.291(2)
95.958(2)
1002.96(10)
2
␣ (°)
␤ (°)
␥ (°)
V (Å3)
Z
Crystal system
Monoclinic
P21/n
1.439
0.91
100(2)
Tetragonal
I-4
1.465
0.93
100(2)
Triclinic
P-1
1.210
0.74
100(2)
Monoclinic
P21/c
1.589
3.05
100(2)
Triclinic
P-1
2.036
3.19
100(2)
Orthorhombic
Pnma
1.992
2.82
100(2)
Triclinic
P-1
1.440
1.28
100(2)
Space group
d
calc (Mg/m3)
␮ (mm−1
T (K)
)
2␪ range (°)
F(000)
2.5–25.9
1272
2.8–27.6
1272
2.3–26.5
1368
2.6–26.8
1024
2.4–27.2
600
2.5–27.1
672
2.8–26.4
444
Rint
0.097
0.050
0.082
0.030
0.055
0.041
0.043
Independent reflns
No. of params
R1, wR2 (all data)a
5911
358
R1 = 0.1000
wR2 = 0.1406
R1 = 0.0597
wR2 = 0.1246
2833
185
R1 = 0.0429
wR2 = 0.0940
R1 = 0.0354
wR2 = 0.0893
15766
767
R1 = 0.0955
wR2 = 0.1195
R1 = 0.0535
wR2 = 0.1076
4448
241
R1 = 0.0250
wR2 = 0.0474
R1 = 0.0193
wR2 = 0.0452
4157
201
R1 = 0.0349
wR2 = 0.0865
R1 = 0.0347
wR2 = 0.0864
1397
82
R1 = 0.0232
wR2 = 0.0540
R1 = 0.0202
wR2 = 0.0522
4069
236
R1 = 0.0501
wR2 = 0.1275
R1 = 0.0480
wR2 = 0.1260
R1, wR2 (>2␴)b
Note: Mo K␣ (␭ = 0.71073 Å). R1 = Α/|Fo| − |Fc|/|Α|Fd; wR2 = [Αw(Fo2 −F22)2/Αw(Fo2)2]1/2
.
were solved using either direct methods or the Patterson option in
SHELXS, and refined by the full-matrix least-squares procedures in
SHELXL.57–58 Non-hydrogen atoms were refined anisotropically.
Hydrogen atoms were located in calculated positions correspond-
ing to standard bond lengths and angles. For compound 1, several
restraints and constraints (FRAG 17, AFIX 173) were used to afford
idealized naphthalene geometry for one of the naphthyl groups.
Disorder was handled by modeling the occupancies of the individ-
ual orientations using free variables to refine the respective occu-
pancy of the affected fragments. For compound 3, disorder on one
of the n-butyl groups was refined using 50/50 split positions. For
compound 8, the hydrogen atom bound to Sn was not found on
the difference map and residual electron density is attributed to
the heavy Sn atom. This is a common problem with locating light
atoms (hydrogen) next to heavy atoms because of their poor scat-
tering abilities. Intermolecular interactions for presented and
published compounds based on a Cambridge Structural Data-
base59 search were determined by the calculation of centroids and
planes feature of the programs Mercury60 and Diamond.61 Table 5
contains crystallographic data and details of measurements and
refinement for compounds 1–6 and 8 (also, please see Supplemen-
tary data).
product was suspended in Et2O, filtered, and washed with Et2O
and subsequently with pentane. The product was then dried in an
oven at 110 °C overnight. Alternatively, (b) H2O was added and
subsequently all of the solvent was removed under reduced pres-
sure. The resulting residue was taken up in pentane and refluxed
until all of the product dissolved. The suspension was filtered
again through celite and washed with pentane. The solvent was
removed under reduced pressure, and the resulting oil was dis-
tilled under reduced pressure. Instead, (c) H2O was added, and
subsequently all of the solvent was removed under reduced pres-
sure. The resulting residue was extracted with a soxhlet apparatus
for 2 h with pentane. The pentane was evaporated under reduced
pressure.
1-naphthyl4Sn (1)
17.0 g (700 mmol, 7 equiv.) Mg in 700 mL THF, 83.4 mL
(600 mmol, 6 equiv.) 1-bromonaphthalene in 150 mL THF, 11.7 mL
(100 mmol, 1 equiv.) SnCl4 in 1 L THF, work-up procedure (a):
1000 mL H2O, 250 mL Et2O, 250 mL Et2O, 250 mL pentane. For
analysis, a small amount was recrystallized from ethylacetate to
obtain colorless crystals. Yield: 72% (45.2 g, 72.0 mmol). M.p.:,
1
3
230–232 °C. H NMR (C6D6, 300 MHz): ␦ 8.33 (d, 4H, J(H4-H3) =
8.3 Hz, H4), 8.12 (d, 4H, 3J(H2-H3) = 6.6 Hz, H2), 7.62 (d, 4H, J(H8-
3
H7) = 8.2 Hz, H8), 7.54 (d, 4H, 3J(H5-H6) = 8.1 Hz, H5), 7.12–7.00 (m,
8H, H6, H7), 6.83 (dd, 2H, H3) ppm. 13C NMR (C6D6, 75.5 MHz): ␦
140.7 (1J(13C-119Sn) = 520 Hz, 1J(13C-117Sn) = 497 Hz, C1), 139.4 (2J(13C-
119Sn) = 34.7 Hz, 2J(13C-117Sn) = 33.8 Hz, C8a), 137.6 (2J(13C-119/117Sn) =
General procedure for Ar4Sn and 2,6-xylyl3SnBr (1–4)
A flask equipped with a dropping funnel and a reflux condenser
was charged with Mg in THF. The dropping funnel was charged
with arylbromide in THF. One mL of dibromoethane was added,
and the solution was heated to start the reaction. The arylbromide
was subsequently added slowly. After complete addition, the re-
action was refluxed for 2 h. A second flask equipped with a me-
chanical stirrer and a reflux condenser was charged with SnCl4 in
THF cooled with an ice bath. The Grignard solution was then
transferred via a cannula to the SnCl4 solution whilst hot to avoid
precipitation of the Grignard reagent. The solution was refluxed
for 2 h and stirred overnight at RT. Three possible work-up proce-
dures were carried out. In one case (a) the solution was filtered
through celite and the solvent evaporated under reduced pres-
sure. To the resulting residue, water was added and then extracted
with dichloromethane. The organic phase was dried over Na2SO4,
filtered, and the solvent evaporated under reduced pressure. The
38.1 Hz, C2), 134.5 (3J(13C-119Sn) = 37.6 Hz, J(13C-117Sn) = 36.4 Hz,
3
C4a), 130.6 (4J(13C-119/117Sn) = 32.2 Hz, C4), 130.3 (3J(13C-119/117Sn) =
11.7 Hz, C8), 129.3 (3J(13C-119/117Sn) = 43.8 Hz, C3), 126.4 (C7), 126.1
(C6) ppm. 119Sn NMR (C6D6, 112 MHz): ␦ –118.8 ppm. Anal. calcd. for
C20H14Sn: C, 76.58; H, 4.50. Found: C, 75.36; H, 4.40.
2-naphthyl4Sn (2)
3.2 g (131 mmol, 4.5 equiv.) Mg in 250 mL THF, 25.9 g (125 mmol,
4.3 eq.) 2-bromonaphthalene in 50 mL THF, 3.4 mL (29.1 mmol,
1 equiv.) SnCl4 in 500 mL of THF, work-up procedure (a): 250 mL l
H2O, 500 mL of dichloromethane, 100 mL Et2O, 100 mL of Et2O,
100 mL pentane. For analysis a small amount was recrystallized
from ethylacetate to obtain colorless crystals. Yield: 56% (10.2 g,
Published by NRC Research Press

Zeppek et al.
563
1
16.2 mmol). M.p.: 199–200 °C. H NMR (C6D6, 300 MHz): ␦ 8.14 (s,
H5), 6.81–6.76 (d, 1H, H3), 2.18 (s, 3H,4J(H7-119/117Sn) = 13.7 Hz,
H6) ppm. 13C NMR (C6D6, 75.5 MHz): ␦ 142.9 (2J(13C-119Sn) = 75.2 Hz,
2J(13C-117Sn) = 72.0 Hz, C2), 136.7 (1J(13C-119Sn) = 1085 Hz, 1J(13C-
117Sn) = 1036 Hz, C1), 134.4 (2J(13C-119Sn) = 77.8 Hz, 2J(13C-117Sn) =
74.4 Hz, C6), 133.3 (4J(13C-119/117Sn) = 23.9 Hz, C4), 131.6 (3J(13C-
119Sn) = 119 Hz, 3J(13C-117Sn) = 114 Hz, C3), 127.2 (3J(13C-119Sn) = 128 Hz,
3J(13C-117Sn) = 122 Hz, C5), 24.3 (3J(13C-119Sn) = 55.3 Hz, 3J(13C-117Sn) =
53.4 Hz, C7) ppm. 119Sn NMR (C6D6, 112 MHz): ␦ –60.7 ppm. Anal.
calcd. for C7H7Cl3Sn: C, 26.59; H, 2.23. Found: C, 26.12; H, 2.13.
4H, J(H1-119/117Sn) = 55.2 Hz, H1), 7.92 (d, 4H, J(H3-H4) = 8.2 Hz,
3
3
3J(H3-119/117Sn) = 40.7 Hz, H3), 7.75 (d, 4H, 3J(H4-H3) = 8.2 Hz,
4J(H4-119/117Sn) = 12.8 Hz, H4), 7.63 (d, 4H, J(H8-H7) = 7.8 Hz, H8),
3
7.45 (d, 4H, 3J(H5-H6) = 7.7 Hz, H5), 7.28–7.16 (m, 8H, H6, H7) ppm.
13C NMR (C6D6, 75.5 MHz): ␦ 138.7 (2J(13C-119Sn = 36.9 Hz, 2J(13C-117Sn =
35.4 Hz, C1), (1J(13C-119Sn = 529 Hz, J(13C-117Sn = 505 Hz, C2), 134.5
1
(4J(13C-119/117Sn = 9.9 Hz, C4a), 134.3 (3J(13C-119Sn = 57.8 Hz, 3J(13C-117Sn =
55.3 Hz, C8a), 133.7 (2J(13C-119Sn = 40.3 Hz, 2J(13C-117Sn = 38.7 Hz, C3), 128.6
(3J(13C-119Sn = 50.6 Hz, 3J(13C-117Sn = 48.3 Hz, C4), 128.3 (5J(13C-119/117Sn =
4.6 Hz, C5), 128.2 (C8), 126.8 (C6), 126.4 (5J(13C-119/117Sn = 4.3 Hz,
C7) ppm. 119Sn NMR (C6D6, 112 MHz): ␦ –117.6 ppm. Anal. calcd. for
C20H14Sn: C, 76.58; H, 4.50. Found: C, 76.64; H, 4.46.
2-naphthylSnCl3 (6)
3.71 g tetra-2-naphthyltin 2 (5.7 mmol, 1 equiv.), 1.99 mL SnCl4
(4.5 g, 17 mmol, 3 equiv.), 160 °C, work-up procedure (b) The re-
sulting solid was recrystallized from chloroform to obtain color-
less crystals. Yield: 90% (7.2 g, 20 mmol). M. p.: 82 °C. 1H NMR (C6D6,
300 MHz): ␦ 7.64 (s, 1H, 3J(H1-119Sn) = 135.4 Hz, 3J(H1-117Sn) =
134.9 Hz, H1), 7.40–7.31 (m, 2H, H4, H6), 7.28–7.23 (m, 2H, H5, H7),
p-n-butylphenyl4Sn (3)
14.3 g (0.59 mol, 5 equiv.) Mg in 270 mL THF, 100 g (0.47 mol,
equiv.) p-n-butylphenylbromide in 30 mL THF, 13.7 mL
4
3
(0.12 mmol, 1 equiv.) SnCl4 in 300 mL of THF, work-up procedure
(b): 10 mL of H2O to quench, refluxed in 800 mL of pentane,
washed with 50 mL pentane. The resulting solid was recrystallized
from n-BuOH in the fridge to obtain colorless crystals. Yield: 65%
(53.9 g, 83 mmol). M.p.: 42 °C. 1H NMR (C6D6, 300 MHz): ␦ 7.73 (d,
8H, 3J(H2-H3) = 7.80 Hz, 3J(1H-119Sn) = 48.1 Hz, 3J(1H-117Sn) = 45.7 Hz,
7.20–7.10 (m, 1H, H3), 7.04 (d, J(H8-H7) = 8.38 Hz, H8).13C NMR
(C6D6, 75.5 MHz): ␦ 136.0 (2J(13C-119Sn) = 74.6 Hz, 2J(13C-117Sn) =
71.5 Hz, C1), 135.1 (4J(13C-119/117Sn) = 23.1 Hz, C4a), 133.4 (3J(13C-
119Sn) = 141.4 Hz, 3J(13C-117Sn) = 135.3 Hz, C8a), 135.2 (1J(13C-119Sn) =
1
1130 Hz, J(13C-117Sn) = 1081 Hz, C2), 130.1 (3J(13C-119Sn) = 124.7 Hz,
3J(13C-117Sn) = 119.3 Hz, C4), 128.8 (5J(13C-119/117Sn = 5.5, C5/C7), 128.7
(5J(13C-119/117Sn = 5.8 Hz, C5/C7), 128.2 (C6), 128.1 (2J(13C-119Sn) =
H2), 7.12 (d, 8H, J(H3-H2) = 7.7 Hz, 4J(1H-119/117Sn) = 13.9 Hz, H3),
3
2
2.52–2.40 (t, 8H, H5), 1.55–1.41 (dd, 8H, H6), 1.30–1.14 (dd, 8H, H7),
0.88–0.77 (t, 12H, H8) ppm. 13C NMR (C6D6, 75.5 MHz): ␦ 143.9
(4J(13C-119/117Sn) = 11.5 Hz, C4), 137.8 (2J(13C-119Sn) = 39.2 Hz,2J(13C-
117Sn) = 36.9 Hz, C2), 135.4 (1J(13C-119Sn) = 535 Hz,1J(13C-117Sn) =
511 Hz, C1), 129.3 (3J(13C-119Sn) = 53.0 Hz,3J(13C-117Sn) = 50.7 Hz, C3),
36.0 (C5), 33.9 (C6), 22.6 (C7), 14.1 (C8) ppm. 119Sn NMR (C6D6,
112 MHz): ␦ –121.5 ppm. Anal. calcd. for C40H52Sn: C, 73.74; H, 8.04.
Found: C, 75.25; H, 8.04.
85.4 Hz, J(13C-117Sn) = 81.8 Hz, C3), 127.4 (4J(13C-119/117Sn = 11.3 Hz,
C8).119Sn NMR (C6D6, 112 MHz): ␦ –63.5 ppm. Anal. calcd. for
C10H7Cl3Sn: C, 34.10; H, 2.00. Found: C, 35.82; H, 2.13.
p-n-butylphenylSnCl3 (7)
2.0 g tetra-p-n-butyltin 3 (3.1 mmol, 1 equiv.), 1.07 mL SnCl4 (2.4 g,
1
9.2 mmol, 3 equiv.), 150 °C, work-up procedure (a) Yield: 87% H
NMR (C6D6, 300 MHz): ␦ 6.99 (d, 2H, 3J(H3-H2) = 7.9 Hz, H3), 6.75 (d,
2H, 3J(H2-H3) = 7.8 Hz, 3J(H2-119/117Sn) = 48.5 Hz, H2), 2.21 (t, 2H, H5),
1.37–1.21 (dd, 2H, H6), 1.20–1.04 (dd, 2H, H7), 0.81 (t, 3H, H8) ppm.
13C NMR (C6D6, 75.5 MHz): ␦ 148.6 (4J(13C-119Sn) = 28.8 Hz, 4J(13C-
117Sn) = 25.4 Hz, C4), 133.9 (2J(13C-119Sn) = 82.2 Hz, 2J(13C-117Sn) =
80.0 Hz, C2), 133.9 (1J(13C-119Sn) = 1137 Hz, 1J(13C-117Sn) = 1083 Hz, C1),
130.5 (3J(13C-119Sn) = 130.2 Hz, 3J(13C-117Sn) = 124.8 Hz, C3), 35.7
(5J(13C-119/117Sn) = 12.4 Hz, C5), 33.4 (6J(13C-119/117Sn = 5.8 Hz, C6), 22.5
(C7), 14.0 (C8) ppm. 119Sn NMR (C6D6, 112 MHz): ␦ –58.2 ppm.
2,6-xylyl3SnBr (4)
7.59 g (0.25 mol, 7.8 equiv.) Mg in 300 mL THF, 46.3 g (0.25 mol,
6.3 equiv.) 2,6-xylylbromide in 60 mL THF, 4.9 mL (0.04 mol,
1 equiv.) SnCl4 in 100 mL of THF, work-up procedure (c) 1 L of
pentane. The resulting solid was recrystallized from pentane to
obtain colorless crystals. Yield: 90% (16.9 g, 36 mmol). M.p.: 175 °C.
1H NMR (C6D6, 300 MHz): ␦ 7.03–6.96 (t, 3H, H4), 6.85 (d, 6H,
3J(H3-H4) = 7.47 Hz,4J(1H-119/117Sn) = 32.8 Hz, H3), 2.45 (s, 18H,3J(1H-
119/117Sn) = 6.50 Hz, CH3) ppm. 13C NMR (C6D6, 75.5 MHz): ␦ 145.0
(1J(13C-119Sn) = 571 Hz,1J(13C-117Sn) = 546 Hz, C1), 144.5 (2J(13C-119Sn) =
General procedure for Ar3SnH and ArSnH3
A flask furnished with a reflux condenser and a dropping funnel
was charged LiAlH4 pellets and Et2O. A solution of arytltin trichlo-
ride in Et2O was added slowly via the dropping funnel while cool-
ing to either 0 °C or –30 °C. The reaction mixture was stirred for 1 h
and allowed to warm up to RT. Subsequently, degassed water was
added. The phases were separated via a cannula, and the aqueous
layer washed twice with Et2O. The combined organic phases were
extracted with saturated sodium tartrate in degassed water, and
the resulting organic phase dried over CaCl2. For 2,6-xylyl3SnH (8),
the solvent was evaporated under reduced pressure to afford a
solid product. For p-n-butylphenylSnH3 (9), the solvent was evap-
orated gently at 200 mbar (1 bar = 100 kPa), and the product was
distilled at RT using the turbomolecular pump, while the receiv-
ing flask was placed in a dewar filled with liquid nitrogen to
obtain a colorless liquid.
43.9 Hz,2J(13C-117Sn)
= =
42.0 Hz, C2), 130.1 (3J(13C-119Sn)
52.7 Hz,3J(13C-117Sn) = 50.5 Hz, C3), 26.0 (3J(13C-119Sn) = 41.8 Hz,
3J(13C-117Sn) = 40.1 Hz, CH3) ppm. 119Sn NMR (C6D6, 112 MHz): ␦
–131.6 ppm. Anal. calcd. for C24H27BrSn: C, 56.07; H, 5.29. Found: C,
54.67; H, 5.48.
General procedure for ArSnCl3 (5–7)
The corresponding tetraaryl stannane was combined with 3
equiv. of SnCl4 in a Schlenk flask. The mixture was heated up to
150–160 °C using an oil bath and stirred for 1 h to obtain complete
conversion. Residual SnCl4 was removed under reduced pressure
to obtain a dark brown residue. The mixture was subjected to
fractionated distillation under reduced pressure to afford pure
product in the case of liquid compounds (work-up procedure a).
For solid products, the reaction mixture was suspended in dichlo-
romethane, filtered through celite and the solvent evaporated
under reduced pressure to afford solid compounds (work-up pro-
cedure b).
2,6-xylyl3SnH (8)
5.38 g tri-2,6-xylyltinbromide 4 (10.5 mmol, 1 equiv.) in 40 mL
Et2O, 0.60 g LAH pellets (15.7 mmol, 1.5 equiv.) in 40 mL Et2O,
50 mL degassed H2O, 2 × 40 mL Et2O. The resulting solid was
recrystallized from toluene to obtain colorless crystals. Yield: 57%
(2.59 g, 59.5 mmol). M.p.: 139 °C. 1H NMR (C6D6, 300 MHz): ␦ 7.09–
o-tolylSnCl3(5)
13.4 g tetra-o-tolyltin (28 mmol, 1 equiv.), 9.7 mL SnCl4 (21.6 g,
83 mmol, 3 equiv.), 150 °C, work-up procedure (a), Compound was
crystallized neat at 4 °C. Yield: 95% (33.8 g, 106 mmol). M. p.: 9 °C.
1H NMR (C6D6, 300 MHz): ␦ 7.21 (d, 1H,3J(H6-H5) = 8.5 Hz,4J(H6-
119/117Sn) = 64.6 Hz, H6), 7.06–6.97 (dd, 1H, H4), 6.91–6.82 (dd, 1H,
3
1
7.02 (t, 3H, H4), 6.91 (d, 6H, J(H3-H4) = 7.6, H3), 6.86 (s, 1H, J(1H-
119Sn) = 1776 Hz, 1J(1H-117Sn) = 1697 Hz, Sn-H), 2.32 (s, 6H, CH3) ppm.
13C NMR (C6D6, 75.5 MHz): ␦ 145.0 (2J(13C-119/117Sn) = 32.5 Hz, C2),
142.9 (1J(13C-119Sn) = 534 Hz,1J(13C-117Sn) = 511 Hz, C1), 129.3 (4J(13C-
Published by NRC Research Press

564
Can. J. Chem. Vol. 92, 2014
119/117Sn) = 9.4 Hz, C4), 127.7 (3J(13C-119Sn) = 43.8 Hz,3J(13C-117Sn) =
41.5 Hz, C3), 25.8 (3J(13C-119Sn) = 42.6 Hz,3J(13C-117Sn) = 40.3 Hz,
CH3) ppm.119Sn NMR (C6D6, 112 MHz): ␦ –286.6 (1J(119/117Sn-1H) =
1780 Hz) ppm. Anal. calcd. for C10H7Cl3Sn: C, 66.24; H, 6.49. Found:
C, 67.94; H, 6.78.
(18) Coffer, P. K.; Dillon, K. B.; Howard, J. A. K.; Yufit, D. S.; Zorina, N. V. Dalton
Trans. 2012, 41 (15), 4460. doi:10.1039/c2dt12369j.
(19) Bojan, R. V.; López-de-Luzuriaga, J. M.; Monge, M.; Olmos, M. E. J. Organomet.
Chem. 2010, 695 (22), 2385. doi:10.1016/j.jorganchem.2010.07.019.
(20) Sharma, H. K.; Cervantes-Lee, F.; Mahmoud, J. S.; Pannell, K. H. Organometallics
1999, 18 (3), 399. doi:10.1021/om9805234.
(21) Baxter, J. L.; Holt, E. M.; Zuckerman, J. J. Organometallics 1985, 4 (2), 255.
doi:10.1021/om00121a009.
(22) Greene, P. T.; Bryan, R. F. J. Chem. Soc. A 1971, 2549. doi:10.1039/J19710002549.
(23) Leonhardt, T.; Latscha, H. P. Z. Naturforsch., B: Chem. Sci. 1997, 52, 25.
(24) Kräuter, T.; Neumüller, B. Z. Naturforsch., B: Chem. Sci. 1998, 53, 503.
(25) Miles, D.; Burrow, T.; Lough, A.; Foucher, D. J. Inorg. Organomet. Polym. Mater.
2010, 20 (3), 544. doi:10.1007/s10904-010-9376-3.
(26) Batsanov, A. S.; Cornet, S. M.; Dillon, K. B.; Goeta, A. E.; Thompson, A. L.;
Yu Xue, B. Dalton Trans. 2003, (12), 2496. doi:10.1039/b302544f.
(27) Weidenbruch, M.; Schäfers, K.; Pohl, S.; Saak, W.; Peters, K.;
von Schnering, H. G. J. Organomet. Chem. 1988, 346 (2), 171. doi:10.1016/0022-
328X(88)80113-X.
(28) Schittelkopf, K.; Fischer, R. C.; Meyer, S.; Wilfling, P.; Uhlig, F. Appl. Organ-
omet. Chem. 2010, 24 (12), 897. doi:10.1002/aoc.1740.
(29) Meyer, E. A.; Castellano, R. K.; Diederich, F. Angew. Chem., Int. Ed. 2003, 42
(11), 1210. doi:10.1002/anie.200390319.
(30) Jennings, W. B.; Farrell, B. M.; Malone, J. F. Acc. Chem. Res. 2001, 34 (11), 885.
doi:10.1021/ar0100475.
p-n-butylphenylSnH3 (9)
5.0 g p-butylphenylSnCl3 7 (14.0 mmol, 1 equiv.) in 40 mL Et2O
1.1 g LiAlH4 pellets (27.9 mmol, 2 equiv.) in 40 mL Et2O, 50 mL
1
degassed H2O, 2 × 40 mL Et2O. Yield: 83% (2.95 g, 11.5 mmol). H
NMR (C6D6, 300 MHz): 7.30 (d, 2H, 3J(H2-H3) = 6.96, 3J(H2-119/117Sn) =
55.9 Hz, H2), 6.99 (d, 2H, 3J(H3-H2) = 7.0 Hz, 3J(H3-119/117Sn) =
24.8 Hz, H3), 5.05 (s, 3H, 1J(1H-119Sn = 1913 Hz, 1J(1H-117Sn = 1828 Hz,
Sn-H), 2.47–2.37 (t, 2H, H5), 1.52–1.39 (dd, 2H, H6), 1.30–1.15 (dd, 2H,
H7), 0.09–0.80 (t, 3H, H8). 13C NMR (C6D6, 75.5 MHz): 143.8 (4J(13C-
2
119/117Sn = 11.9 Hz, C4), 138.1 (2J(13C-119Sn) = 45.2 Hz, J(13C-117Sn) =
42.7 Hz, C2), 129.1 (3J(13C-119Sn) = 62.6 Hz, 3J(13C-117Sn) = 56.3 Hz, C3),
129.0 (1J(13C-119Sn) = 571.2 Hz, 1J(13C-117Sn) = 545.5 Hz, C1), 35.9 (C5),
33.9 (C6), 22.6 (C7), 14.1 (C8) ppm.119Sn NMR (C6D6, 112 MHz): ␦
–344.6 ppm (1J(119/117Sn-1H) = 1910 Hz) ppm. Anal. calcd. for
C10H16Sn: C, 47.11; H, 6.40. Found: C, 47.88.; H, 6.38.
(31) Janiak, C. J. Chem. Soc., Dalton Trans. 2000, 3885. doi:10.1039/b003010o.
(32) Hunter, C. A.; Sanders, J. K. M. J. Am. Chem. Soc. 1990, 112 (14), 5525. doi:10.
1021/ja00170a016.
(33) Nayak, S. K.; Sathishkumar, R.; Row, T. N. G. CrystEngComm 2010, 12 (10),
3112. doi:10.1039/c001190h.
(34) Brown, P.; Mahon, M. F.; Molloy, K. C. J. Organomet. Chem. 1992, 435 (3), 265.
doi:10.1016/0022-328X(92)83397-Z.
(35) Kozeshkov, K. A. Ber. Dtsch. Chem. Ges. B 1929, 62B, 996. doi:10.1002/cber.
19290620438.
(36) Buckton, G. B. Justus Liebigs Ann. Chem. 1859, 112 (2), 220. doi:10.1002/jlac.
18591120214.
(37) Kozeshkov, K. A. Ber. Dtsch. Chem. Ges. B 1933, 66 (11), 1661. doi:10.1002/cber.
19330661109.
(38) Kozeshkov, K. A.; Nadj, M. M. Ber. Dtsch. Chem. Ges. B 1934, 5, 717. doi:10.1002/
cber.19340670502.
(39) Finholt, A. E.; Bond, A. C.; Wilzbach, K. E.; Schlesinger, H. I. J. Am. Chem. Soc.
1947, 69 (11), 2692. doi:10.1021/ja01203a041.
Supplementary data
Supplementary data are available with the article through the
journal Web site at http://nrcresearchpress.com/doi/suppl/10.1139/
cjc-2013-0503. CCDC 969150-969156 contain the supplementary
crystallographic data for compounds 1–6 and 8 respectively.
These data can be obtained, free of charge, via http://www.ccdc.
cam.ac.uk/products/csd/request (Or from the Cambridge Crystallo-
graphic Data Centre, 12 Union Road, Cambridge CB2 1E2, UK; fax:
+44 1223 33603; or e-mail: deposit@ccdc.cam.ac.uk).
(40) Dillard, C. R.; McNeill, E. H.; Simmons, D. E.; Yeldell, J. B. J. Am. Chem. Soc.
1958, 80 (14), 3607. doi:10.1021/ja01547a031.
(41) Ingham, R. K.; Rosenberg, S. D.; Gilman, H. Chem. Rev. 1960, 60 (5), 459.
doi:10.1021/cr60207a002.
(42) Wharf, I. Inorg. Chim. Acta 1989, 159 (1), 41. doi:10.1016/S0020-1693(00)
80893-2.
Acknowledgements
This work was supported by the NAWI Graz project, a collabo-
ration between the Graz University of Technology and the Graz
University and the COST Action 1302 “Smart Inorganic Polymers”.
(43) Brock, C. P.; Dunitz, J. D. Acta Crystallogr., Sect. B: Struct. Crystallogr. Cryst.
Chem. 1982, 38 (8), 2218. doi:10.1107/S0567740882008358.
(44) Pichler, J.; Torvisco, A.; Uhlig, F. Can. J. Chem. 2013, doi:10.1139/cjc-2013-0504.
(45) Preut, H.; Huber, F. Acta Crystallogr., Sect. B: Struct. Crystallogr. Cryst. Chem.
1979, B35, 744. doi:10.1107/s0567740879004635.
(46) Dakternieks, D.; Lim, A. E. K.; Tiekink, E. R. T. Main Group Met. Chem. 2000,
23, 325. doi:10.1515/mgmc.2000.23.5.325.
(47) Zard, S. Z. Radical Reactions in Organic Synthesis; Oxford University Press, 2003.
(48) Choffat, F.; Smith, P.; Caseri, W. J. Mater. Chem. 2005, 15 (18), 1789. doi:10.
1039/b417401c.
(49) Bukalov, S. S.; Leites, L. A.; Lu, V.; Tilley, T. D. Macromolecules 2002, 35, 1757.
doi:10.1021/ma011249j.
(50) Ahmad, S. U.; Beckmann, J.; Duthie, A. Chem. Asian J. 2010, 5 (1), 160. doi:10.
1002/asia.200900436.
(51) Johnson, B. P.; Almstätter, S.; Dielmann, F.; Bodensteiner, M.; Scheer, M. Z.
Anorg. Allg. Chem. 2010, 636 (7), 1275. doi:10.1002/zaac.201000029.
(52) Bernal, J. D. Proc. R. Soc. Lond. A 1924, 106 (740), 749. doi:10.1098/rspa.1924.
0101.
(53) Schneider-Koglin, C.; Behrends, K.; Dräger, M. J. Organomet. Chem. 1993, 448
(1–2), 29. doi:10.1016/0022-328X(93)80063-H.
(54) Bullpitt, M.; Kitching, W.; Adcock, W.; Doddrell, D. J. Organomet. Chem. 1976,
116 (2), 161. doi:10.1016/S0022-328X(00)91791-1.
(55) Schaeffer, C. D.; Lefferts, J. L.; Zuckerman, J. J. Org. Magn. Reson. 1984, 22 (2),
125. doi:10.1002/mrc.1270220215.
(56) Blessing, R. Acta Crystallogr., Sect. A: Found. Crystallogr. 1995, 51 (1), 33. doi:10.
1107/S0108767394005726.
(57) Sheldrick, G. Acta Crystallogr., Sect. A: Found. Crystallogr. 1990, 46 (6), 467.
doi:10.1107/S0108767390000277.
(58) Sheldrick, G. Acta Crystallogr., Sect. A: Found. Crystallogr. 2008, 64 (1), 112.
doi:10.1107/S0108767307043930.
(59) Allen, F. H. Acta Crystallogr., Sect. B: Struct. Sci. 2002, B58, 380. doi:10.1107/
s0108768102003890.
(60) Macrae, C. F.; Bruno, I. J.; Chisholm, J. A.; Edgington, P. R.; McCabe, P.;
Pidcock, E.; Rodriguez-Monge, L.; Taylor, R.; van de Streek, J.; Wood, P. A.
J. Appl. Crystallogr. 2008, 41 (2), 466. doi:10.1107/S0021889807067908.
(61) Putz, H.; Brandenburg, K. Diamond - Crystal and Molecular Structure
Visualization; 3.2i; 2012, Crystal Impact: Bonn, Germany.
References
(1) Schneider-Koglin, C.; Mathiasch, B.; Dräger, M. J. Organomet. Chem. 1994, 469
(1), 25. doi:10.1016/0022-328X(94)80074-X.
(2) Zeppek, C.; Pichler, J.; Torvisco, A.; Flock, M.; Uhlig, F. J. Organomet. Chem.
2013, 740, 41. doi:10.1016/j.jorganchem.2013.03.012.
(3) Chieh, P. C.; Trotter, J. J. Chem. Soc. A 1970, 911. doi:10.1039/j19700000911.
(4) Belskii, V. K.; Simonenko, A. A.; Reikhsfeld, V. O.; Saratov, I. E. J. Organomet.
Chem. 1983, 244, 125. doi:10.1016/S0022-328X(00)98592-9.
(5) Karipides, A.; Oertel, M. Acta Crystallogr., Sect. B: Struct. Crystallogr. Cryst. Chem.
1977, 33 (3), 683. doi:10.1107/S0567740877004464.
(6) Karipides, A.; Wolfe, K. Acta Crystallogr., Sect. B: Struct. Crystallogr. Cryst. Chem.
1975, 31 (2), 605. doi:10.1107/S0567740875003366.
(7) Wharf, I.; Belanger-Gariepy, F. Acta Crystallogr., Sect. E: Struct. Rep. Online
2003, 59 (8), 661. doi:10.1107/S1600536803016167.
(8) Shaikh, N. S.; Parkin, S.; Lehmler, H.-J. Organometallics 2006, 25 (17), 4207.
doi:10.1021/om060456a.
(9) Wharf, I.; Lebuis, A.-M. Main Group Met. Chem. 2000, 23, 497. doi:10.1515/
mgmc.2000.23.9.497.
(10) Bokii, N. G.; Zakharova, G. N.; Struchkov, Y. T., J. Struct. Chem. 1970, 11 (5),
828. doi:10.1007/bf00743390.
(11) Geller, J. M.; Butler, I. S.; Gilson, D. F. R.; Morin, F. G.; Wharf, I.;
Bélanger-Gariépy, F. Can. J. Chem. 2003, 81 (11), 1187. doi:10.1139/v03-115.
(12) Wharf, I.; Simard, M. G.; McGinn, K. Acta Crystallogr., Sect. C: Cryst. Struct.
Commun. 1995, 51 (2), 236. doi:10.1107/S010827019400987X.
(13) Geller, J.; Wharf, I.; Belanger-Gariepy, F.; Lebuis, A.-M.; Butler, I. S.;
Gilson, D. F. R. Acta Crystallogr., Sect. C: Cryst. Struct. Commun. 2002, 58 (9),
m466. doi:10.1107/S0108270102012362.
(14) Wharf, I.; Simard, M. G. Acta Crystallogr., Sect. C: Cryst. Struct. Commun. 1991, 47
(8), 1605. doi:10.1107/S0108270191000537.
(15) Wharf, I.; Simard, M. G. J. Organomet. Chem. 1997, 532 (1–2), 1. doi:10.1016/
S0022-328X(96)06782-4.
(16) Wharf, I.; Lebuis, A.-M.; Roper, G. A. Inorg. Chim. Acta 1999, 294 (2), 224.
doi:10.1016/S0020-1693(99)00342-4.
(17) Wharf, I.; Lebuis, A.-M. Acta Crystallogr., Sect. C: Cryst. Struct. Commun. 1996, 52
(12), 3025. doi:10.1107/S0108270196012115.
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