Attachment of chelating ligand pockets to tinorganyl moieties

Article abstract of DOI:10.1002/ejic.201400089

Several approaches have been undertaken to realize the synthesis of a new tinorganyl compound with a 2,2′,6′,2″-terpyridine moiety. A synthesis pathway consisting of five steps with an overall yield of 51% was successful in producing Ph₃Sn(CH₂)₃OPhttpy [HOttpy = 2,6-bis(2′-pyridyl)-4′-(p-hydroxyphenyl)pyridine], and insight has been gained into (partial) halogenation reactions with this unprecedented tinorganyl compound. Halogenation with hydroiodic acid produced a new dinuclear complex cation that resulted from head-to-tail coordination of two monocations. Furthermore, synthesis and yields of already known intermediates have been optimized. The products were analyzed and identified by ¹¹⁹Sn NMR, ¹H NMR, and ¹³C NMR spectroscopy and ESI mass spectrometry, as well as by means of single-crystal X-ray diffraction. A new compound Ph₃SnR, comprising a 2,2′,6′,2″- terpyridine-functionalized ligand R, has been synthesized in a five-step procedure. On attempting to halogenate this compound, a partially iodinated derivative was obtained that forms a head-to-tail connected dimer in the salt [(PhISn(CH₂)₃OPhttpy)₂](I₃) ₂ with the terpyridine units acting as chelating ligands. Copyright

Full text of DOI:10.1002/ejic.201400089

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DOI:10.1002/ejic.201400089
Attachment of Chelating Ligand Pockets to Tinorganyl
Moieties
Beatrix E. K. Barth,[a] Klaus Harms,[a] and Stefanie Dehnen*[a]
Keywords: Tin / N ligands / Halogenation
Several approaches have been undertaken to realize the syn-
thesis of a new tinorganyl compound with a 2,2Ј,6Ј,2ЈЈ-terpyr-
idine moiety. A synthesis pathway consisting of five steps
with an overall yield of 51% was successful in producing
produced a new dinuclear complex cation that resulted from
head-to-tail coordination of two monocations. Furthermore,
synthesis and yields of already known intermediates have
been optimized. The products were analyzed and identified
by 119Sn NMR, 1H NMR, and 13C NMR spectroscopy and ESI
mass spectrometry, as well as by means of single-crystal X-
ray diffraction.
Ph3Sn(CH2)3OPhttpy [HOttpy
= 2,6-bis(2Ј-pyridyl)-4Ј-(p-
hydroxyphenyl)pyridine], and insight has been gained into
(partial) halogenation reactions with this unprecedented
tinorganyl compound. Halogenation with hydroiodic acid
Until now, the latter has been quite rare; it has only been
known for chelating ligands comprising acetate or amine
groups, whereas there have not been any examples known
for further chelating groups, such as polypyridine ligands.
The intramolecular attack of the tin atom by the donor
atoms of the chelating ligand is directed by the steric and
electronic situation at the tin atom, which in turn is in-
fluenced by the nature of the additional ligands R. Elec-
tron-withdrawing substituents, such as halide ligands, for
instance, enhance the acidity of the tin atom and therefore
facilitate intramolecular coordination.[6]
Introduction
Organotin(IV) compounds do not only play a prominent
role in current organoelement chemistry research because
of their numerous applications,[1] but they are also well
known for their multifaceted coordination chemistry that
comes with various coordination modes and coordination
numbers for the Sn atom, which range from 4 to 6 in most
cases. With the introduction of appropriate chelating li-
gands these values can be exceeded (up to a coordination
number of 8).[2]
There are two common modes for installing chelating
ligands at tinorganyl moieties: A reaction of free ligands
with the tin moiety,[1e,1f,3] or the pre-connection of the
ligand with the tin atoms by a Sn–C bond away from the
chelating unit. In this case, the chelating ligand may then
coordinate to the tin atom,[1e,4] or, keep away from the tin
atom to produce a vacant chelating pocket to the tin atom,
which bears the additional opportunity to trap further
metal atoms (Scheme 1).[4a,5]
Results and Discussion
One of our current aims regarding the formation and
properties of functionalized tin chalcogenide clusters[7] is
the installation of chelating ligands on the Sn/S cluster sur-
faces for further metal atom/ion trapping. For this, we are
currently extending organotin chemistry towards polypyr-
idyl ligands.[8] The syntheses of organotin trihalides for con-
version with chalcogenide sources is usually preferred over
organotin compounds of the general type R3SnRf; Rf de-
notes the functional ligand Rf that is next to three organic
groups that are usually replaced by halide ligands by
Kocheshkov redistribution reactions with SnX4 (X = Cl,
Br).[5d,9]
In the following we describe a synthesis pathway used to
obtain the novel organotin precursor [Ph3Sn(CH2)3-
OPhttpy] [2; 2,6-bis(2Ј-pyridyl)-4Ј-(p-hydroxyphenyl)pyr-
idine = HOPhttpy], bearing a 2,2Ј,6Ј,2ЈЈ-terpyridine moiety.
It is known that for Rf, comprising an unoccupied terpyr-
idyl group, the application of a Kocheshkov redistribution
reaction is ruled out, since SnX4 does not only halogenate
Scheme 1. Schematic representation of known attachment modes
of chelating ligands at SnIV organyl compounds. D denotes electro-
negative donor atom (N, P, O, S).
[a] Fachbereich Chemie and Wissenschaftliches Zentrum für
Materialwissenschaften der Universität Marburg,
Hans-Meerwein-Straße, 35043 Marburg, Germany
E-mail: dehnen@chemie.uni-marburg.de
http://www.uni-marburg.de/fb15/ag-dehnen
Supporting information for this article is available on the
WWW under http://dx.doi.org/10.1002/ejic.201400089.
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the tin atom, but may at the same be captured by the ligand mild lithiation of triphenyltin hydride by in situ-generated
pocket.[9a] This also affects other halogenation reactions lithium diisopropylamide (Scheme 2). Indeed, fewer by-
like those that are performed by using boron, titanium, bis- products formed and much better yields (71%) were real-
muth, or mercury halide compounds.[10] To avoid this, a ized than under the reaction conditions reported by Weich-
halogenation reaction can be achieved by means of simple mann et al. (38%)[14] or by Christoffers et al. (3%).[15] Com-
electrophilic substitution reactions, if the tinorganyl accords pound 1 was then reacted in the planned manner to pro-
have the general formula DL–CH2–SnR3 (DL = chelating/ duce compound 2 in 72% yield (Scheme 2) as a colorless
donor ligand, R = Ph, Cy, AcO).[11] As we report herein, solid. NMR investigations of 2 (Figures S6–S8) indicate
reaction of 2 with aqueous HI solution indeed leads to (par- that the observed J(119Sn–13C) coupling constants for
tial) iodination; however, the high affinity of the terpyridyl SnCH2 (δ = 7.1 ppm, J = 391 Hz), CH2 (δ = 26.4 ppm, J =
unit to SnIV was further enhanced by the attachment of the 19.6 Hz) and CH2O (δ = 70.7 ppm, J = 66.0 Hz), and the
halide substituent. Hence, we isolated the dinuclear com- 119Sn NMR signal at δ = –99.3 ppm (Figure S8) are in good
plex {[PhISn(CH2)3OPhttpy]2}(I3)2 (3). It represents a coor- agreement with those reported for the known compound
dination dimer with the terpyridyl ligand of one of the or- Ph3Sn(CH2)3NMe2, with a four-coordinate tin atom.[16]
ganotin monoiodides coordinating to the tin atom of the The 119Sn NMR chemical shift reported for Ph3SnBu (δ =
other.
–101.5 ppm) is also very similar.[17] The calculations of the
First attempts to produce compound 2 by reacting allyl C–Sn–C bond angle θ of 2 in solution depending on the
bromide with HOPhttpy, followed by hydrostannylation of 1J(119Sn13C) coupling constants were realized by following
this allyl compound,[12] succeeded in the synthesis of the two different methods.[18] A simple linear correlation as
allyl terpyridine derivative, but led to undesirable redistri- given by Lockhart et al.[18a] leads to an estimate of θ =
bution processes for the final hydrostannylation step, as al- 111Ϯ5°. According to the method by Holecˇek et al.[18b]
ready reported for similar reactions.[11a] Hence, a new syn- the angle is θ = 114Ϯ17°. Both results correlate with the
thesis method was chosen and is described below experimentally found values for the C–Sn–C angles in 2 that
(Scheme 2). As a final step, we planned the coupling of range from 108.5(2)° (C21–Sn1–C14) to 109.26(19)° (C15–
HOPhttpy with (3-chloropropyl)triphenylstannane (1) by a Sn1–C14).
Williamson ether synthesis.
Compound 2 is soluble in chlorinated solvents, and crys-
HOPhttpy was synthesized in a one-pot reaction based tallizes in the monoclinic space group P21. The molecular
on reaction conditions published by Wang and Hanan et structure of 2 is shown in Figure 1, the arrangement of the
al.[13] For the synthesis of 1, hydrostannylation of allyl molecules in the unit cell is shown in Figure 2. Compound
chloride/allyl bromide was attempted with triphenyltin 2 comprises a 2,2Ј,6Ј,2ЈЈ-terpyridine unit, in which the ter-
hydride in the presence of AIBN at 50 °C. However, this minal pyridine rings are rotated such that the nitrogen
method was a failure, as larger amounts of byproducts were atoms point towards opposite directions. The three pyridine
obtained. Hence, an optimized synthesis route based on the rings are not exactly coplanar. Their planes deviate from
method reported by Pinoie et al. was chosen instead;[11b]
a
each other by 12.7(3)° (pyridine ring including N2 in rela-
Scheme 2. Synthesis pathway for the terpyridine functionalized tinorganyl 2 with an overall yield of 51%, and subsequent reaction to
form the dinuclear complex cation within compound 3.
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tion to central pyridine ring) or by 4.5(3)° (pyridine ring
including N3 in relation to the central pyridine ring).
During the reaction of 2 with HI/H2O, the cleavage of
two Sn–C(phenyl) bonds per molecule obviously took place
to yield PhRSnI2 as an intermediate species. We assume
that after this step, traces of I2 removed one of the iodide
ligands from this intermediate, to produce (I3)– anions with
the [RSnPhI]+ cationic complexes. An intermolecular reac-
tion of the latter finally formed the complex dicationic di-
mer in 3 by a head-to-tail coordination. This replenishes
the already known organotin dications in the literature.[23]
Since the reaction of 2 with HI/H2O was carried out under
strict exclusion of air and light, we assume that the com-
mercially available HI solution that was used as received,
already contained I2 (in agreement with its brown color).
Compound 3 crystallizes as yellow needles in the triclinic
Figure 1. Molecular structure of the 2,2Ј,6Ј,2ЈЈ-terpyridine-func-
tionalized tinorganyl in 2. Hydrogen atoms are omitted for clarity.
Thermal ellipsoids are drawn at 50% probability.
¯
space group P1 and has a crystallographic inversion sym-
metry. The molecular structure is provided in Figure 3, the
packing of cations and anions is shown in Figure 4.
Figure 2. Arrangement of the molecules in the crystal structure of
2. H atoms and disordered solvent molecules are omitted for clar-
ity. C atoms are denoted as sticks. Thermal ellipsoids are drawn at
50% probability.
Figure 3. Molecular structure of the complex dication in 3 with
(I3)– counterions. Hydrogen atoms are omitted for clarity. Thermal
ellipsoids are drawn at 50% probability.
This unit is attached to a phenyl group and linked by O1
to a propylene spacer that connects the chelating ligand
with the tin atom. The planes defined by the phenyl ring
and the central pyridine ring of the terpyridine unit also
deviate by 15.5(2)° from each other. Apart from this bulky
ligand, the tin atom is bound to three distorted phenyl
groups (for selected angles see Table S1). In contrast to
many O-functionalized tinorganyl compounds[5c,6,7c,19] O1
does not undergo an intermolecular OǞSn coordination,
which is, however, common for triphenyltin propyl ether de-
rivatives.[20]
Eventually it turned out that only treatment of 2 with a
HI/H2O solution (57%) led to a reaction towards a tin hal-
ide product. Compound 3 formed after stirring the reaction
mixture for 2 weeks. Nevertheless, similar to further
attempts of halogenation[5c,11b,11c,21,22] an insoluble, yellow
Figure 4. Arrangement of the molecules in the crystal structure of
3. H atoms are omitted for clarity. C atoms are denoted as sticks.
Thermal ellipsoids are drawn at 50% probability.
The terpyridine–Sn–I units contribute to a distorted oc-
solid was produced, which was filtered and washed with tahedral coordination environment around the tin atoms
EtOH; from the filtrate, yellow crystals of 3 were obtained and each unit further binds to one phenyl group and one
by layering with n-hexane. The concentration of 3 in the aliphatic propylene unit. The latter exhibits a slight C–Sn–
reaction mixture is too low for the detection of 119Sn NMR C bending towards the iodide ligand in support of a better
signals. Upon treatment of the product with coordinating, bite of the chelating Phttpy unit [C30i–Sn1–C22
non-protic solvents like pyridine or THF, further reaction 165.06(17)°, i = –x, 1 – y, 1 – z]. The propylene group is
took place such that the mixture turned into a pink color, stretched in a way that excludes any π–π stacking between
again with the lack of any 119Sn NMR signals.
the phenyl or pyridine rings of the Phttpy building blocks.
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Mean planes including atoms C7, C8, C9 and C7i, C8i,
C9i (i = –x, 1 – y, 1 – z) of the chelating ligands are
5.618(3) Å from each other. The void does not include any
electron density, which might be assigned as solvent mole-
cule atoms. Sn–N distances range from 2.277(4) Å (Sn1–
N1) to 2.320(4) Å (Sn1–N3) [Sn1–N2 2.238(4) Å] and are
slightly smaller than the Sn–N bonds published for haloge-
nated tinorganyl compounds with N-donor ligands.[24]
An unexpectedly long Sn–I distance of 3.1038(5) Å oc-
3 mbar) for several hours. Silica gel used for chromatography (par-
ticle size 0.063–0.2 mm) was obtained from Macherey–Nagel.
Chemicals (Aldrich, Fluka, Lancaster, and Merck) were used with-
out further purification. HI solution (57% in H2O, purity 99.99%)
was obtained from Sigma–Aldrich (no. 210013). EDX spectro-
scopic analyses were performed using the EDX device Voyager 4.0
of Noran Instruments coupled with the electron microscope Cam-
Scan CS 4DV. Data acquisition was performed with an acceleration
voltage of 20 kV and 100 s accumulation time. For the analyses
multiple single crystals of 3 and the light yellow precipitate were
curs, which is much larger than distances of already pub- used. Sn–L and radiation emitted by the atoms was analyzed.
lished tinorganyl compounds. However, to the best of our
knowledge, a C2N3I coordination environment for tin has
been found only once by Gustavson et al. for the tin ana-
(3-Chloropropyl)triphenylstannane (1): According to a method re-
ported by Pinoie et al.[11b] a solution of n-butyllithium (1.6 m,
9.36 mmol) was added to a solution of diisopropylamine (0.95 g,
logue of the tetraphenyl cyclopentadienyl anion that was 9.36 mmol) in THF (16 mL) at 0 °C. After 10 min, Ph3SnH (4.01 g,
not further analyzed by X-ray diffraction.[25] This might be
11.41 mmol) was added and the mixture was stirred for 20 min at
room temperature. The clear yellow solution was added dropwise
the reason for the observed difference from that of the re-
to
a chilled solution of 1-bromo-3-chloropropane (1.47 g,
ported Sn–I distances. The three pyridine rings are nearly
coplanar. The mean planes of the pyridine rings, including
N3 or N2, deviate from the mean plane of the central pyr-
idine by only 5.7(2)° (py-N3) and 2.0(2)° (py-N1). The
phenyl group is even more distinctly displaced from the
mean terpyridine plane, of which it deviates by 29.4(2)°.
This comes along with H bonding interactions of the
9.36 mmol) in THF (16 mL). The colorless solution was stirred for
12 h at room temperature. Dichloromethane (20 mL) was added
under air, and the mixture was washed with saturated aqueous
solutions of NH4Cl (15 mL), NaHCO3 (15 mL), and brine (15 mL).
It was dried with MgSO4, filtered, and concentrated in vacuo. Pure
compound 1 was isolated as a white solid after purification by
chromatography with dichloromethane/n-hexane (90:10), yield
1
nearby triiodide anions [3.11 Å for H18···I3 and 3.16 Å for 2.83 g, 71%. H NMR (400 MHz, CDCl3): δ = 7.63–7.45 (m, 6 H,
ortho-Ph), 7.42–7.34 (m, 9 H, meta/para-Ph), 3.53 (t, 2 H, CH2-Cl),
2.25–2.01 (m, 2 H, CH2-CH2Cl), 1.69–1.44 (m, 2 H, Sn-CH2) ppm.
13C NMR (100 MHz, CDCl3): δ = 138.4 (1JC,Sn = 497.4 Hz, 3 C,
Sn-ArC), 137.2 (6 C, Ar ortho-C), 129.3 (3 C, Ar para-C), 128.8 (6
H20···I3i (i = x, 1 + y, z)] that are shorter than the sum of
the van der Waals radii.[26]
C, Ar meta-C), 48.3 (3JC,Sn = 84.8 Hz, 1 C, CH2Cl), 30.1 (2JC,Sn
=
C,
Conclusions
16.2 Hz,
1
C, CH2-CH2C), 8.2 (1JC,Sn
=
381.7 Hz,
1
SnCH2) ppm. 119Sn NMR (149 MHz, CDCl3): δ = 99.7 ppm. MS
(ESI): m/z (%) = 429.0 (24) [M + H]+, 351.0 (53) [M – Ph]+.
C21H21ClSn (427,56): calcd. C 58.99, H 4.95, Cl 8.29, Sn 27.76;
found C 59.21, H 4.89, Cl 8.31, Sn 27.69.
Herein we report on recent success in the extension of
organostannane chemistry by the attachment of a multipyr-
idyl ligand. This served to enrich the common pool of che-
lating alcohol or ester ligands at organotin moieties. A syn-
thesis route has been developed that allows good yields for
(3-chloropropyl)triphenylstannane (1) as the intermediate
for the preparation of the 2,2Ј,6Ј,2ЈЈ-terpyridine-decorated
tinorganyl (2) in five steps with an overall yield of 51%.
Attempts of a halogenation of the tin atoms in compound
2 have been undertaken for chloride, bromide, as well as
iodide ligands. This was, however, only possible in the case
of (partial) iodination, which yielded compound 3. The lat-
ter comprises a head-to-tail dimer of two tin complexes in
a rare coordination environment. The products have been
(tppy-3-Oxopropyl)triphenylstannane (2): NaH (7.561 mmol,
0.302 g) was washed with n-pentane (3 mL) several times under an
inert atmosphere. DMF (20 mL) was added and a suspension
of 2,6-bis(2Ј-pyridyl)-4Ј-(p-hydroxyphenyl)pyridine (HOPhttpy;
0.47 mmol, 0.17 g) in DMF (3 mL) was added slowly at room tem-
perature. It was stirred for 90 min, in that time the evolution of gas
was observed. Afterwards, 1 (6.258 mmol, 2.954 g) in DMF
(25 mL) was added to the orange solution. The mixture was heated
to 70 °C for 1.5 h and cooled to room temperature. After quench-
ing with aqueous KOH (10%, 30 mL), the mixture was extracted
with dichloromethane (80 mL) several times. It was dried with
MgSO4 and the volatiles were removed in vacuo. The product was
purified by recrystallization from ethyl acetate. Colorless needles of
2 were obtained within 1 d by slow evaporation of a dichlorometh-
ane solution, yield 3.22 g (4.505 mmol), 72%. 1H NMR (400 MHz,
CDCl3): δ = 8.75–8.71 (m, 2 H, NCH), 8.70 (s, 2 H, NCCH), 8.69–
8.64 (m, 2 H, NCCH), 7.87 (dd, 3J = 1.8, 7.7 Hz, 2 H, NCCHCH),
7.84–7.78 (m, 2 H, Ph), 7.68–7.47 (m, 6 H, Sn-Ph), 7.42–7.28 (m,
11 H, Sn-Ph), 6.93–6.85 (m, 2 H, Ph), 4.00 (t, 3J = 6.3 Hz, 2 H,
OCH2), 2.42–2.10 (m, 2 H, OCH2CH2), 1.82–1.50 (m, 2 H,
SnCH2) ppm. 13C NMR (100 MHz, CDCl3): δ = 160.0 (1 C, OC),
156.5 (2 C, NC), 155.9 (2 C, NC), 149.9 (1 C, NCCHC), 149.2 (2
C, NCH), 138.8 (1JC,Sn = 493.1 Hz, 3 C, SnPh-C), 137.1 (6 C,
SnPh-CH), 136.9 (2 C, NCHCHCH), 130.7 (1 C, Ph-C), 129.1 (3
C, SnPh-CH),128.7 (6 C, SnPh-CH), 128.5 (2 C, OCCHCH) 123.8
(2 C, NCHCH), 121.5 (2 C, NCCH), 118.4 (2 C, NCCH), 115.0 (2
1
characterized by means of H NMR, 13C NMR, and 119Sn
NMR spectrometry, mass spectrometry and/or single-crys-
tal X-ray diffraction analysis, and EDX spectroscopy.
Experimental Section
General Methods: All manipulation steps were performed under an
Argon atmosphere, unless otherwise noted. All solvents were dried
and freshly distilled prior to use: dimethylformamide (DMF), tetra-
hydrofuran (THF). All synthesis steps were performed with strict
exclusion of air and external moisture (Ar atmosphere at a high-
vacuum, double-manifold Schlenk line). Diisopropylamine (DIA)
was dried with calcium hydride (CaH2), distilled, and immediately
used in reaction. All solvents were dried and freshly distilled prior
to use. Water was degassed by applying a dynamic vacuum (10–
C, OCCH), 70.7 (3JC,Sn = 66.0 Hz, 1 C, OCH2), 26.4 (2JC,Sn
=
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Table 1. Crystallographic and refinement details of compounds 2·CH2Cl2 and 3.
2·CH2Cl2
3
Empirical formula
Mr [gmol–1]
Crystal system, space group
a, b, c [Å]
C42H35N3OSn, CH2Cl2
801.34
monoclinic, P21
11.4995(6), 11.3321(4), 14.4554(7)
C60H50I8N6O2Sn2
2139.64
¯
triclinic, P1
8.5663(3), 10.1406(3), 18.4266(6)
α, β, γ [°]
90, 95.501(4), 90
1875.06(15)
86.995(2), 78.805(1), 87.894(1)
1567.48(9)
V [Å3]
Z
2
0.86
1
4.78
μ [mm–1]
Crystal size [mm]
Tmin., Tmax.
Measurements
Independent reflections
Observed reflections [IϾ2σ(I)]
Rint
0.15ϫ0.08ϫ0.05
0.421, 0.624
10105
6886
5827
0.023
0.14ϫ0.06ϫ0.03
0.69, 0.87
29987
5836
5158
0.033
θmax [°]
25.9
25.5
R[F2 Ͼ 2σ(F2)], wR(F2), S
Parameters
0.028, 0.058, 0.89
509
0.028, 0.063, 1.08
352
Restraints
H atom treatment
124
0
constrained parameters
constrained parameters
w = 1 / [σ2(Fo22) + (0.0298P)2]
w = 1 / [σ2(Fo22) + (0.0163P)2 + 10.2837P]
2
2
where P = (Fo + 2Fc )/3
where P = (Fo + 2Fc )/3
Δρmax, Δρmin (eÅ–3)
Absolute structure
0.57, –0.42
2.27, –1.62
–
Flack x determined using 2381 values
[(I+) – (I–)]/[(I+) + (I–)]
–0.036 (13)
Absolute structure parameter
–
19.6 Hz,
1 = 390.9 Hz, 1 C, nance (NMR) spectroscopy, energy dispersive X-ray (EDX) spec-
C, OCH2CH2), 7.1 (1JC,Sn
SnCH2) ppm. 119Sn NMR (149 MHz, CDCl3): δ = –99.3 ppm. MS troscopy, and on the synthesis of 3.
(ESI+): m/z (%) = 718.2 (100) [M + H]+.
{[PhISn(CH2)3OPhttpy]2}(I3)2 (3): Triphenylstannane (2) (0.15 mg,
0.209 mmol) was dissolved in dichloromethane (7 mL) and cooled
to –60 °C. A HI/H2O solution (57%, 0.1 mL, 0.758 mmol) was
Acknowledgments
This work was supported by the Deutsche Forschungsgemeinschaft
added and the flask was covered with aluminum foil to darken and
warm it slowly to room temperature. The mixture was stirred for
2 w and the light yellow slurry was filtered and washed with EtOH
to isolate the precipitate (160 mg, mmol, 72%). Attempts to recrys-
tallize the precipitate from hot ethanol did not lead to crystalline
material but layering of the (saturated) filtrate with n-hexane
yielded yellow needles of 3. EDX (crystals): I/Sn calcd: 4:1; found
3.89:0.96, EDX (yellow precipitate): I/Sn found: 4.1:0.9.
(DFG) within the framework of the Research Training Group
GRK1782. We additionally thank Nicholas Rau and Uwe Justus
for their help in the lab.
[1] a) M. Gielen, Appl. Organomet. Chem. 2002, 16, 481–494; b)
P. Yang, M. Guo, Coord. Chem. Rev. 1999, 185–186, 189–211;
c) W. T. Piver, Environ. Health Perspect. 1973, 4, 61–79; d) M.
Gielen, A. G. Davies, K. Pannell, E. Tiekink, in: Tin Chemis-
try: Fundamentals, Frontiers, and Applications, Wiley-VCH,
Single-Crystal X-ray Diffraction Data: T = 100 K, graphite mono-
chromator, area detector system Stoe IPDS2[27] (2) or Bruker D8
Quest[28] (3). Both structures were solved by direct methods in
SHELXS97 and refined by full-matrix least-squares refinement
against F2 in SHELXL97[29] or SHELXL-2013[30] with anisotropic
displacement parameters for the non-hydrogen atoms. Absorption
corrections were performed by semi-empirical methods,[31] using
multi-scanned reflections. Where possible, H atoms were inserted
assuming idealized geometry and refined riding on their parent
atoms with Ueq = n·Ueq (parent atom), where n = 1.2 (n = 1.5 for
H atoms in methyl groups). Absolute structure determination was
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Published Online: ᭿
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Date: 03-04-14 17:11:30
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Tinorganyl Moieties
B. E. K. Barth, K. Harms,
S. Dehnen* ........................................ 1–7
A new compound Ph3SnR, comprising a
2,2Ј,6Ј,2ЈЈ-terpyridine-functionalized
ligand R, has been synthesized in a five-
step procedure. On attempting to halogen-
ate this compound, a partially iodinated
derivative was obtained that forms a head-
to-tail connected dimer in the salt
[(PhISn(CH2)3OPhttpy)2](I3)2 with the ter-
pyridine units acting as chelating
ligands.
Attachment of Chelating Ligand Pockets
to Tinorganyl Moieties
Keywords: Tin / N ligands / Halogenation
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