An unusual reaction of (β-dimethylaminoethoxy)triethyltin with phenyltin trichloride. The first X-ray structural evidence of the existence of complexes R2SnXY·R2SnXY (R = Alkyl, Aryl; X, Y = Hal, OR, X ≠ Y) both as unsymmetrical addu

Article abstract of DOI:10.1002/ejic.200600527

The substituent exchange reaction of PhSnCl₃ with [Et ₃Sn-(OCH₂CH₂NMe₂)] gives rise unexpectedly to the unsymmetrical adduct [Ph₂SnCl₂· Ph₂Sn(OCH₂CH₂

Full text of DOI:10.1002/ejic.200600527

FULL PAPER
DOI: 10.1002/ejic.200600527
An Unusual Reaction of (β-Dimethylaminoethoxy)triethyltin with Phenyltin
Trichloride. The First X-ray Structural Evidence of the Existence of
Complexes R SnXY·R SnXY (R = Alkyl, Aryl; X, Y = Hal, OR, X ϶ Y)
2
2
Both as Unsymmetrical Adducts [R SnX ·R SnY ] and Symmetrical Dimers
2
2
2
2
[
R SnXY]
2
2
[
a,b]
[b]
[c]
Ivan A. Portnyagin,
Mikhail S. Nechaev, Victor N. Khrustalev,*
[a]
[a]
[c]
[b]
Nikolay N. Zemlyansky, Irina V. Borisova, Mikhail Yu. Antipin, Yuri A. Ustynyuk,
and Valery V. Lunin[
b]
Keywords: Complexation / Tin / Dimerization / Stannanes / X-ray diffraction
The substituent exchange reaction of PhSnCl
OCH CH NMe )] gives rise unexpectedly to the unsymmet- of Grignard reagents” have symmetrical dimeric structures,
rical adduct [Ph SnCl ·Ph Sn(OCH CH NMe ] (2). It has i.e., can be formulated as [Bu Sn(OMe)(OAc)] and [Et Sn-
been unambiguously proved for the first time that com- (OMe)Cl] , respectively. Both types of structures, viz., un-
pounds of the RSnX type are able to undergo the hydro- symmetrical adduct (2) and symmetrical dimer (5, 6), have
carbon substituent redistribution reaction. The analogous tin
complexes [Et SnCl ·Et Sn(OMe) ] (5) and [Bu Sn(OAc)
Bu Sn(OMe) ] (6), which have ligands other than β-dimethyl-
3
with [Et
3
Sn-
aminoethoxy and could be considered as “organotin analogs
(
2
2
2
2
2
2
2
2
2
)
2
2
2
2
2
3
been characterized by X-ray diffraction analysis.
(© Wiley-VCH Verlag GmbH & Co. KGaA, 69451 Weinheim,
Germany, 2006)
2
2
2
2
2
2
·
2
2
Introduction
here on the surprising results of the interaction between (β-
dimethylaminoethoxy)triethyltin and -phenyltin trichloride.
Very recently, we have found that the reaction of
PhGeCl3 with [Et Ge(OCH CH NMe )] affords [PhGe-
Redistribution reactions are a convenient and widely
used method for the synthesis of organometallic com-
3
2
2
2
[
1]
pounds. It has been shown previously that penta- and
hexacoordinate organotin compounds such as [Me Sn-
[3f]
(
OCH CH NMe ) Cl] in high yield. However, the analo-
2 2 2 2
n
gous reaction in the case of tin unexpectedly results in the
unsymmetrical adduct [Ph SnCl ·Ph Sn(OCH CH -
NMe ) ] as the main reaction product.
Ar4–n] and [Bu SnArCl], which contain electron-donating
2
2
2
2
2
2
groups in the aryl ligands, are more active towards redistri-
bution, and related (transmetallation), reactions than tetra-
coordinate tin(IV) derivatives.[ Therefore, the redistri-
bution reactions of hypercoordinate organotin compounds
2
2
2]
[
R SnX4–n] containing electron-donating groups in the Results and Discussion
n
functional substituents X but not in the hydrocarbon sub-
stituents R, have been of significant interest. As a continua-
The reaction was carried out by the gradual addition of
tion of our investigations into the chemistry of (β-dimethyl- [Et
Sn(OCH CH NMe )] to a PhSnCl solution in diethyl
3
2 2 2 3
aminoethoxy)germanium and -tin derivatives,[ we report ether or tetrahydrofuran. In our opinion, it proceeds in
3]
three stages. In the first stage, diphenyldichloro- and dichlo-
rodialkoxystannanes are formed. The formation of these
products apparently proceeds by the initial formation of a
[
[
[
a] A. V. Topchiev Institute of Petrochemical Synthesis, Russian
Academy of Sciences,
[PhSn(OCH CH NMe )Cl ] intermediate, which can fur-
2
2
2
2
2
9, Leninsky Prospect, 119991 Moscow, Russian Federation
ther disproportionate by two paths: either by the exchange
of Ph and OCH CH NMe substituents (path a) or by the
b] Department of Chemistry, M. V. Lomonosov Moscow State
University,
Leninskie Gory, 119899 Moscow, Russian Federation
c] A. N. Nesmeyanov Institute of Organoelement Compounds,
Russian Academy of Sciences,
2
2
2
exchange of Cl and OCH CH NMe substituents (path b).
2 2 2
Path
[Cl Sn(OCH
PhSn(OCH CH NMe ) Cl] (1) and PhSnCl , and a subse-
a
gives rise immediately to [Ph SnCl ] and
2 2
2
8 Vavilova str., 119991, Moscow, Russian Federation
2
CH NMe ) ], whereas path b first gives rise to
2 2 2 2
Fax: +7-495-135-5085
[
2
2
2 2
3
E-mail: vkh@xray.ineos.ac.ru
Supporting information for this article is available on the
WWW under http://www.eurjic.org or from the author.
quent interchange of the Ph and Cl substituents affords
[Ph SnCl ] and [Cl Sn(OCH CH NMe ) ] (Scheme 1).
2
2
2
2
2
2 2
Eur. J. Inorg. Chem. 2006, 4271–4277
© 2006 Wiley-VCH Verlag GmbH & Co. KGaA, Weinheim
4271

V. N. Khrustalev et al.
Table 1. Selected bond lengths [Å] and angles [°] for 1.
FULL PAPER
Sn(1)–O(1)
Sn(1)–O(2)
Sn(1)–C(1)
2.024(3) Sn(1)–N(2)
2.032(3) Sn(1)–N(1)
2.163(4) Sn(1)–Cl(1)
2.306(3)
2.340(3)
2.5242(11)
93.56(13)
O(1)–Sn(1)–O(2) 89.90(14) C(1)–Sn(1)–N(1)
O(1)–Sn(1)–C(1) 170.46(15) N(2)–Sn(1)–N(1) 168.42(11)
O(2)–Sn(1)–C(1) 95.82(14) O(1)–Sn(1)–Cl(1) 83.51(10)
O(1)–Sn(1)–N(2) 93.60(12) O(2)–Sn(1)–Cl(1) 168.11(10)
3
Scheme 1.The first stage of the reaction of [PhSnCl ] with
O(2)–Sn(1)–N(2) 81.38(13) C(1)–Sn(1)–Cl(1)
C(1)–Sn(1)–N(2) 94.80(13) N(2)–Sn(1)–Cl(1)
O(1)–Sn(1)–N(1) 78.80(12) N(1)–Sn(1)–Cl(1)
O(2)–Sn(1)–N(1) 89.82(12)
92.10(11)
89.15(9)
98.55(8)
3 2 2 2
[Et Sn(OCH CH NMe )].
Scheme 1 was confirmed by an NMR spectroscopic
study of the products of the reaction between the mono-
chloroorganostannane 1, which was prepared by an inde-
pendent method involving reverse order of the reagent mix-
ing (see below), and trichlorophenylstannane. In accord-
ance with the multinuclear NMR spectroscopy data, the re-
action mixture contains [Ph SnCl ] and [Cl Sn(OCH CH -
Proof of the structure of 2 came from a single-crystal X-
ray diffraction analysis (Figure 2, Table 2), which revealed
that 2 is the adduct [Ph SnCl ·Ph Sn(OCH CH NMe ) ]
formed by the bridging oxygen atoms of the β-dimethylami-
noethoxy ligands, with an unsymmetrical arrangement of
the substituents at the tin atoms. It is located on a crystallo-
2
2
2
2
2
2 2
2
2
2
2
2
NMe ) ]. The latter was identified by comparison of its
2
2
NMR spectral characteristics with those of the compound
prepared by treatment of HgCl2 with [Sn(OCH CH -
2
2
graphic C axis that passes through the tin atoms. The tin
2
NMe ) ].
2
2
atoms are hexacoordinate, with the phenyl groups in the
trans configuration. The C–Sn–C angle at Sn1 [132.6(3)°]
deviates substantially from the value of 180° (the phenyl
rings are shifted towards the longer SnǟN coordination
bonds), whereas that at Sn2 is essentially linear [177.3(3)°].
The basal plane of Sn1 is defined by an N O donor set
A single-crystal X-ray diffraction analysis of 1 (Figure 1,
Table 1) provided proof for the proposed structure and re-
vealed that the tin atom is hexacoordinate with one carbon,
one chlorine, two oxygen, and two nitrogen atoms, with an
overall slightly distorted octahedral cis-cis-trans configura-
tion, respectively.
2
2
defined by two chelating β-dimethylaminoethoxy ligands
with very long SnǟN bond lengths [2.766(4) Å]. Two chlo-
rine and two oxygen atoms in the cis configuration make
up the basal plane of Sn2. The bond angles in the equato-
rial planes vary from 70.8(1)° to 147.8(2)° for Sn1 and from
66.2(2)° to 105.44(7)° for Sn2. Thus, the geometry of Sn1
is best described as skew-trapezoidal bipyramidal, while
that of Sn2 is best described as distorted octahedral.
Figure 1.View of compound 1. The hydrogen atoms have been
omitted for clarity. Displacement ellipsoids are scaled to the 50%
probability level. The coordination bonds are shown by open lines.
It is important to note that, in contrast to [PhGe-
(
OCH CH NMe ) Cl], which tends to ionize in hydrogen-
2 2 2 2
bond-donor solvents such as CHCl3 to form the ionic
pentacoordinate form [PhGe(OCH CH NMe ) ][Cl] rather
2
2
2 2
than the neutral hexacoordinate form,[ compound 1 exists Figure 2.View of complex 2. The hydrogen atoms have been omit-
3f]
ted for clarity. Thermal ellipsoids are scaled to the 40% probability
level. The coordination bonds are shown by open lines.
only in the neutral hexacoordinate form.
The second stage is obviously the alkoxylation reaction
of [Ph SnCl ], which yields [Ph Sn(OCH CH NMe ) ], and
2
2
2
2
2
2 2
the third stage is the complexation reaction between
Ph SnCl ] and [Ph Sn(OCH CH NMe ) ], which yields the [2.242(3) Å] bond lengths in the four-membered Sn O ring
The covalent Sn–O [2.091(3) Å] and coordination SnǟO
[
2
2
2
2
2
2 2
2
2
final poorly soluble complex 2.
are significantly different and close to the corresponding
4272
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© 2006 Wiley-VCH Verlag GmbH & Co. KGaA, Weinheim
Eur. J. Inorg. Chem. 2006, 4271–4277

2 2
First Complexes R SnXY·R SnXY (R = Alk, Ar; X, Y = Hal, OR, X ϶ Y)
FULL PAPER
Table 2. Selected bond lengths [Å] and angles [°] for 2.[a]
have reported the existence of unsymmetrical adducts in
solution by studying the interaction of [R Sn(OMe) ] with
2
2
Sn(1)–O(1)
Sn(1)–C(1)
2.091(3)
2.112(5)
Sn(2)–C(11)
Sn(2)–O(1)
2.150(5)
2.242(3)
[
R SnCl ] or [R Sn(OAc) ] (R = alkyl) by calorimetric, diel-
2 2 2 2
[8]
Sn(1)–N(1)
O(1)–Sn(1)–O(1)
O(1)–Sn(1)–C(1)
O(1)–Sn(1)–C(1)
C(1)–Sn(1)–C(1)
O(1)–Sn(1)–N(1)
O(1)–Sn(1)–N(1)
C(1)–Sn(1)–N(1)
C(1)–Sn(1)–N(1)
N(1)–Sn(1)–N(1)
2.766(4)
Sn(2)–Cl(1)
C(11)–Sn(2)–O(1)
C(11)–Sn(2)–O(1)
O(1)–Sn(2)–O(1)
C(11)–Sn(2)–Cl(1)
O(1)–Sn(2)–Cl(1) 160.36(9)
C(11)–Sn(2)–Cl(1)
O(1)–Sn(2)–Cl(1)
Cl(1)–Sn(2)–Cl(1) 105.44(7)
Sn(1)–O(1)–Sn(2) 111.10(14)
2.5178(14)
89.13(16)
88.62(17)
66.15(17)
91.36(15)
cometric, dielectrometric, and cryoscopic methods. How-
ever, as was shown later by Davies and co-workers, the
structure of these complexes in solution is additionally com-
plicated by the occurrence of the equilibria presented in
Scheme 2. These authors suggested that complexes of the
type R SnXY·R SnXY could be considered to be “or-
ganotin analogs of Grignard reagents”. However, no un-
ambiguous evidence of the structure of the complexes
R SnXY·R SnXY was available until now. It should be
i
i
71.66(18)
113.44(17)
104.69(17)
132.6(3)
70.77(14)
141.13(13)
81.65(16)
85.56(17)
147.8(2)
i
i
i
i
i
i
90.27(14)
94.21(9)
2
2
[9]
i
i
i
i
C(11)–Sn(2)–C(11) 177.3(3)
2
2
noted that in the paper cited above, the authors gave prefer-
ence to the symmetrical structure of type II for these com-
plexes.
[
a] Symmetry transformations used to generate equivalent atoms:
i: –x, y, –z + 1/2.
Taking into account the possible application of these re-
actions to the solution of different synthetic and applied
[
10]
bond lengths in previously investigated mononuclear hexa- problems,
we have decided to fill this gap. To this end,
coordinate diphenyltin complexes.[ The Sn–C and Sn–Cl we carried out the reactions of diethyltin dichloride with
4]
bond lengths are also similar to those found in other related dimethoxydiethyltin and dibutyltin diacetate with dime-
dichloro- and diphenyltin compounds.[
4,5]
thoxydibutyltin. The products obtained were studied by X-
It is of interest that the result of the reaction of [PhSnCl3] ray diffraction analysis. It turned out that they consist of
with [Et Sn(OCH CH NMe )] depends to a great extent on symmetrical dimers [Et Sn(Cl)(OMe)]2 (5) and [Bu Sn-
3
2
2
2
2
2
the order of reagent mixing. Upon the reverse order of mix- (OAc)(OMe)] (6) (Figures 3 and 4 and Tables 3 and 4),
2
ing, i.e., when [PhSnCl ] is added to [Et Sn(OCH - respectively, with Sn atoms linked by bridging methoxy
3
3
2
CH NMe )] solution, di(alkoxy)chlorophenylstannane (1) is groups in the crystal. The coordination geometry around
2
2
produced in high yield instead of 2. Moreover, the use of the metal atoms is a strongly distorted trigonal bipyramid
an excess of [Et Sn(OCH CH NMe )] does not allow the with the two C atoms and the covalently bonded O atom
3
2
2
2
complete substitution of all three chlorine atoms in of the bridging methoxy group in the equatorial plane. The
PhSnCl ] with β-dimethylaminoethoxy groups. For the coordinated O atom of the bridging methoxy group and Cl
[
3
sake of comparison, we also carried out the same reaction or OAc substituents for 5 and 6, respectively, occupy the
for the alkyltin derivatives [MeSnCl ] and [EtSnI ]. How- axial positions. The distortion from the ideal trigonal-
3
3
ever, despite the utilization of similar reactions, in the case bipyramidal geometry is especially apparent in the C–Sn–C
of the alkyltin derivatives, the reactions stopped after the and O–SnǟO angles. The tin atoms in these compounds
first step, affording [MeSn(OCH CH NMe ) Cl] (3) and can also be regarded as [4+1]-coordinate, i.e. they represent
2
2
2 2
[
EtSn(OCH CH NMe ) I] (4), respectively, in high yields. model compounds along the transformation path tetrahe-
2 2 2 2
As for 1, compounds 3 and 4 exist only in the neutral hexa- dron ↔ trigonal bipyramid.
coordinate form.
Note that the disposition of the substituents implies the
It is very important to point out that unique phenyl presence of an intrinsic inversion center in both 5 and 6.
group migration from [PhSnCl ] takes place in the reaction However, in the crystal, the crystallographically imposed in-
3
described here. Phenyl group migration has previously been version center is retained only in the case of 5. In the crystal
–
observed only for the ionic complexes [PhSnHal ] or structure of 6, two out of the four butyl groups adopt dif-
4
2
–
[
PhSnHal ] , in which such migration is promoted by fluo- ferent conformations and are slightly disordered (Figure 4);
5
[6,7]
ride ion or tributylphosphane.
Moreover, in these re- the inversion center is lost because of this.
Similar to 2, the covalent Sn–O and coordination SnǟO
reaction mixture and their structures were not determined bond lengths in the four-membered Sn O rings of 5 and 6
ports the final reaction products were not isolated from the
2
2
unambiguously. In our case, however, only stannanes take are substantially different [2.054(2) and 2.246(2) Å for 5
part in the reaction and the structures of all key products and 2.054(2) and 2.277(2) and 2.058(2) and 2.271(2) Å for
have been determined by elemental analysis, multinuclear 6, respectively]. However, in contrast to 2, these bonds oc-
NMR spectroscopy, and X-ray diffraction. Thus, we have cupy mutually opposite rather than neighboring positions
unambiguously proved for the first time that compounds of in the Sn O rings.
2
2
the type RSnX are able to undergo a redistribution reac-
According to the DFT calculations (see Supporting In-
3
tion of the hydrocarbon substituent. A more detailed verifi- formation), there are no complexes of type I on the poten-
cation of the supposed reaction scheme will be the subject tial energy surfaces corresponding to the interactions of
of further investigations.
[Et SnCl ] with [Et Sn(OMe) ] and [Bu Sn(OAc) ] with
2 2 2 2 2 2
Complex is the first compound of the type [Bu Sn(OMe) ]. The rearrangement of X and OMe substit-
2
2
2
R SnX ·R SnY whose structure has been determined by uents to yield monomeric [R Sn(OMe)X] is exothermic
2
2
2
2
2
X-ray diffraction. Previously, Kocheshkov and co-workers (∆H0 = –1.5 kcalmol
–1
for R = Et, X = Cl and
Eur. J. Inorg. Chem. 2006, 4271–4277
© 2006 Wiley-VCH Verlag GmbH & Co. KGaA, Weinheim
www.eurjic.org
4273

V. N. Khrustalev et al.
FULL PAPER
Scheme 2.The equilibria of “organotin analogs of Grignard reagents” in solution.[9]
Table 4. Selected bond lengths [Å] and angles [°] for 6.
Sn(1)–O(2)
Sn(1)–C(5)
Sn(1)–C(9)
Sn(1)–O(3)
Sn(1)–O(1)
O(2)–Sn(1)–C(5) 102.24(10)
O(2)–Sn(1)–C(9) 109.69(10)
C(5)–Sn(1)–C(9) 144.82(11)
2.0538(18)
2.121(3)
2.137(3)
2.160(2)
2.2769(19)
Sn(2)–O(1)
2.0577(18)
2.129(3)
2.133(3)
2.1558(19)
2.2714(19)
108.79(10)
Sn(2)–C(19)
Sn(2)–C(15)
Sn(2)–O(5)
Sn(2)–O(2)
O(1)–Sn(2)–C(15)
C(19)–Sn(2)–C(15) 143.19(11)
O(1)–Sn(2)–O(5)
C(19)–Sn(2)–O(5)
C(15)–Sn(2)–O(5)
O(1)–Sn(2)–O(2)
C(19)–Sn(2)–O(2)
C(15)–Sn(2)–O(2)
O(5)–Sn(2)–O(2)
Sn(2)–O(1)–Sn(1)
Sn(1)–O(2)–Sn(2)
84.57(7)
99.91(9)
98.12(10)
69.74(7)
88.72(10)
88.74(10)
154.24(7)
110.09(8)
110.44(8)
O(2)–Sn(1)–O(3)
C(5)–Sn(1)–O(3) 100.27(9)
84.87(8)
C(9)–Sn(1)–O(3)
O(2)–Sn(1)–O(1)
C(5)–Sn(1)–O(1)
C(9)–Sn(1)–O(1)
O(3)–Sn(1)–O(1) 154.22(7)
O(1)–Sn(2)–C(19) 104.65(10)
96.97(10)
69.70(7)
89.50(9)
88.04(10)
Figure 3.View of complex 5. The hydrogen atoms have been omit-
ted for clarity. Displacement ellipsoids are scaled to the 50% prob-
ability level. The coordination bonds are shown by open lines.
Conclusions
The isolation of complexes 2, 5, and 6 provides evidence
for the existence of complexes R SnXY·R SnXY (R = Alk,
2
2
Ar; X, Y = Hal, OR, X ϶ Y) both as unsymmetrical
adducts [R SnX ·R SnY ] and symmetrical dimers
2
2
2
2
[
R SnXY] . Moreover, it has been unambiguously proved
2 2
for the first time that compounds of the type [RSnX ] are
3
able to undergo a hydrocarbon substituent redistribution
reaction. The similarity of the redistribution reactions of
hypercoordinate organotin compounds containing electron-
donating groups both in the hydrocarbon R and in the
functional X substituents indicates that the chemical prop-
erties of these compounds are determined primarily by the
coordination mode of the tin atom rather than by the types
of ligands. We believe that our findings open-up alluring
prospects for the investigation of different transmetallation
processes.
Figure 4.View of complex 6. The hydrogen atoms have been omit-
ted for clarity. Displacement ellipsoids are scaled to the 50% prob-
ability level. The coordination bonds are shown by open lines.
Table 3. Selected bond lengths [Å] and angles [°] for 5.[a]
Sn(1)–O(1)
Sn(1)–C(4)
Sn(1)–C(2)
2.0539(19) Sn(1)–O(1)ii
2.2464(19)
2.5101(8)
2.125(3)
2.126(3)
Sn(1)–Cl(1)
O(1)–Sn(1)–C(4) 106.93(9)
O(1)–Sn(1)–C(2) 108.53(10)
O(1)–Sn(1)–Cl(1)
C(4)–Sn(1)–Cl(1)
C(2)–Sn(1)–Cl(1)
Cl(1)–Sn(1)–O(1) 161.79(5)
Sn(1)–O(1)–Sn(1) 110.06(9)
91.85(6)
93.26(8)
92.56(8)
Experimental Section
C(4)–Sn(1)–C(2) 143.82(11)
ii
ii
O(1)–Sn(1)–O(1)
C(4)–Sn(1)–O(1)
C(2)–Sn(1)–O(1)
69.94(9)
91.89(10)
93.56(9)
General Procedures: All manipulations were carried out under puri-
fied argon using standard Schlenk and high-vacuum-line tech-
niques. The commercially available solvents were purified by con-
ventional methods and distilled immediately prior to use.
ii
ii
ii
[
a] Symmetry transformations used to generate equivalent atoms:
ii: –x, –y + 1, –z.
],[11]
[11]
[11]
[
PhSnCl
3
[MeSnCl
3
],
[EtSnI
(5),
3
],
[Et
3
Sn(OCH
2
CH
2
-
)],[3a] [Et
Sn(Cl)(OMe)]
[8]
and [Bu
Sn(OAc)(OMe)]
NMe
(
2
2
2
2
2
6)[ were synthesized as described earlier. NMR spectra were re-
8]
–
3.0 kcalmol–1 for R = Bu, X = OAc). Their further dimeri-
corded with a Bruker AM-360 NMR spectrometer at 360.134 MHz
0
1
13
zation leads to complexes of type II (∆H = –16.2 and ( H) and 90.555 MHz ( C) for samples in CDCl or CD Cl .
3
2
2
–
1
–
14.2 kcalmol , respectively).
4
Chemical shifts are relative to SiMe for H, C or indirectly refer-
4274
www.eurjic.org
© 2006 Wiley-VCH Verlag GmbH & Co. KGaA, Weinheim
Eur. J. Inorg. Chem. 2006, 4271–4277

2 2
First Complexes R SnXY·R SnXY (R = Alk, Ar; X, Y = Hal, OR, X ϶ Y)
FULL PAPER
enced to TMS via the solvent signals. The accuracy of the coupling
constants is ±0.1 Hz, and the accuracy of chemical shift measure-
solid was 1.33 g (49.7% scaled to the amount of [PhSnCl
168.7–169 °C. C32 Sn (792.94): calcd. C 48.47, H 5.08,
N 3.53; found C 48.30, H 5.30, N 3.55. H NMR (CD
2.36 (br. s, 12 H, NMe ), 2.73–2.78 (br. m, 4 H, NCH ), 3.91–3.96
(br. m, 4 H, OCH ), 7.87–7.91, 7.10–7.50 (two m, 20 H, Ph) ppm.
3
]). M.p.
H
40Cl
2
N
2
O
2
2
1
13
1
ments is ±0.01 ppm for H and ±0.05 ppm for C. Melting points
were measured in sealed capillaries with a SANYO Gallenkamp
PLC melting point apparatus without any additional corrections.
Elemental analyses were performed on a Carlo Erba EA1108
CHNS-O elemental analyzer.
2 2
Cl ): δ =
2
2
2
1
3
C NMR (CD
60.43, 61.06 (NCH
29.03, 129.40 (C ), 130.11, 130.51 (C
2
Cl
2
): δ = 45.45 (br., NMe
2
), 45.60, 45.92 (NMe
2
),
),
2
), 62.48 (br., OCH
2
), 128.87, 129.10 (C
m
1
p
o
), 136.03, 136.20 (C
i
) ppm.
[PhSn(OCH
2
2 2 2 3
CH NMe ) Cl] (1): A solution of [PhSnCl ] (3.78 g,
1
2.50 mmol) in thf (20 mL) was added to an intensely stirred solu-
Reaction of [PhSn(OCH
Experiment): A solution of 1 (0.52 g, 1.3 mmol) and [PhSnCl
(0.39 g, 1.3 mmol) in thf (10 mL) was mixed in a vacuum of
2 2 2 2 3
CH NMe ) Cl] (1) With [PhSnCl ] (NMR
tion of [Et
3
Sn(OCH
2
CH
2
NMe
2
)] (11.85 g, 40.35 mmol) in 70 mL
3
]
of thf. The solution was stirred for 2 h. The solvent was then re-
moved under vacuum to about one sixth of the initial volume and
–
3
10 Torr. The mixture was stored for 1 h at about 20 °C, then thf
was removed by evacuation and CD Cl (1 mL) was introduced.
The solution was transferred to a 5-mm NMR tube and sealed.
70 mL of hexane was added. A white crystalline precipitate was
2
2
obtained, filtered, and washed three times with hexane (in 30 mL
portions) and dried in vacuo. The yield was 3.05 g (60%). M.p.
1
13
According to the H and C NMR spectra, the solution contained
Sn(OCH CH NMe ] and [Ph SnCl ] as the main products.
: H NMR (CD Cl ): δ = 7.60–7.67 (m, 3 H, Ph), 7.81–
2 2
), 7.84 (m, JSn,H = 81.2 Hz, 2 H, Ph) ppm. C NMR (CD Cl ): δ =
1
6
29–131 °C. C14
.87; found C 40.98, H 6.55, N 6.40. H NMR ([D
N), 2.62–2.68, 2.76–2.86 (two br. m, 4 H, NCH
.81–3.86, 3.93–3.99 (two br. m, 4 H, OCH ), 7.10–7.40 (m, 3 H,
H
25ClN
2
O
2
Sn (407.50): calcd. C 41.26, H 6.18, N [Cl
2
2
2
2
)
2
2
2
1
1
8
]thf): δ = 2.29
Ph
2
SnCl
2
3
2
2
13
(br. s, 12 H, Me
2
2
3
4
2
3
2
130.32 ( J = 85.1 Hz, C ), 132.48 ( J = 18.4 Hz, C
i
), 137.50 (C ) ppm.
m
p
), 135.57 ( J =
Ph), 8.12–8.40 (br. s, JSn,H = 99.0 Hz, 2 H, Ph) ppm. 13C NMR 63.6 Hz, C
3
o
(
1
1
[D
8
]thf): δ = 46.12 (br., Me
2
N), 58.59 (NCH
2
), 63.47 (OCH
), 129.52 ( JSn,C = 21.6 Hz, C
), 148.99 (C ) ppm.
2
),
),
3
4
2 2 2 2 2 2 2 2 2
[Cl Sn(OCH CH NMe ) ]: A solution of [Sn(OCH CH NMe ) ]
28.60 ( JSn,C = 112/108 Hz, C
38.04 (br., JSn,C = 61.7 Hz, C
m
p
2
(1.76 g, 5.96 mmol) in thf (15 mL) was quickly added to an in-
tensely stirred solution of HgCl (1.62 g, 5.96 mmol) in thf (20 mL).
A large amount of heavy dark-grey precipitate appeared immedi-
)] (7.82 g, 26.63 mmol) in thf (30 mL) was added ately. The mixture was stirred for 30 min and stored overnight. Af-
o
i
2
[Ph
2
SnCl
2
·Ph
NMe
2 2 2 2 2 3
Sn(OCH CH NMe ) ] (2): A solution of [Et Sn-
(OCH CH
2
2
2
slowly to a stirred solution of [PhSnCl
3
] (4.08 g, 13.50 mmol) in
ter filtration, the solvent was removed under vacuum to about one
sixth of the initial volume. After addition of hexane (50 mL) a
white crystalline precipitate was obtained. This was filtered under
argon, washed with hexane, and dried in vacuo. The yield was
Et O (50 mL) or thf (50 mL) at room temperature. A large amount
2
of white precipitate appeared immediately. After stirring the mix-
ture for 2 h and storing it overnight the white precipitate was fil-
tered, washed with benzene, and dried in vacuo. The yield of white
8 2 2 2
2.12 g (97%). M.p. 205 °C (with decomp.). C H20Cl N O Sn
Table 5. Crystallographic data for 1, 2, 5, and 6.
1
2
5
6
Empirical formula
FW
T [K]
C
407.50
120
14
H
25ClN
2
O
2
Sn
C
792.94
120
32
H
40Cl
2
N
2
O
2
Sn
2
C
486.59
100
10
H
26Cl
2
O
2
Sn
2
C
645.98
100
22 48 6 2
H O Sn
Crystal size [mm]
Crystal system
Space group
a [Å]
b [Å]
c [Å]
0.2×0.2×0.1
monoclinic
0.2×0.2×0.2
monoclinic
C2/c
18.208(3)
10.1149(11)
19.274(3)
90
0.3×0.2×0.2
orthorhombic
Pbca
8.5007(16)
13.843(3)
14.118(3)
90
0.3×0.2×0.2
monoclinic
P2
1
8.2721(4)
20.433(2)
8.3571(5)
90
P2
1
/c
11.496(2)
8.7351(17)
16.660(3)
90
α [°]
β [°]
90.947(6)
90
1672.7(5)
4
116.799(5)
90
3168.4(8)
4
90
90
1661.4(6)
4
1.945
100.660(5)
90
1388.17(17)
2
γ [°] 3
V [Å ]
Z
D
–3
c
[gcm ]
1.618
1.662
1.545
F(000)–
824
1.690
1584
1.777
944
3.316
656
1.829
1
µ [mm ]
2
θ
max [°]
56
54
56
56
Index range
–15 Յ h Յ 15
–23 Յ h Յ 23
–12 Յ k Յ 12
–24 Յ l Յ 24
14829
3453
2434
3453/0/182
0.0496; 0.1121
0.0712; 0.1206
1.038
–11 Յ h Յ 11
–18 Յ k Յ 18
–18 Յ l Յ 18
15113
1984
1927
1984/0/73
0.0248; 0.0548
0.0260; 0.0555
1.018
–10 Յ h Յ 10
–27 Յ k Յ 26
–11 Յ l Յ 11
13583
6565
6515
6565/10/272
0.0210; 0.0537
0.0213; 0.0538
1.022
–
–
11 Յ k Յ 11
19 Յ l Յ 22
No. of reflections collected
No. of unique reflections
No. of reflections with I Ͼ 2σ(I)
Data/restraints/parameters
R1; wR2 [I Ͼ 2σ(I)]
13779
3972
3010
3972/6/181
0.0401; 0.0986
0.0570; 0.1100
1.009
R1; wR2 (all data)
GOF on F2
Tmin; Tmax
0.676; 0.878
0.660; 0.730
0.390; 0.500
0.590; 0.690
Eur. J. Inorg. Chem. 2006, 4271–4277
© 2006 Wiley-VCH Verlag GmbH & Co. KGaA, Weinheim
www.eurjic.org
4275

V. N. Khrustalev et al.
FULL PAPER
(
7
2
365.87): calcd. C 26.26, H 5.51, N 7.66; found C 26.05, H 5.41, N
mechanisms of chemical reactions and processes”. We thank Dr.
1
.40. H NMR (CD
.86 (m, 4 H, CH N), 3.80–3.85 (m, 4 H, CH
Cl ): δ = 46.78, 46.87 (two s, Me
N), 58.03 (3JSn,C = 24.5 Hz,
N), 63.02 ( JSn,C = 57.5 Hz, CH O) ppm.
2
Cl
2
): δ = 2.73, 2.74 (two s, 12 H, Me); 2.83– M. G. Kuznetsova for performing the multinuclear NMR measure-
O) ppm. 13C NMR ments.
2
2
(CD
2
2
2
2
CH
2
2
[
MeSn(OCH
CH NMe )] (6.65 g, 23.33 mmol) in Et
wise to a stirred solution of [MeSnCl
Et O (30 mL). After two hours of stirring an abundant white pre-
2
CH
2
NMe
2
)
2
Cl] (3): A solution of [Et
O (20 mL) was added drop-
] (2.80 g, 11.66 mmol) in
3
Sn(OCH
2
-
[1] Ch. Elschenbroich, A. Salzer, Organometallics: A Concise In-
troduction, Wiley-VCH, Weinheim, New York, Basel, Cam-
bridge, 1992.
2
2
2
3
[
2] a) R. A. Varga, C. Silvestru, C. Deleanu, Appl. Organomet.
Chem. 2005, 19, 153–160; b) S. H. L. Thoonen, H. van Hoek,
E. de Wolf, M. Lutz, A. L. Spek, B.-J. Deelman, G. van Koten,
J. Organomet. Chem. 2006, 691, 1544–1553.
2
cipitate had formed. This was filtered, washed with hexane, and
dried in vacuo. The yield was 2.49 g (61.8%). M.p. 139–140 °C.
C
3
=
4
9
H
23ClN
2 2
O Sn (345.45): calcd. C 31.29, H 6.71, N 8.11; found C
[
3] a) N. N. Zemlyansky, I. V. Borisova, M. G. Kuznetsova, V. N.
Khrustalev, Yu. A. Ustynyuk, M. S. Nechaev, V. V. Lunin, J.
Barrau, G. Rima, Organometallics 2003, 22, 1675–1681; b)
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nometallics 2003, 22, 5441–5446; c) V. N. Khrustalev, M. Yu.
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V. V. Lunin, J. Barrau, G. Rima, J. Organomet. Chem. 2004,
1
2
1.05, H 6.80, N 7.97. H NMR (CD
2
Cl
99.0/103.6 Hz, 3 H, MeSn), 2.57 (br. s, 12 H, Me
H, CH N), 3. 78 (br. m, 4 H, CH
O) ppm. 13C NMR (CD
N), 58.74 (br., CH N), 63.61 (br.,
2
): δ = 0.71 (br. s, JSn,H
N), 2.70 (br.,
Cl ):
2
2
2
2
2
δ = 10.80 (MeSn), 46.27 (Me
CH
2
2
2
O) ppm.
[EtSn(OCH
2
CH
)] (4.47 g, 15.21 mmol) in thf (25 mL) was added drop-
(4.04 g, 7.64 mmol) in Et
30 mL). The mixture was stirred for 2 h and stored overnight. The
2 2 2 3 2
NMe ) I] (4): A solution of [Et Sn(OCH -
689, 478–483; d) V. N. Khrustalev, I. A. Portnyagin, N. N. Zem-
CH
2
NMe
2
lyansky, I. V. Borisova, Yu. A. Ustynyuk, M. Yu. Antipin, J.
Organomet. Chem. 2005, 690, 1056–1062; e) V. N. Khrustalev,
I. A. Portnyagin, N. N. Zemlyansky, I. V. Borisova, M. S. Ne-
chaev, Yu. A. Ustynyuk, M. Yu. Antipin, V. V. Lunin, J. Or-
ganomet. Chem. 2005, 690, 1172–1177; f) V. N. Khrustalev,
I. A. Portnyagin, I. V. Borisova, N. N. Zemlyansky, Yu. A. Us-
tynyuk, M. Yu. Antipin, M. S. Nechaev, Organometallics 2006,
25, 2501–2504.
wise to a stirred solution of EtSnI
(
solvent was removed in vacuo to about one sixth of the initial vol-
ume, then 50 mL of hexane was added to give a white crystalline
precipitate. This was filtered under argon, washed with hexane, and
dried in vacuo. The yield was 1.90 g (56%). M.p. 108–109 °C.
3
2
O
10 2 2
C H25IN O Sn (450.93): calcd. C 26.64, H 5.59, N 6.21; found C
1
[4] a) F. Caruso, D. Leonesi, F. Marchetti, E. Rivarola, M. Rossi,
V. Tomov, C. Pettinari, J. Organomet. Chem. 1996, 519, 29–44;
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M. H. Chisholm, E. E. Delbridge, J. C. Gallucci, New J. Chem.
2004, 28, 145–152.
2
6.35, H 5.78, N 6.15. H NMR (CD
CH CH Sn), 1.73 (m, 2 H, CH CH Sn), 2.63 (br. s, 12 H, Me
.72 (br., 4 H, CH N), 3.80 (br. m, 4 H, CH
CD Cl ): δ = 10.49 (br., CH CH Sn), 13.39 ( JSn,C = 64.4 Hz,
CH Sn), 46.82 (br., Me N), 58.66 (CH N), 63.32 (CH O) ppm.
2
Cl
2
): δ = 1.20 (m, 3 H,
N),
O) ppm. C NMR
3
2
3
2
2
13
2
(
CH
2
2
2
2
2
3
2
3
2
2
2
2
X-ray Crystal Structure Determination: Data were collected on a
Bruker three-circle diffractometer equipped with a SMART 1000
CCD detector and corrected for absorption using the SADABS
program.
and SAINTPlus
[
12]
[13]
Data reduction was performed with the SMART
[
14]
programs (see Table 5 for details). The struc-
tures were solved by direct methods and refined by full-matrix le-
ast-squares on F2 with anisotropic thermal parameters for non-
[
5] a) E. G. Martinez, A. S. Gonzalez, J. S. Casas, J. Sordo, U. Ca-
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0
sellato, R. Graziani, U. Russo, J. Organomet. Chem. 1993, 463,
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91–96; b) F. Caruso, M. Giomini, A. M. Giuliani, E. Rivarola,
be determined unambiguously due to the specific centrosymmetric
arrangement of the heavy tin atoms as well as most of the substitu-
ents (see above). All calculations were carried out using the
SHELXTL program (PC Version 5.10).[
CCDC-607745 through -607748 contain the supplementary crystal-
lographic data for this paper. These data can be obtained free of
charge from The Cambridge Crystallographic Data Centre via
www.ccdc.cam.ac.uk/data_request/cif.
J. Organomet. Chem. 1994, 466, 69–75; c) M. J. Cox, S. Rai-
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15]
1
996, 506, 253–258; f) S.-G. Reoh, S.-H. Ang, S.-B. Teo, H.-K.
Fun, K.-L. Khew, C.-W. Ong, J. Chem. Soc., Dalton Trans.
997, 465–468; g) P. A. Boo, J. S. Casas, E. E. Castellano,
1
Supporting Information (see also the footnote on the first page of
this article): Details of the quantum-chemical calculations.
M. D. Couce, E. Freijanes, A. Furlani, U. Russo, V. Scarcia, J.
Sordo, M. Varela, Appl. Organomet. Chem. 2001, 15, 75–81.
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[
159.
[
[
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Gur’yanova, E. M. Panov, N. A. Slovokhotova, K. A. Ko-
cheshkov, Dokl. Akad. Nauk SSSR 1965, 163, 880–883; b)
N. N. Zemlyansky, I. P. Gol’dstein, E. N. GurЈyanova, O. P.
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kov, Izv. Akad. Nauk SSSR 1967, 728–735.
Acknowledgments
This work was supported financially by the Russian Foundation
for Basic Research (projects nos. 04-03-32662 and 04-03-32549) and
the Russian Academy of Sciences within the frame of the subprog-
ram “Theoretical and experimental study of chemical bonding and
[9] A. C. Chapman, A. G. Davies, P. G. Harrison, W. McFarlane,
J. Chem. Soc. C 1970, 821–824.
4276
www.eurjic.org
© 2006 Wiley-VCH Verlag GmbH & Co. KGaA, Weinheim
Eur. J. Inorg. Chem. 2006, 4271–4277

2 2
First Complexes R SnXY·R SnXY (R = Alk, Ar; X, Y = Hal, OR, X ϶ Y)
FULL PAPER
[
10] a) T. N. Mitchell, J. Organomet. Chem. 1975, 92, 311–319; b)
A. Boaretto, D. Marton, G. Tagliavini, J. Organomet. Chem.
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[13] Bruker AXS, SMART, v. 5.059, Bruker AXS, Madison, Wis-
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[14] Bruker AXS, SAINTPlus, v. 6.01, Bruker AXS, Madison, Wis-
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[15] G. M. Sheldrick, SHELXTL, v. 5.10, Bruker AXS, Madison,
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1
1
[
11] K. A. Kocheshkov, N. N. Zemlyansky, N. I. Sheverdina, E. M.
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Received: June 6, 2006
Published Online: September 13, 2006
[
12] G. M. Sheldrick, SADABS, v. 2.01, Bruker AXS, Madison,
Wisconsin, USA, 1998.
Eur. J. Inorg. Chem. 2006, 4271–4277
© 2006 Wiley-VCH Verlag GmbH & Co. KGaA, Weinheim
www.eurjic.org
4277