Functionalised tetraarylstannanes Sn[C6H4-R]4 (R=-CH(CH2O)2, -CH=O, -COOH, -CH=N-NH-C6H3-2,4-(NO2)2, -CH2OH, -CO-NH-CH2-COO-CH3</

Article abstract of DOI:10.1016/j.jorganchem.2004.02.012

Reaction of tin tetrachloride with the appropriate Grignard reagent gave Sn[C₆H₄-CH(OCH₂)₂] ₄ (2), which was transformed to Sn[C₆H₄-CHO]₄ (3) and its hydrazido and ami

Full text of DOI:10.1016/j.jorganchem.2004.02.012

Journal of Organometallic Chemistry 689 (2004) 1546–1552
www.elsevier.com/locate/jorganchem
Functionalised tetraarylstannanes Sn[C6H4-R]4 (R ¼ –CH(CH2O)2,
–CH@O, –COOH, –CH@N–NH–C6H3-2,4-(NO2)2, –CH2OH,
–CO–NH–CH2–COO–CH3, –CH[N(C2H4)2O]2)
a,
a,b
a,b
Michael Veith *, Andreas Rammo a,b, Christian Kirsch, , Lucie Khemtemourian
,
ꢀ
b
Dominique Agustin
a
Anorganische Chemie, Fachbereich 8.11, Universit€at des Saarlandes, Postfach 151150 Saarbr€ucken D-66041, Germany
b
Laboratoire de Chimie Inorganique et Matꢀeriaux Molꢀeculaires, UMR 7071 du CNRS, Batiment F - 4e Etage, Universitꢀe Pierre et Marie Curie,
4 Place Jussieu, Case 42, 75252 Paris Cedex 05, France
Received 14 October 2003; accepted 4 February 2004
Abstract
Reaction of tin tetrachloride with the appropriate Grignard reagent gave Sn[C6H4–CH(OCH2)2]4 (2), which was transformed to
Sn[C6H4–CHO]4 (3) and its hydrazido and amino derivatives Sn[C6H4–CH@N–NH–C6H3-2,4-(NO2)2]4 (5) and Sn{C6H4–
CH[N(C2H4)2O]2}4 (8). Oxidation of (3) produced Sn[C6H4–COOH]4 (4) while reduction of (3) gave Sn[C6H4–CH2–OH]4 (6). From
the acid 4, an amino acid Sn[C6H4–CO–NH–CH2–CO–OCH3]4 (7) could be obtained by reaction with the methyl ester of glycine.
All compounds were isolated in pure form with yields of 40–64% and were characterised by spectroscopic means (heteronuclear
NMR) or by X-ray structure determination (3).
Ó 2004 Elsevier B.V. All rights reserved.
Keywords: Organostannanes; Functionalisation; Branched species; Peptidic coupling with organotin compounds
1. Introduction
compounds [9]. Tetraorganotin derivatives of the gen-
eral formula Sn[C6H4–R]4 (R ¼ para-substituent) [10]
are stable under such conditions and have therefore
found our interest. Representatives of such tetraorg-
anotin derivatives carrying different organic function-
alities in para-position like Sn[C6H4–CH(OCH2)2]4 (2)
and Sn[C6H4–CHO]4 (3) have already been de-
scribed by Drefahl and Lorentz [11] and Hon et al.
[12]. These compounds were so far only character-
ised by elemental analysis. In this paper, we report
about modified syntheses of these compounds and
their complete characterisation using modern spectro-
scopic methods, as multinuclear NMR, IR, mass
spectrometry and X-ray diffraction. Furthermore, we
report about the transformation or derivatisation of
Sn[C6H4–CHO]4 (3) into hydrazones, diamines or the
corresponding alcohol (6) and acid (4). Finally, we
describe the use of 4 to bind to amino acids, in view of
a possible labelling of amino acids by use of 119Sn
NMR spectroscopy.
Organostannanes have attracted considerable atten-
tion in the last 50 years. Basic studies on their physical
[1], spectroscopic (particularly mass spectrometry [2],
NMR [3] and IR [4] spectroscopy) and catalytic
properties [5] have been performed. Organic tin(IV)
compounds also show a wide range of applications [6]
as PVC-stabilizers, as oxidising agents for rubber, as
catalysts for polymers and agricultural fungicides. The
anti-tumoral effect of tin(IV) compounds is further-
more a very interesting application in medicine [7,8].
A necessary prerequisite for the use in medical appli-
cation is the air- and water-stability of tin(IV)
* Corresponding author. Present address: Institut fuer Anorganische
Chemie, Universitaet des Sarrlandes, Im Stadtwald, 66123 Saarbrcken,
Germany. Tel.: +681-302-3415; fax: +681-302-3995.
E-mail address: veith@mx.uni-saarland.de (M. Veith).
0022-328X/$ - see front matter Ó 2004 Elsevier B.V. All rights reserved.
doi:10.1016/j.jorganchem.2004.02.012

M. Veith et al. / Journal of Organometallic Chemistry 689 (2004) 1546–1552
1547
2. Results and discussion
action of tin tetrachloride with the Grignard re-
agent of p-bromobenzaldehyde-ethyleneacetal [11,12]
(Scheme 1). The crude product obtained after filtra-
tion from the inorganic salt and after evaporation of
The first step of our reaction sequences was the
synthesis of Sn[C6H4–CH(OCH2)2]4 (2) by the inter-
O
O
O
O
O
+ SnCl4
Sn
2
4
MgBr
- 4 MgBrCl
O
1
O
O
O
O
NO2
+ 4 H2O, p-TSA - 4 HO(CH2)2OH
O2N
NH
H
O
O2N
NH
N
H
H
O
H
N
NO2
+ 4 H2N-NH-[C6H3-2,4-(NO2)2]
- 4 H2O
Sn
3
Sn
5
O2N
O
N
H
H
HN
NO2
O
N
H
H
HN
NO2
+ 8 HN(CH2)2O - 4 H2O
p-TSA
NO2
O
O
N
N
N
N
O
O
Sn
O
N
O
N
N
N
O
O
8
Scheme 1.

1548
M. Veith et al. / Journal of Organometallic Chemistry 689 (2004) 1546–1552
the solvent was redissolved in CH2Cl2 and precipitated
again by addition of ethanol. Repetition of this pro-
cess for three times gave a pure, colorless powder of
high purity.
Removing the protecting acetal group in 2 was
achieved by hydrolysis in the polar solvent THF using
p-TSA as catalyst [13]. After extraction of 3 with
CH2Cl2 and a subsequent work up the corresponding
stannane Sn[C6H4–CH@O]4 (3) [11], containing four
aldehydic functions, was obtained as a yellow solid. In
comparison to the original literature [11], these two
modified procedures lead to higher yields (60%) and
avoid the time-consuming purification of 2 and 3 by
chromatography over aluminium oxide and subsequent
repeated recrystallisation. The reaction from 2 to 3 can
1
easily be followed by H and 13C NMR. The formation
of the aldehyde groups is accompanied by a change of
the hybridisation on the corresponding carbon atom
from sp3 to sp2 that has a dramatic effect in the two
spectra. Whereas the hydrogen resonances of the acetal
moiety in the starting compound 2 appear at 4.10 ppm,
the hydrogen at the new aldehydic function is shifted
to 10.09 ppm. Parallel changes can be observed in 13C
NMR for the carbon atom attached in the para-posi-
tion of the ring by a shift of the signal at 65.3 to
192.3 ppm.
Fig. 1. Molecular structure of Sn[C6H4–CHO]4 (3) (carbon atoms are
ꢁ
light). Mean bond lengths (A) and angles (°): Sn–C: 2.149 (9), C–O:
1.34(2), C–Sn–C: 109.4(5), C–C–O: 116.0(9).
Colourless crystals of Sn[C6H4–CHO]4 (3), suitable
for the X-ray diffraction study could be obtained by
recrystallisation from dichloromethane. The intensity
measurements were performed on a Stoe Image Plate
(IPDS) at 293 K. The structure was solved by direct
methods and refined by the full-matrix least-squares
method on F . All non-hydrogen atoms were refined
anisotropically and hydrogen atoms were kept fixed in
calculated positions. Programs used were SHELX-93
and SHELX-97 [14]. Unfortunately, the refinement of
the X-ray structure of compound 3 could not be per-
formed satisfactorily, because only tiny crystals of 3
were available. Here, we only give a graphic represen-
tation of 3 with some mean bond lengths and angles
(Fig. 1) [15].
In order to test the accessibility of the CO groups
(absorption at 1701 cmꢀ1 of the CO valence stretching
vibration) in 3 for further bonding, the molecule was
reacted with four equivalents of 2,4-dinitrophenyl-
hydrazine to give the hydrazone [13,16,17] Sn[C6H4–
CH@N–NH–C6H3-2,4-(NO2)2]4 (5) as an orange
powder whereas in the reaction of 3 with the primary
amine morpholine each C@O function reacted with
two morpholine molecules [13,17] to form Sn{C6H4–
CH[N (C2H4)2O]2}4 (8) which separated as a pale
brown powder. In both reactions, the released water
was removed continuously with a water separator
(Scheme 1).
Sn[C6H4–CHO]4 (3) gave the water soluble Sn[C6H4–
COOH]4 (4) and Sn[C6H4–CH2–OH]4 (6) in acceptable
yields (see Scheme 2) without scission of the tin–carbon
bond. The products 4 and 6 were obtained as pure
compounds as may be deduced by inspection of the
spectroscopic and analytical data.
As a test reaction for binding acid amides the ox-
idation product Sn[C6H4–COOH]4 (4) was reacted
with the methylester of glycine [18] to yield Sn[C6H4–
CO–NH–CH2–CO–OCH3]4 (7). The reaction was
carried out in THF as a solvent using 1-hydroxyben-
zotriazole (HOBT) and diisopropyldiimide (DICPD)
as coupling reagents (Scheme 3). These auxiliary
substances are frequently used to activate the car-
boxylic groups of the reactant without deprotection of
glycine [13,17]. The target compound 7 could be iso-
lated in an overall yield of 50% and could be fully
characterised by 1H, 13C, 119Sn NMR, IR and mass
spectroscopic means.
The 119Sn NMR spectra have been obtained of all
compounds 2–8. The narrow chemical shift differences
(2: d ¼ ꢀ126:5 ppm; 3: d ¼ ꢀ133:2 ppm; 4: d ¼ ꢀ142:0
ppm, 5: d ¼ ꢀ125:0 ppm; 6: d ¼ ꢀ128:3 ppm; 7:
d ¼ ꢀ131:4, 8: d ¼ ꢀ141:9 ppm) reflect the similar en-
vironment of the tin atoms in the molecules. Only minor
effects can be noticed from the substituents in the para-
positions of the phenyl groups. As expected the 119Sn
NMR spectroscopy may therefore be used in the label-
ling of amino acids when a binding to the acid has been
performed.
Following classical routes the oxidation [13,17], re-
spectively, reduction [13,17] of the aldehydic function in

M. Veith et al. / Journal of Organometallic Chemistry 689 (2004) 1546–1552
1549
O
H
O
H
H2O2, NaClO2, NaH2PO4
NaBH4
Sn
3
O
H
O
H
OH
O
OH
HO
O
OH
Sn
6
Sn
OH
O
HO
4
HO
O
HO
Scheme 2.
Scheme 3.
3. Conclusion
4. Experimental details
The stepwise syntheses of several new organotin
compounds having four identical reactive organic
functionalities were reported in this work. The stability
of the Sn–C bonds towards oxygen and water has
proved to be sufficient to synthesize the presented or-
ganotin derivatives 2–8. Compounds 4 and 6 are water
soluble and may be used in biological environments. We
were successful to bind the glycine methylester to 4,
showing the potential of these molecules as docking
agents: we also could demonstrate the 119Sn NMR
spectroscopy as a labelling tool in the detection of
amino acids.
4.1. General
IR spectroscopy was performed on a Bio-Rad Win-
IR FTIR Spectrometer. 1H, 13C and 119Sn NMR spectra
were obtained on a Bruker AC 200 spectrometer (1H at
200.1 MHz, 13C at 50.3 MHz and 119Sn at 74.63 MHz).
CP/MAS-spectra were recorded on a Bruker MSL 200S.
Mass spectroscopy was performed on a TSQ Quantum
from Thermo Finnigan. C, H, N elemental analyses
were obtained from a LECO (CHN-900) instrument.
SnCl4 was distilled and stored under dry nitro-
gen before use. Diisopropyldiimide (DIPCD) and

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M. Veith et al. / Journal of Organometallic Chemistry 689 (2004) 1546–1552
1-hydroxybenzotriazole (HOTB) were purchased and
used without further purification.
1H NMR (CDCl3): d (ppm) 7.85 (m, 16H, Ar–H), 10.09
(s, 4H, CHO). 13C NMR (CDCl3): d (ppm) 129.6 (s,
CHAr), 137.1 (s, Cq-Ar), 137.3 (s, CHAr), 144.5 (s, Cq-Ar),
192.3 (s, CHO). 119Sn NMR (CDCl3) d (ppm) )133.2 (s).
IR (KBr disk): 802 cmꢀ1 (Ar), 1701 cmꢀ1 (CHO), 2926
cmꢀ1 (alk). Anal. Calc. for C28H20O4Sn: C, 62.37; H,
3.74. Found: C, 62.44; H, 3.83%. CI-MS (CHCl3): m=z
Calc. for C28H20O4120Sn: 540.03 (M)þ. Found: 541.11
(M + H)þ (correct isotopic set of signals and intensities).
4.2. Sn[C6H4–CH(OCH2)2]4 (2)
A solution of 17.00 g (74.7 mmol) of p-bromobenz-
aldehyde-ethyleneacetal in 80 mL THF was slowly added
over a period of 30 min to 1.93 g (79.4 mmol) of Mg
turnings. In order to start the reaction a crystal of I2 was
added. The dropwise addition was continued in that way
that the solution continued to reflux. To complete the
reaction, the mixture was still heated to 70 °C for 20 min.
After cooling down to room temperature, insoluble parts
like unreacted magnesium, were filtered off. In the next
step, a solution of 1.15 g (4.40 mmol) of freshly distilled
tin tetrachloride in 8 mL benzene was added dropwise.
The reaction mixture was refluxed for 8 h, whereas the
desired product 2 precipitated. By treating the reaction
mixture with a saturated solution of NH4Cl at 0 °C the
precipitate dissolved and two layers were obtained.
The organic layer was separated and washed with water.
The water layer was treated with CHCl3. The combined
organic layers were washed again with water resulting in
a clear yellow solution, which was dried over anhydrous
CaCl2. Removal of the solvent provided a brown oil,
which dissolved in less CH2Cl2. After addition of 200 mL
of dry ethanol a suspension was formed. Under reduced
pressure the CH2Cl2 was removed (2 is soluble in
CH2Cl2!). Compound 2 was filtered off and dried in
vacuum (10ꢀ2 Torr). Impurities were in the filtrate. To
raise the purity of 2 the solid was washed again with dry
ethanol, filtered and dried under reduced pressure. The
4.2 g (60%) of 2 was obtained as a white powder. M.p.
268°. 1H NMR (CDCl3): d (ppm) 4.10 (m, 16H, O–CH2),
5.79 (s, 4H, Ar–CH<), 7.52 (m, 16H, Ar–H). 13C NMR
(CDCl3): d (ppm) 65.3 (s, O–CH2), 103.6 (s, Ar–CH<),
126.5 (s, CHAr), 127.3 (s, Cq-Ar), 137.2 (s, CHAr), 138.9 (s,
Cq-Ar). 119Sn NMR (CDCl3) d (ppm) )126.5 (s). IR (KBr
disk): 812 cmꢀ1 (Ar ring), 1365 cmꢀ1 (C–O–C), 1472
cmꢀ1 (CH2), 2965 cmꢀ1 (CH alkane). Anal. Calc. for
C36H36O8Sn: C, 60.44; H, 5.07. Found: C, 60.44; H,
5.17%. CI-MS (CHCl3): m=z Calc. for C36H36O8120Sn:
716.14 (M)þ. Found: 717.21 (M + H)þ (correct isotopic
set of signals and intensities).
4.4. Sn[C6H4–COOH]4 (4)
To a solution of 0.400 g (0.74 mmol) of 3 in 10 mL
THF was added a solution of 0.023 g (0.18 mmol)
NaH2PO4 in 300 lL of water and 300 lL of an aqueous
solution of H2O2 (35% concentration). After stirring for
5 min, 0.470 g (1.3 mmol) NaClO2 in 5 mL H2O were
added over a period of 30 min. The mixture was stirred
overnight at room temperature. After evaporation of
THF, the residue was diluted with 15 mL water and
extracted with CH2Cl2 (3 ꢁ 25 mL). The organic layer
was stored over anhydrous MgSO4, concentrated and
dried in vacuo resulting a white solid 4 (0.295 g, 65%).
6
1
M.p. dec. >200°. H NMR (d -DMSO): d (ppm) 7.80
(m, 4H, Ar–H), 13.01 (s, 1H, COOH). 13C NMR (d6-
DMSO): d (ppm) 130.5 (s, CHAr), 133.4 (s, Cq-Ar), 138.4
(s, CHAr), 144.6 (s, Cq-Ar), 168.6 (s, COOH). 119Sn NMR
(d6-DMSO) d (ppm) )142.0 (s). IR (KBr disk): 832 cmꢀ1
(Ar ring), 1690 cmꢀ1 (C@O), 3025 cmꢀ1 (OH). Anal.
Calc. for C28H20O8Sn: C, 55.76; H, 3.34. Found: C,
55.13; H, 3.88%. CI-MS (DMSO): (m=z) Calc. for
C28H20O8120Sn: 604.01. Found: 639.01 (M + H2S + H)þ
(correct isotopic set of signals and intensities).
4.5. Sn[C6H4–CH@N–NH–C6H3-2,4-(NO2)2]4 ꢂ 2C7H8
(5)
A solution of 0.5 g (0.93 mmol) 3, 0.74 g 2,4-dini-
trophenylhydrazine and 40 mL dry toluene was refluxed
for 20 h. In order to shift the equilibrium to the side of
the products a water separator was used. The formed
precipitate was filtered off and washed with 20 mL dry
toluene. After drying under reduced pressure (10ꢀ3
Torr) compound 8 was obtained as an orange powder.
M.p. 245° dec. 1H NMR (DMSO): d (ppm) 2.29 (s, CH3
(toluene)), 7.20 (m, ArH (toluene)), 7.50–8.00 (m, Ar–
H), 8.20 (m, Ar–H), 8.71 (s, CH@N), 8.83 (m, Ar–H).
13C NMR (DMSO): d (ppm) 21.2 (s, CH3 (toluene)),
116.9 (s, CAr (hydrazine ligand)), 123.2 (s, CAr (hydra-
zine ligand)), 125.5 (s, CAr (toluene)), 127.6 (s, CAr
(hydrazine ligand)), 128.4 (s, CAr (toluene)), 129.0 (s,
CAr (toluene)), 129.8 s, (CAr (hydrazine ligand)), 130.0
(s, CAr), 135.0 (s, CAr (hydrazine ligand)), 137.2 (s, CAr
(toluene)), 137.4 (s, CAr), 137.6 (s, CAr), 140.8 (s,
CH@N), 144.6 (s, CAr), 149.3 (s, CAr (hydrazine li-
gand)). 119Sn (CP-MAS): d (ppm) )125.0. IR (KBr
4.3. Sn[C6H4–CHO]4 (3)
To a solution of 2.0 g (2.80 mmol) of compound 2 in
90 mL THF were added 30 mL H2O and 0.2 g (0.90
mmol) p-toluenesulfonic acid. The reaction mixture was
refluxed for 8 h under nitrogen. Compound 3 was ex-
tracted with dichloromethane (5 ꢁ 20 mL) and washed
two times with 20 mL of water. The organic phase was
separated and dried over anhydrous CaCl2. Removal of
the solvent under reduced pressure (10ꢀ2 Torr) provided
compound 3 as a yellow powder (1.0 g, 65%). M.p. 180°.

M. Veith et al. / Journal of Organometallic Chemistry 689 (2004) 1546–1552
1551
disk): 833 cmꢀ1 (Ar ring), 1619 cmꢀ1 (C@N), 3105 cmꢀ1
(CAr@CAr), 3288 cmꢀ1 (NH). Anal. Calc. for
C52H36N16O16Sn ꢂ 2C7H8: C, 54.90; H, 3.63; N, 15.22.
Found: C, 55.18; H, 3.58; N, 14.95%.
(0.62 g, 64%) was obtained as a pale brown powder.
1
M.p. 180° dec. H NMR (CDCl3, without toluene): d
(ppm) 2.49 (m, CH2), 3.00 (s, Ar–CH–N), 3.71 (m,
CH2), 7.20–7.70 (m, Ar–H). 13C NMR (CDCl3, without
toluene): d (ppm) 49.5 (s, CH2), 67.5 (s, CH2), 88.9 (s,
CH), 125.7 (s, CHAr), 129.2 (s, CHAr), 136.5 (s, CHAr),
137.7 (s, CHAr). 119Sn (CDCl3): d (ppm) )141.9. IR
(KBr disk): 876 cmꢀ1 (Ar ring), 1116 cmꢀ1 (C–O–C),
1453 cmꢀ1 (CH2), 2811–2957 cmꢀ1 (CHAr; CH2), 3443
cmꢀ1 (C–N). Anal. Calc. for C60H84N8O4Sn ꢂ 1.5C7H8:
C, 65.02; H, 7.43; N, 8.60. Found: C, 64.91; H, 7.47; N
8.57%.
4.6. Sn[C6H4–CH2–OH]4 (6)
To a solution of 0.100 g (0.18 mmol) 3 was added 10
mL THF. After 5 min stirring, 0.028 g (0.74 mmol)
NaBH4 was added over a period of 10 min at 0 °C. After
one hour of further stirring, 1 mL of a solution of 0.1 N
NaOH was added at room temperature. The reaction
mixture was extracted with 10 mL CH2Cl2 and the
combined organic layers were dried over anhydrous
Na2SO4. Removal of the solvent provided the com-
pound 6 (0.395 g, 40%) as a white powder. M.p. dec.
>200°. 1H NMR (d6-DMSO): d (ppm) 4.56 (m, 8H,
CH2), 7.52 (m, 16H, Ar–H). 13C NMR (d6-DMSO): d
(ppm) 64.5 (s, CH2), 128.7 (s, CHAr), 137.1 (s, Cq-Ar),
137.8 (s, CHAr), 145.4 (s, Cq-Ar). 119Sn NMR (d6-
DMSO) d (ppm) )128.3 (s). IR (KBr disk): 802 cmꢀ1
(Ar ring), 1464 cmꢀ1 (CH2), 2841 cmꢀ1 (CH2), 3272
cmꢀ1 (OH).
Acknowledgements
We thank the Deutsche Forschungsgemeinschaft for
€
the financial support in the ‘‘Europaisches Graduier-
tenkolleg GRK 532: Physikalische Methoden in der
Strukturellen Erforschung Neuer Materialien’’. All the
authors thank Dr. M. Angotti from the research group
of Pharmaceutical Chemistry of Prof. Dr. R.W. Hart-
€
mann at the ‘‘Universitat des Saarlandes’’ in Sa-
arbrucken for the mass spectrometry measurements.
4.7. Sn[C6H4–CONH–CH2–COOCH3]4 (7)
€
Dr. F. Picard is also thanked for the fruitful scientific
discussions.
In 10 mL THF, 0.500 g (0.829 mmol) of 4 was dis-
solved and 0.416 g (3.32 mmol) of H2N–CH2–OOCH3,
505 lL (3.75 mmol) of Et3N and 0.067 g (0.497 mmol)
HOBT were added to this mixture at 0 °C. The solution
was maintained at pH 5. Then 5.568 lL (3.75 mmol)
DIPCD was added. This mixture was stirred at 0 °C for
30 min and warmed up to room temperature overnight.
The crude material was purified by filtration and by
vacuum drying. Compound 7 (0.350 g, 50%) was ob-
tained as white powder. 1H NMR (CDCl3): d (ppm) 3.52
(s, CH2), 3.70 (s, O–CH3), 7.38–7.74 (m, Ar–H). 13C
NMR (CDCl3): d (ppm) 41.5 (s, CH2), 52.0 (s, O–CH3),
127.0 (s, CHAr), 134.4 (s, Cq-Ar), 136.7 (s, CHAr), 140.8
(s, Cq-Ar), 167.5 (s, C@O), 170.3 (s, C@O). 119Sn NMR
(CDCl3): d (ppm) )131.4 (s). IR (KBr disk): 802 cmꢀ1
(Ar ring), 1259 cmꢀ1 (C–O ester), 1380 cmꢀ1 (CH2,
CH3), 1533, 1647 and 3349 cmꢀ1 (CO–NH), 1755 cmꢀ1
(C@O ester), 2876 cmꢀ1 (OCH3), 2971 cmꢀ1 (CH2
and CH3). CI-MS (CHCl3): m=z Calc. for
References
[1] (a) M. Lequan, C. Branger, J. Simon, T. Thami, E. Chauchard,
A. Persoons, Adv. Mater. 6 (1994) 851;
(b) M. Lequan, C. Branger, J. Simon, T. Thami, E. Chauchard,
A. Persoons, Chem. Phys. Lett. 229 (1994) 101;
(c) C. Fiorini, J.-M. Nunzi, P. Raimond, C. Branger, M. Lequan,
R.-M. Lequan, Synth. Met. 115 (2000) 127.
[2] J.M. Miller, Y. Luo, I. Wharf, J. Organomet. Chem. 542 (1997)
89.
[3] (a) G. Barbieri, F. Taddei, J. Chem. Soc., Perkin Trans. 10 (1972)
1323;
(b) G. Matsubayashi, H. Koezuka, T. Tanaka, Org. Magn. Res. 5
(1973) 529;
(c) S.V. Petrosyan, Progr. Nucl. Magn. Res. Spect. 11 (1975) 115;
(d) G. Eng, C.R. Dillard, Inorg. Chim. Acta 31 (1978) 227;
(e) I. Wharf, Can. J. Spectr. 31 (1986) 27;
C40H40O12N4120Sn + H:
889.17.
Found:
889.40
(M + H)þ (correct isotopic set of signals and intensities).
(f) C. Schneider-Koglin, B. Mathiasch, M. Draeger, J. Organo-
met. Chem. 448 (1993) 39;
(g) I. Wharf, M.G. Simard, J. Organomet. Chem. 532 (1997) 1;
(h) M. Charisse, A. Zickgraf, H. Stenger, E. Brau, C. Desmar-
quet, M. Drager, S. Gerstmann, D. Dakternieks, J. Hook,
Polyhedron 17 (1998) 4497;
4.8. Sn{C6H4–H[N(CH2)2O]2}4 ꢂ 1.5C7H8 (8)
A solution of 0.450 g (0.84 mmol) 3, 1.160 g (13.35
mmol) morpholine and 0.100 g pTSA in 25 mL toluene
was refluxed for 12 h. The released water was removed
with a water separator. The formed precipitate was fil-
tered off, washed with 20 mL dry toluene and dried in
vacuum (10ꢀ3 Torr) at room temperature. Compound 5
(i) I. Wharf, Inorg. Chim. Acta 159 (1989) 41;
(j) C. Schneider-Koglin, B. Mathiasch, M. Draeger, J. Organo-
met. Chem. 469 (1994) 25.
[4] (a) S. Griffiths, A.W. Derwish, J. Mol. Spectrosc. 11 (1963) 81;
(b) I. Wharf, A. Bastone, E.J. Bures, J. Can. J. Appl. Spectr. 41
(1996) 122.

1552
M. Veith et al. / Journal of Organometallic Chemistry 689 (2004) 1546–1552
[5] (a) S. Oi, S. Fukita, Y. Inoue, Chem. Commun. 22 (1998) 2439;
(b) K. Fugami, K. Kawata, T. Enokido, Y. Mishiba, S.
Hagiwara, Y. Hirunuma, D. Koyama, M. Kameyama, M.
Kosugi, J. Organomet. Chem. 611 (2000) 433;
(k) I. Wharf, M.G. Simard, J. Organomet. Chem. 332 (1987) 85;
(l) I. Wharf, M.G. Simard, H. Lamparski, Can. J. Chem. 68
(1990) 1277;
(m) G. Deleris, M. Bayle, G. Lain, J. Susperregui, A. Petsom,
Synth. Commun. 25 (1995) 1831;
(c) T. Ohe, T. Wakita, S.-I. Motofusa, C.S. Cho, T. Ohe, S.
Uemura, Bull. Chem. Soc. Jpn. 73 (2000) 2149;
(d) T. Ohe, S.-I. Motofusa, T. Ohe, S. Uemura, Bull. Chem. Soc.
Jpn. 74 (2001) 1343;
(n) M. Schurmann, A. Silvestri, G. Ruisi, M.A. Girasolo, A.B.
Paulsen, F. Huber, R. Barbieri, J. Organomet. Chem. 584 (1999)
293;
(e) T. Ohe, S. Uemura, Tetrahedron Lett. 43 (2002) 1269.
[6] J.R. Stemniski, G.R. Wilson, J.O. Smith, K.L. McHugh, ASLE
(Am. Soc. Lubrication Engrs.) Trans. 7 (1964) 43.
[7] G. Eng, Y.Z. Zhang, D. Whalen, R. Ramsammy, L.E. Khoo, M.
DeRosa, Appl. Organomet. Chem. 8 (1994) 445.
[8] G. Marcel, Appl. Organomet. Chem. 16 (2002) 481.
[9] H. Gillman, J. Organomet. Chem. 15 (1950) 994.
[10] (a) V.S. Griffiths, G.A.W. Derwish, J. Mol. Spectrosc. 7 (1961)
233;
(o) I. Wharf, A.-M. Lebuis, Main Group Met. Chem. 23 (2000)
497;
(p) V.Y. Lu, T.D. Tilley, Macromolecules 33 (2000) 2403;
(q) M.A.A. l-Araj, A.A.S. El-Khaldy, O.S.M. Nasman, Main
Group Met. Chem. 25 (2002) 301.
[11] G. Drehfahl, D. Lorentz, J. Pract. Chem. 24 (1964).
[12] Y.S. Hon, C.F. Lee, R.J. Chen, P.H. Szu, Tetrahedron 57 (2001)
5991.
[13] B.S. Furniss, A.J. Hannaford, V. Rogers, P.W.G. Smith, A.R.
Tatchell (Eds.), Textbook of Practical Organic Chemistry, fifth
ed., Addison-Wesley, London-New York, 1996.
[14] G.M. Sheldrick, Programme for Structure Determination, Vers.
(b) R.G. Neville, Can. J. Chem. 1 (1963) 814;
(c) G. Drefahl, D. Lorenz, J. Prakt. Chem. 24 (1964) 106;
(d) B.W. Rockett, M. Hadlington, W.R. Poyner, J. Appl. Polym.
Sci. 18 (1974) 745;
€
SHELX-93 and SHELX-97, Gottingen, Germany.
(e) M. Gielen, H. Mokhtar-Jamai, Bull. Soc. Chim. Belg. 84
(1975) 197;
[15] Crystallographic data for 3: C28H20O4Sn, Mr ¼ 539:13 g molꢀ1
,
ꢁ
monoclinic, P2=c, a ¼ 10:815ð2Þ, b ¼ 6:7980ð1Þ, c ¼ 19:986ð4Þ A,
3
b ¼ 103:12ð3Þ°, V ¼ 1431:0ð4Þ A , Z ¼ 2, dcalc: ¼ 1:252 Mg/m3,
ꢁ
(f) F.G. Thorpe, S.W. Breuer, G.M. Pickles, T. Spencer, J.C.
Podesta, J. Organomet. Chem. 145 (1978) C26;
(g) D.W. Allen, J.S. Brooks, R. Formstone, J. Organomet. Chem.
172 (1979) 299;
F ð000Þ ¼ 540, diffractometer used: Stoe Image Plate (IPDS), T ¼
293 K, 1.9° 6 h 6 24°, data/restraints/parameters ¼ 4071/0/108,
Full-matrix-least-squares on F 2, R1 ¼ 8:73. The refinement could
not be continued because of the poor data due to the tiny crystals.
[16] K. Paulrannan, T. Chen, R. Hale, Tetrahedron 56 (2000) 8071.
[17] Th. Eicher, L.F. Tietze, Organisch-chemisches Grundpraktikum,
Georg Thieme, Stuttgart-New York, 1993.
(h) K.C. Molloy, J.J. Zuckerman, H. Schumann, G. Rodewald,
Inorg. Chem. 19 (1980) 1089;
(i) H. Schumann, G. Rodewald, U. Rodewald, J.L. Lefferts, J.J.
Zuckerman, J. Organomet. Chem. 187 (1980) 305;
(j) G.M. Pickles, T. Spencer, F.G. Thorpe, A.B. Chopa, J.C.
Podesta, J. Organomet. Chem. 260 (1984) 7;
[18] K. Tilley, M. Akhtar, D. Gani, J. Chem. Soc., Perkin Trans. 1
(1994) 3079.