Comparative assessment of weak intramolecular coordinations at tin in functionalized mono-organotin trichlorides and mono-organotrialkynyltins by multinuclear solution NMR

Article abstract of DOI:10.1016/S0022-328X(98)00944-9

The intramolecular coordination behaviors of MeOOC(CH₂)₂SnCl₃ and MeOOC(CH₂)₂Sn(CC-Ph)₃ are compared, using multinuclear NMR, including ¹H-¹¹⁹Sn-HMQC spectroscopy. While MeOOC(CH₂)₂SnCl₃ exhibits intramolecular coordination to tin in solution, through the carbonyl oxygen, unlike CH₃COO(CH₂)₃SnCl₃ which coordinates through the alkoxy oxygen, no firm evidence could be obtained for the existence of such an interaction in MeOOC(CH₂)₂Sn(CC-Ph)₃. This is ascribed to the lower electronegativity of an alkynyl group, as compared to a chlorine atom, a result which is, however, in contrast with the fact that hydroxy-functionalized vinylSnPh₃ compounds are known from literature to exhibit such weak intramolecular coordinations.

Full text of DOI:10.1016/S0022-328X(98)00944-9

Journal of Organometallic Chemistry 572 (1999) 233–238
Comparative assessment of weak intramolecular coordinations at tin in
functionalized mono-organotin trichlorides and
mono-organotrialkynyltins by multinuclear solution NMR
Rudolph Willem a,*, Monique Biesemans a, Pascale Jaumier b, Bernard Jousseaume b
a High Resolution NMR Centre (HNMR), Free Uni6ersity of Brussels (VUB), Pleinlaan 2, B-1050 Brussels, Belgium
b Laboratoire de Chimie Organique et Organome´tallique, UMR 5802, Uni6ersite´ Bordeaux I, 351 Cours de la Libe´ration,
F-33405 Talence Cedex, France
Received 2 July 1998; received in revised form 19 August 1998
Abstract
The intramolecular coordination behaviors of MeOOC(CH2)2SnCl3 and MeOOC(CH2)2Sn(CꢀC–Ph)3 are compared, using
1
multinuclear NMR, including H–119Sn-HMQC spectroscopy. While MeOOC(CH2)2SnCl3 exhibits intramolecular coordination
to tin in solution, through the carbonyl oxygen, unlike CH3COO(CH2)3SnCl3 which coordinates through the alkoxy oxygen, no
firm evidence could be obtained for the existence of such an interaction in MeOOC(CH2)2Sn(CꢀC–Ph)3. This is ascribed to the
lower electronegativity of an alkynyl group, as compared to a chlorine atom, a result which is, however, in contrast with the fact
that hydroxy-functionalized vinylSnPh3 compounds are known from literature to exhibit such weak intramolecular coordinations.
© 1999 Elsevier Science S.A. All rights reserved.
Keywords: Intramolecular coordination; Multinuclear solution NMR; Tin
1. Introduction
dynamic equilibrium, the monomeric form of the C3
ester 1, with the alkoxy oxygen coordinating to tin, is
predominant, independently of the concentration, while
by contrast, the oligomeric form predominates increas-
ingly upon concentration increase for the C4/C5 esters
2 and 3 [7]. In ROOC(CH2)2SnCl3 esters [11–14], the
carbonyl oxygen coordinates intramolecularly to tin, in
the crystalline state (R=Me [11], compound 4; R=i-
Pr [12]) as well as in CH2Cl2 [13].
On the other hand, mild hydrolysis of functionalized
mono-organotrialkynyltin compounds, RSn(CꢀCR%)3, is
a convenient route to functionalized mono-organotin
oxides [17,18], because it by-passes the tricky route
through the more unstable organotin trichlorides and
trialkoxides [1]. This enables a more optimal control of
the hydrolysis conditions [17,18]. Determining whether
the tin atom in RSn(CꢀCR%)3 compounds, with R con-
taining a Lewis base, has still sufficient Lewis acidity to
enable an intramolecular coordination should allow the
Mono-organotin trichlorides are of interest as pre-
cursors of tin containing organic–inorganic hybrid ma-
terials and clusters [1–6]. The presence of a functional
group on the carbon chain influences their stability
because of its coordination to tin, dependent on its
nature, the chain length and the solvent [7–15]. ꢀ-
(Trichlorostannyl)alkyl acetates (CH3COO(CH2)n-
SnCl3, n=3–5, respectively compounds 1–3) in
solution [7] are fast equilibrium mixtures of a monomer
with intramolecular coordination and an oligomer with
intermolecular coordination. The C4 ester [16], 2, is a
cyclodimer in the solid state, with coordination from
the carbonyl oxygen to tin. In the solution mixture in
* Corresponding author. Tel.: +32-2-629-32-82; fax: +32-2-629-
32-81; e-mail: rwillem@vub.ac.be.
0022-328X/99/$ - see front matter © 1999 Elsevier Science S.A. All rights reserved.
PII: S0022-328X(98)00944-9

234
R. Willem et al. / Journal of Organometallic Chemistry 572 (1999) 233–238
understanding of their higher stability as compared to
mono-organotin trichlorides [17,18]. Such a weak coor-
dination is plausible, vinyltriphenyltin compounds of
the type HO–CRR%–CHꢁCH–SnPh3 exhibiting such
an interaction [19–25].
2.3. Synthesis of hex-5-enyltrichlorotin, 10
To a solution of diisopropylamine (5.0 g, 50 mmol)
in 40 ml of THF, 20 ml of butyllithium in hexane (2.5
M, 50 mmol) were added at 0°C. After 5 min, tricyclo-
hexylstannane [1] (14.8 g, 40 mmol) in 25 ml of THF
was added, followed after 15 min by 1-bromohex-5-ene
(8.0 g, 50 mmol). The solution was stirred for 2 h at
room temperature. Subsequently, it was hydrolyzed,
decanted and dried with MgSO4. After evaporation of
the solvents, the compound was distilled in a Kugelrohr
apparatus: yield 61%; b.p. 110°C (0.001 mm). Tin tetra-
chloride (10.4 g, 40 mmol) was added slowly to a
solution of hex-5-enyltricyclohexyltin (10.8 g, 24 mmol)
in 40 ml of petroleum ether. After 30 min at 50°C, 140
ml of petroleum ether and 120 ml of acetonitrile were
added and the mixture stirred for 3 h at room tempera-
ture. After decantation, the acetonitrile phase was
washed three times with 100 ml of petroleum ether.
After evaporation of the solvent, the product was dis-
tilled in a Kugelrohr apparatus: yield 27%; b.p. 90°C
(0.001 mm).
This report presents a study of the coordination
behavior in CD2Cl2 solution of CH3OOC(CH2)2-
Sn(CꢀCPh)3, 5, a novel derivative for which no crystals
suitable for X-ray diffraction studies, were obtained.
Our analysis [7,15] uses 1H, 13C, 119Sn [26–28], 17O
1
1D-NMR [29], gradient assisted [30–34] H–119Sn [35–
37] Heteronuclear Multiple Quantum Correlation
(HMQC) [38,39] as well as IR spectroscopy. The NMR
studies were performed on both compounds 4 and 5 in
parallel, taking the well-known [11–14] intramolecular
CD2Cl2 solution coordination behavior of 4 as a refer-
ence. The possible existence of a py–dy interaction
between a vinylic group and a tin atom is also ad-
dressed for 4-pentenyltin trichloride (10) and 5-hex-
enyltin trichloride (11), the NMR and coordination
characteristics of which are compared with those of
compounds 1–3.
2.4. Synthesis of pent-4-enyltrichlorotin, 11
2. Experimental section
Pent-4-enyltrichlorotin 11 was prepared as 10 from
the corresponding pent-4-enyltricyclohexyltin; yield
33%; b.p. 90°C (0.001 mm).
2.1. General
All reactions were carried out under a dry nitrogen
atmosphere. Petroleum ether, THF and toluene were
distilled from sodium benzophenone ketyl prior to use.
Diisopropylamine was distilled on KOH. Acetonitrile
and dichloromethane were distilled on CaH2. Tin tetra-
chloride was distilled before use. 6, 7 [40] and 8 [41] (see
Table 2) were prepared from the corresponding trichlo-
rides according to established procedures. Compound 9
[42] was obtained by transmetallation of tetrak-
is(phenylethynyl)tin with t-butylmagnesium chloride.
2.5. IR spectroscopy
IR spectra in CCl4 were recorded on a Perkin Elmer
Paragon 1000 apparatus.
2.6. NMR experiments
The samples were prepared by dissolving 10 or 100
mg of 4, 15 or 135 mg of 5, in 500 ml of CD2Cl2, 20 or
100 mg of 10, 11 and 12 in 500 ml of C6D6. The
solutions were prepared in vacuo under moisture free
conditions with dichloromethane-d2 from freshly
opened ampules, into NMR tubes which were subse-
quently sealed. All 1H-, 13C-, 119Sn- and 17O-NMR
spectra were recorded at 303 K, unless otherwise indi-
cated, on a Bruker AMX500 spectrometer as previously
described [7,15,34,35,43,44]. Chemical shifts were refer-
enced to the residual solvent peak and converted to the
standard Me4Si scale by adding 5.32 and 53.8 ppm for
1H and 13C nuclei. For 119Sn chemical shifts, J=
37.290665 MHz [45,46] was used. 17O chemical shifts
were referenced to external deionised water at 313 K.
The 17O-NMR spectrum of 4 was recorded in CD2Cl2
at 303 K from a solution containing ca. 200 mg sample
per 0.5 ml of solvent. Under such conditions, no signal
was obtained for 5. Accordingly, the 17O-NMR spec-
trum of 5 was recorded in C6D6 at 343 K from a
2.2. Synthesis of
[2-(methoxycarbonyl)ethyl]tris(phenylethynyl)tin, 5
In a three-necked flask at 0°C, a solution of 10 ml of
butyllithium (2.5 M, 25 mmol) was added to pheny-
lacetylene (2.58 g, 25.2 mmol) in degassed toluene (the
use of undegassed toluene resulted in the formation of
some [2-(butoxycarbonyl)ethyl]tris(phenylethynyl)tin).
After 20 min at room temperature, the lithium reagent
was added dropwise to a solution of [2-(methoxycar-
bonyl)ethyl]trichlorotin [9] (2.28 g, 7.2 mmol) in 30 ml
of dry degassed toluene at −78°C. After 3 h the
mixture was allowed to reach room temperature, stirred
for one additional hour and filtered on dry MgSO4
under nitrogen. The solvents were evaporated at room
temperature under high vacuum and the product chro-
matographed on dry Florisil with dichloromethane as a
solvent: yield 59%; m.p. 66°C.

R. Willem et al. / Journal of Organometallic Chemistry 572 (1999) 233–238
235
nated by y-charge transfers [50], while pure |-electron
density increases induce high frequency 17O shifts
[49,51]. By contrast, the very similar 17O chemical shifts
of 5 (356 and 135 ppm) as compared to those of methyl
butyrate taken as a reference (352 and 137 ppm) do not
support the existence of an intramolecular donor–ac-
ceptor interaction in 5. It should be outlined, however,
that the 17O data of 5 refer to a higher temperature (348
K) than for 4 (303 K), because, unlike 4, no 17O-NMR
signal is visible at room temperature for 5, maybe just
because of an exchange phenomenon involving re-
versible formation and dissociation of the CꢁO“Sn
interaction in 5.
solution with similar concentration. For the purpose of
comparison, the 17O-NMR spectrum of methyl butyrate
was recorded in CD2Cl2 at 303 K. The gradient pulsed
1
proton detected 1D H–119Sn-HMQC correlation spec-
tra were acquired as illustrated recently [7,15,34,37].
3. Results and discussion
Organotrialkynyltins were obtained by phenylethyny-
lation [40,41] of the corresponding trichlorides with
phenylethynyllithium, except 9 which could not be pre-
pared by this method as the corresponding t-butyl-
trichlorotin decomposes in tin dichloride and t-butyl
chloride [47]. The latter compound 9 was obtained by
transmetallation of tetrakis(phenylethynyl)tin with t-
butylmagnesium chloride [42].
Table 1
NMR
data
of
(PhCꢀC)3SnCH2CH2COOCH3
(5)
and
Cl3SnCH2CH2COOCH3 (4) in CD2Cl2 at 303 Ka
The NMR data obtained from CD2Cl2 solutions of 4
and 5 are given in Table 1. Being essentially concentra-
tion independent—unless otherwise specified—only the
NMR parameters from the diluted solutions are given
(see Section 2). The 119Sn chemical shift of 4 changes to
low frequency by only 2 ppm upon a 10-fold concentra-
tion increase, indicating essentially the absence of any
intermolecular coordination, unlike the C4/C5 esters 2
and 3 [7]. The NMR data of 4 confirm the structure
previously proposed from IR data in solution and
X-ray data in the crystalline state (Scheme 1) [11–14].
Though the coordinations of 1 and 4 are strikingly
different, this difference can be rationalized in terms of
the formation of a stable, almost planar, five-membered
ring, upon intramolecular coordination. Coordination
from the carbonyl oxygen in 1 would require the forma-
tion of a seven-membered ring, the higher flexibility of
which destabilizes the intramolecular coordination, as
demonstrated earlier [7]. For analogous reasons, in-
tramolecular coordination is not favoured in 2 and 3,
explaining that cyclodimerization with involvement of
the carbonyl oxygen is preferred [7]. The two different
structures are in full agreement with the non-observa-
tion, for 4, of a 1H–119Sn-HMQC correlation peak
between the OCH3 1H and the 119Sn resonances, in
contrast with the existence of an intense correlation
between the OCH2 1H and the 119Sn resonances of 1 [7].
Unlike 4, none of the NMR data of 5 as such
indicate any possibility of coordination. This specially
holds true for 17O-NMR data. The significant low
frequency shift of the 17O carbonyl resonance of 4 by
−29 ppm, coupled to essentially a negligible change of
its 17O methoxy resonance by +4 ppm with respect to
methyl butyrate confirms the intramolecular carbonyl
oxygen coordination. It is well recognized that interac-
tions of oxygen lone pairs cause a low frequency shift
of the 17O resonance [48,49] when the determinant
electron density increase at the oxygen atom is domi-
Compound (PhCꢀC)3
Cl3SnCH2CH2COOCH3
SnCH2CH2COOCH3 (5)b (4)c
13C
CH2(h)
11.5; 1J(13C–119/117Sn)=
25.0; 1J(13C–119/117Sn)=
695/665
835/798
CH2(i)
29.6; 2J(13C–119/117Sn):
28.1; 2J(13C–119/117Sn)=
41d
72/69
182.0
56.1
–
CꢁO
OCH3
C1ꢀ
176.0
52.6
89.4; 1J(13C–119/117Sn)=
833/796
C2ꢀ
109.2; 2J(13C–119/117Sn)=
–
–
169/161
Cipso
123.1; 3J(13C–119/117Sn):
18d
Cortho
Cmeta
Cpara
132.5
128.7
129.3
–
–
–
119Sn
−257.4
−115.0
1H
CH2(h)
CH2(i)
OCH3
Hortho
1.64; 2J(1H–119Sn):82e
2.26; 2J(1H–119Sn):109e
2.89; 3J(1H–119Sn):132e 2.94; 3J(1H–119Sn):198e
3.77
7.54
3.98
–
–
Hmeta+para 7.36
17Of
CꢁO
(352)g,h 356i
(137)g,h 135i
323g
141g
OCH3
a Chemical shifts referencing as in Section 2. Coupling constants in
Hz.
b 15 mg/0.5 ml.
c 10 mg/0.5 ml.
d Unresolved nJ(13C–119Sn) and nJ(13C–117Sn) coupling constants.
e nJ(1H–119Sn) coupling constants in Hz (in brackets), as deter-
mined from 1D 1H–119Sn-HMQC spectra.
f With respect to water.
g Concentration: ca. 200 mg/0.5 ml CD2Cl2.
h 17O chemical shifts of methyl butyrate in CD2Cl2 at 303 K: CꢁO
352; OCH3 137.
i From a C6D6 solution at 348 K.

236
R. Willem et al. / Journal of Organometallic Chemistry 572 (1999) 233–238
to be a useful structure indicator to further evidence
this proposal.
The multinuclear NMR data for 4-pentenyltin
trichloride (10) and 5-hexenyltin trichloride (11) are
given in Table 3. Though slightly more sensitive to the
1
concentration (especially for the H h-CH2 resonances
showing a high frequency shift of 0.1–0.2 ppm upon
5-fold concentration increase), no informative concen-
tration effects on the 1H- and 13C-NMR parameters
are observed. Henceforth, as in Table 1, only diluted
1
solution H- and 13C-NMR data are provided in Table
3, also because these are most relevant for the assess-
ment of the existence of an intramolecular py–dy in-
teraction from the double CꢁC bond to tin. For
119Sn-NMR, however, the data are provided at two
Scheme 1.
1
concentrations. The H-, 13C- and 119Sn-NMR data for
The IR data lie essentially in the same line. While 4
displays a solution w(C=O) stretch frequency at 1660
cm−1 [13], 5 exhibits its w(CꢁO) stretch at 1729 cm−1
(with some shoulder at 1740 cm−1), comparable to
those of simple non-stannylated esters like methyl ac-
etate, around 1740 cm−1 [13], and to that of methyl
hexyltin trichloride (12) are provided for comparison.
Comparing the 1H- and 13C-NMR data of
Cl3Sn(CH2)3CHꢁCH2 (10) and Cl3Sn(CH2)4CHꢁCH2
(11) with those of Cl3Sn(CH2)5CH3 (12), reveals the
total absence of any evidence for the existence of an
intramolecular coordination from the CHꢁCH2 moiety
to tin, at the level of h-CH2 and i-CH2 1H and 13C
chemical shifts as well as the nJ(1H–119Sn) and
nJ(13C–119/117Sn) coupling constants. The 119Sn-NMR
chemical shifts lead to the same conclusion, despite the
lack of self-consistency in the slight concentration de-
pendence they display, in the alkenyltin trichlorides 10
and 11, as well as hexyltin trichloride 12 and butyltin
trichloride [15]. We have no explanation to this appar-
ently disparate concentration effect in both the alkyl-
and alkenyltin trichlorides, but they are both slight
and obviously unrelated to intramolecular coordina-
tion from a functionality in the R group, whatsoever.
1D 1H–119Sn-HMQC experiments reveal the exis-
tence of correlations between the 119Sn resonance and
butyrate at 1742 cm−1
,
determined here for
comparison.
As 4, the 1D H–119Sn-HMQC spectrum of 5 dis-
plays only correlation signals with the 119Sn resonance
at the level of both CH2 1H resonances, no such corre-
lation being observed for the OCH3 resonance, even
with very long HMQC preparation periods [38,39].
Also the 2J(1H–119Sn) and 3J(1H–119Sn) coupling
constants are significantly larger in 4 than in 5, in
agreement with a higher degree of five-coordination in
4 than in 5.
1
In order to further assess the possible existence of
an intramolecular CꢁO“Sn interaction in 5, we com-
pared its NMR data with those of four other mono-
organotris(phenylethynyl)tin
compounds
[40–42]
where such an interaction cannot be observed because
of the absence of a functional group in the organic
moiety R. Table 2 gives a summary of the most rele-
1
the H resonance of all the protons of the 4-pentenyl
chain of 10, including the vinylic ones. In the case of
11, the terminal vinylic CH2 protons do not exhibit a
correlation, but the vinylic CH and all methylene pro-
tons of the 5-hexenyl chain do. This indicates that
correlations between the 119Sn resonance are observ-
able up to the m-protons, albeit with an intensity de-
crease, at a given constant HMQC preparation time,
as the distance from the tin atom increases, indicating
that in 10 and 11 correlations are observable up to
6J(1H–119Sn) couplings. For comparison, for 12, such
correlations are observed only up to the l-protons
(5J(1H–119Sn) couplings) [7]. These results should be
interpreted with care. Indeed the observability of such
remote couplings in 10 and 11 are traced to a better
transmission of long range couplings through the car-
bon chain due to the presence of the sp2 carbons of
the double CꢁC bond of 10 and 11, not present in 12,
vant data. Despite some dispersion in the J(13C–119/117
1
Sn)(C sp3) coupling constant values (R group), it ap-
pears that the value of 5 is significantly higher than
that
of
the
four
other
non-functionalized
(PhCꢀC)3SnR compounds 6–9. This holds especially
true upon comparison of compounds 5 and 7, which
are most isostructural and thus best comparable in
this respect. In parallel, the 119Sn resonance of 5 is low
frequency-shifted by 15 to 25 ppm with respect to
those of compounds 6–9. Taken together, this data
comparison favours the existence of a very weak in-
tramolecular CꢁO“Sn interaction in 5. Thus, this in-
dicates that the absence of evidence in the 17O-NMR
data of 5 might well be related to the temperature
effect discussed above. On the other hand, the J(13C–
1
119/117Sn)(Cꢀ) coupling constant value does not appear

R. Willem et al. / Journal of Organometallic Chemistry 572 (1999) 233–238
237
Table 2
Comparison of NMR data of (PhCꢀC)3SnCH2CH2COOCH3 (5) with those of other (PhCꢀC)3SnR compounds
Compound
l
119Sn
1J(13C–119/117Sn)(C sp3)
1J(13C–119/117Sn)(Cꢀ)
(PhCꢀC)3SnCH2CH2COOCH3 (5)
(PhCꢀC)3SnCH3 (6)
(PhCꢀC)3SnCH2CH2CH2CH3 (7)
(PhCꢀC)3SnCH(CH3)2 (8)
(PhCꢀC)3SnC(CH3)3 (9)
−257.4
−239.0
−242.0
−235.5
−232.9
695/665
625/598
633/605
833/796
849/814
780/746
731/698
709/679
669/639
a
a Not observed.
NMR data of 10 and 11 on the one hand, 12 on the
other hand (see Table 3).
and not to an effective py–dy interaction. Three pieces
of evidence disfavour the latter interpretation. First,
while plausible in 10 it is not in 11, because only the
CH protons and not the CH2 protons of the vinyl
group do exhibit a correlation. Second, while the corre-
lations first decrease but again increase in intensity as
the alkyl chain of the C4/C5 esters 2 and 3 is traversed
[7], these correlation intensities decrease through the
alkyl chain of the alkenyltin trichlorides 10 and 11.
Third, no other NMR data favour the presence of a
py–dy interaction, as evidenced by a comparison of the
4. Conclusion
For mono-organotin trichlorides with an ester func-
tional group, it can be concluded that the carbonyl
oxygen rather than the alkoxy oxygen of an ester
function is the preferred intramolecular coordination
site, provided the donor–acceptor interaction leads to a
stable ring, e.g. a five-membered one. Only if larger
rings, which are more destabilized by thermal flexibility,
are generated from the intramolecular coordination
with the carbonyl oxygen, does the molecule favour the
alkoxy oxygen coordination from the ester function, in
order to give rise to a more rigid and planar stable
five-membered ring. Unlike mono-organotin trichlo-
rides with ester functions, which generate intramolecu-
lar donor–acceptor interactions from the carbonyl
oxygen to tin, the corresponding mono-organotri-
alkynyltin can generate at most a much weaker interac-
tion between the functional group and the tin atom,
with an unspecified coordination mode, if any. In com-
parison with chlorine atoms, the electronegative effect
of the alkynyl groups is not strong enough to induce on
the metal an electronic deficiency which would be bal-
anced by inter- or intramolecular coordination. To
some extent the absence of a marked donor–acceptor
interaction in such functionalized mono-organotri-
alkynyltin compounds is surprising, as it is well estab-
lished that functionalized vinyltriphenyltin compounds
of the type HO–CRR%-CHꢁCH–SnPh3 (R and R% alkyl
groups) do exhibit a weak intramolecular donor–accep-
tor interaction, despite the lower electronegativity of
the phenyl group, as compared to the alkynyl group
[19–25]; this in turn confirms the stronger donor capac-
ity of the hydroxy function, with respect to the ester
function, as demonstrated recently in comparative in-
vestigations on intramolecular coordinations in HO–
(CH2)nSnCl3 [15] and CH3COO–(CH2)nSnCl3 [7]
derivatives. Finally, unlike trichlorostannylesters, corre-
sponding trichlorostannyl olefins cannot interact in-
tramolecularly with tin, thus ruling out the possible
existence of a py–dy interaction.
Table 3
NMR data of Cl3Sn(CH2)3CHꢁCH2 (10), Cl3Sn(CH2)4CHꢁCH2 (11)
and Cl3Sn(CH2)5CH3 (12) in C6D6 at 303 Ka
Compound
10b
11b
12b
13C
C(h)
C(i)
C(k)
C(l)
C(m)
C(ƒ)
31.3 [659/628]c 31.7 [643/615]c 32.2 [648/620]c
23.7 [58]d
35.5 [116]e
135.9
24.1 [59]d
31.3 [121]e
32.8
24.6 [59]d
31.9 [115]e
30.9
117.4
137.5
22.4
–
115.5
14.0
1H
C(h)
C(i)
C(k)
C(l)
C(m)
C(ƒ)
1.17 [87]f
1.21 [202]g
1.61
5.32
4.90, 4.86
–
1.16 [87]f
1.16 [195]g
0.99
1.66
5.52
1.19 [87]f
1.19 [190]g
1.08
0.92
0.92
4.91, 4.89
0.79
119Sn
100 mg/0.5 ml −9
20 mg/0.5 ml
+6
+7
−3 (−2)h
+5 (+1)h
0
a Chemical shifts referencing as in Section 2. Coupling constants in
Hz.
b Concentration: 20 mg/0.5 ml.
c 1J(13C–119Sn) and 1J(13C–117Sn) coupling constants.
d Unresolved 2J(13C–119Sn) and 2J(13C–117Sn) coupling constants.
e Unresolved 3J(13C–119Sn) and 3J(13C–117Sn) coupling constants.
f 2J(1H–119Sn) coupling constants as determined from 1D 1H–
119Sn-HMQC spectra.
g 2J(1H–119Sn) coupling constants as determined from 1D 1H–
119Sn-HMQC spectra.
h 119Sn chemical shifts of BuSnCl3 given for comparison [15].

238
R. Willem et al. / Journal of Organometallic Chemistry 572 (1999) 233–238
[23] F. Kayser, M. Biesemans, A. Delmotte, R. Hendrix, P.
Acknowledgements
Malschaert, I. Verbruggen, B. Mahieu, M. Gielen, R. Willem,
Bull. Soc. Chim. Belges 103 (1994) 273.
The financial support of the Fund for Scientific Re-
search Flanders (Belgium; grant NR G0192.98) is grate-
fully acknowledged (R.W., M.B.). Partial funding of
this research by contract ERBCHRX-CT94-0610 of the
Human Capital and Mobility (HCM) Programme of
the European Union is acknowledged (B.J., R.W.). B.J.
is indebted to Sipcam-Phyteurop for generous gifts of
chemicals.
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