Structure of N,C,N-chelated organotin(IV) fluorides

Article abstract of DOI:10.1016/j.jorganchem.2007.06.055

The set of starting tri-, di- and monoorganotin(IV) halides containing N,C,N-chelating ligand (L^NCN = {1,3-[(CH₃)₂NCH₂]₂C₆H₃}^-) has been prepared (1-5) and two compoun

Full text of DOI:10.1016/j.jorganchem.2007.06.055

Journal of Organometallic Chemistry 692 (2007) 4287–4296
www.elsevier.com/locate/jorganchem
Structure of N,C,N-chelated organotin(IV) fluorides
a
b
c
a,
a
*
˚
´
´ ˇ
´
´ˇ
´
ˇ
ˇ
ˇ
Petr Novak , Ivana Cısarova , Lenka Kolarova , Ales Ruzˇicka , Jaroslav Holecek
a
ˇ
Department of General and Inorganic Chemistry, Faculty of Chemical Technology, University of Pardubice, na´m. Cs. legiı´ 565, CZ-532 10,
Pardubice, Czech Republic
Department of Inorganic Chemistry, Faculty of Natural Science, Charles University in Prague, Hlavova 2030, 128 40 Praha 2, Czech Republic
ˇ
Department of Analytical Chemistry, Faculty of Chemical Technology, University of Pardubice, na´m. Cs. legiı´ 565, CZ-532 10, Pardubice, Czech Republic
b
c
Received 9 February 2007; received in revised form 20 June 2007; accepted 28 June 2007
Available online 4 July 2007
Abstract
The set of starting tri-, di- and monoorganotin(IV) halides containing N,C,N-chelating ligand (LNCN = {1,3-[(CH3)2NCH2]2C6H3}ꢀ)
has been prepared (1–5) and two compounds structurally characterized ([LNCNPh2Sn]+I3ꢀ (1c), LNCNSnBr3 (5)) in the solid state. These
compounds were reacted with KF with 18-crown-6, NH4F or LCNnBu2SnF to give derivatives containing fluorine atom(s). Triorgano-
tin(IV) fluorides LNCNMe2SnF (2a) and LNCNnBu2SnF (3a) revealed monomeric structural arrangement with covalent Sn–F bond both
in the coordinating and non-coordinating solvents, except the behaviour of 3a that was ionized in the methanol solution at low temper-
ature. The products of fluorination of LNCNSnPhCl2 (4) and 5 were described by NMR in solution as the ionic hypervalent fluorostan-
ꢀ
nates or the oligomeric species reacting with chloroform, methanol or moisture to zwitterionic monomeric stannate LNCN(H)+SnF4
(5c), which was confirmed by XRD analysis in the solid state.
Ó 2007 Elsevier B.V. All rights reserved.
Keywords: Organotin(IV) fluorides; N,C,N-ligand; Structure
1. Introduction
zag’’ F-Sn–F chains [5]. These compounds have relatively
high melting points, and are rather insoluble in common
organic solvents, which is a limitation in the studies of their
structure and reactivity. Only a small number of com-
pounds containing bulky ligands, e.g., Sn[C(SiMe2Ph)3]-
Me2F [6], Sn[C(SiMe3)3]Ph2F [6], Sn(C6H2Me3-2,4,6)3F
[7] and Sn(CH2SiMe3)3F [8], with a four-coordinated tin
central atom, are monomeric with a Sn–F terminal single
One of the goals in the chemistry of tri-, di- and mono-
organotin(IV) compounds is to prepare and structurally
characterize monomeric organotin fluorides, which are of
great interest due to their ability to undergo the metathet-
ical halide for fluoride exchange reactions with different
kinds of organometallic halides [1]. The latest published
application of triorganotin(IV) fluorides, namely Ph3SnF,
deals with liquid–solid phase-transfer catalyzed fluorina-
tions of alkyl halides and sulfonates, where Ph3SnF acts
as a phase-transfer catalyst via continuous formation of
lipophilic Ph3SnF2 anions entering organic phase in the
form of potassium salt [2–4].
The structures of many tri- and a limited number of
diorganotin fluorides have been determined and found to
be either oligo- or polymeric with the ‘‘rod-like’’ or ‘‘zig-
˚
bond distance about 1.96A [9].
In the case of diorganotin difluorides, only a limited
number of monomeric species are known, because a whole
class of these compounds tends to form insoluble polymeric
chains or nets via intermolecular associations [10], or
hypervalent complexes with excess of fluoride ion, which
were studied at ꢀ100 °C by 19F and 119Sn NMR spectros-
copy [11]. Only one purely monomeric diorganotin com-
pound has been described in the solid state by
crystallographic techniques [12]. It is a quinoline substi-
tuted dialkyltin difluoride (Fig. 1A) which was prepared
by reaction of alkyltin(II) compound with tin(II) fluoride
ꢀ
*
Corresponding author. Tel.: +420 466037151; fax: +420 466037068.
˚
E-mail address: ales.ruzicka@upce.cz (A. Ruzˇicˇka).
0022-328X/$ - see front matter Ó 2007 Elsevier B.V. All rights reserved.
doi:10.1016/j.jorganchem.2007.06.055

4288
P. Nova´k et al. / Journal of Organometallic Chemistry 692 (2007) 4287–4296
O
O
NMe2
H
F
F
N
N
F
NMe2
Sn
NMe2
O
P
Sn
O
P
O
Sn
F
SiMe3
Sn
F
F
EtO
EtO
OEt
F
H
F
Me2N
OEt
SiMe3
A
B
C
D
Fig. 1. Structure of monomeric diorganotin difluorides.
in boiling THF. The fluorine and nitrogen atoms occupy
the equatorial plane both mutually in cis-fashion and car-
bons are in the apical positions of the distorted octahedron.
There are two more compounds published aspire to apper-
tain to this group. These compounds are monomeric in
solution, but dimeric in the solid state because bridging
water molecule(s) are present in their structure. Both com-
pounds with [(CH3)2N(CH2)3] [13] and {2,6-[P(O)(OEt)2]2-
4-t-Bu-C6H2} [14] ligands (Fig. 1B and C), respectively,
having tin in ‘‘all-trans’’ deformed octahedron coordina-
tion geometry, one of fluorine atoms from the first part
of molecule being connected to the second part by one or
two oxygen atom bridges.
Another two compounds as the product of rearrange-
ments [15] or reactions of B with an excess of fluoride ion
or amine originated from ligand quarternization [16] have
been reported. The X-ray based investigations of some
difluorotriorganostannates appeared as well [17,18]. Con-
cerning monomeric monoorganotin(IV) fluoride only one
monomeric compound has been prepared by reaction of
tris(2,6-dimethoxyphenyl)methanol with SnF2 in diluted
H2SO4 providing tris(2,6-dimethoxyphenyl)methylstannyl-
trifluoride [19]. The tin atom in this compound is seven-
coordinated and described by the authors as the distorted
monocapped-trigonal-antiprism with Sn–F bond lengths
C6H3}-) with the main focus on the structure of the respec-
tive fluorides.
2. Results and discussion
The representative group of tri-, di- and monoorgano-
tin(IV) halides (Scheme 1) has been chosen in order to
study the differences in structure of products of their fluo-
rination by different methods (KF in biphasic system, KF
with 18-crown-6, NH4F or LCNnBu2SnF).
The iodo-derivative of compound 1, 1b (LNCNPh2SnI)
has been used previously for the preparation of some
organotin carboxylates [26]. Applying the same synthetic
procedure, we obtained 1c only, which showed the same
spectral parameters described previously for 1b. Com-
pound 1c is ionic with the known structure [27] of five-
coordinated stannylium ion and the triiodide takes the
place of the counter anion (Fig. 2). Unfortunately, this spe-
cies did not reveal reactivity towards the fluorinating
agents used because of its ionic character. Fluorination of
2 by KF and 18-crown-6 in benzene yielded LNCNMe2SnF
(2a) which revealed a similar structural behaviour (e.g. five-
coordinated tin atom d (119Sn) = ꢀ83.5 (d); 1J(119Sn,
19F) = 2160 Hz) in solution as previously reported in ana-
log LCNMe2SnF[20] with a five-coordinated tin centre
and the dynamic exchange of nitrogen donors.
˚
from 1.948(7) to 1.975(6) A.
Compound 3a, prepared in biphasic system ether/water,
revealed the same structural behaviour in non-coordinating
solvents as was found for 2a with retained covalent Sn–F
bond (in CDCl3 at 300 K d (119Sn) = ꢀ96.0 ppm (d);
1J(119Sn, 19F) = 2195 Hz; d (119Sn) = ꢀ107.1 ppm (d);
1J(119Sn, 19F) = 2286 Hz; CDCl3 (235 K); d (119Sn) =
ꢀ107.7 ppm (d); 1J(119Sn, 19F) = 2320 Hz; toluene-d8,
Recently, we have reported triorganotin(IV) fluorides of
general formula LCNR2SnF, where LCN is {2-
[(CH3)2NCH2]C6H4}ꢀ and R are alkyl (Me, nBu, tBu) or
aryl (Ph) groups of different steric bulk and electronic
properties [20]. The compounds have five-coordinated tin
and are able to fluorinate titanocene dichloride essentialy
quantitatively. In our latest reports in this field, we
reported the di- [21] (Fig. 1D) and monoorganotin(IV)
[22] fluorides wearing the same ligand. These compounds
are presumably tri- or tetranuclear species with rather
low solubility in common organic solvents and we used
them as a part of selective and sensitive carriers for fluoride
ion recognition [23]. In our latest paper, we reported the
structure and fluorination ability of C,N-chelated n-butyl-
tin(IV) fluorides [24] towards organochlorosilanes, chloro-
phosphine and some metal halides.
LNCNSnR1R2R3
1; R1=R2=R3=Ph
N(CH3)2
Sn
2'
3'
2; R1=R2=Me, R3=Cl
3; R1=R2=nBu, R3=Cl
4; R1=Ph, R2=R3=Cl
5; R1=R2=R3=Br
1'
4'
N(CH3)2
1
3
2
nBu =
4
Ph =
4
1
In this paper, we would like to expand our contributions
[25] on the structure of N,C,N-chelated tri-, di- and mono-
2
3
organotin(IV)
halides
(LNCN = {1,3-[(CH3)2NCH2]2-
Scheme 1.

P. Nova´k et al. / Journal of Organometallic Chemistry 692 (2007) 4287–4296
4289
was observed [25a]. The dynamic process (Fig. 3) was
determined on the basis of VT 119Sn and 19F NMR spectra
in methanol. There, one singlet resonance at ꢀ165.9 ppm
corresponding to the structural type depicted in Fig. 3 as
type B and the broad doublet at ꢀ198.8 ppm with
1J(119Sn, 19F) = 2294 Hz related to the type A, as a result
of dissociation of Sn–F bond at room temperature, are
observed. At 260 K new singlet at +53.4 ppm appeared in
the spectrum. Such downfield shift is characteristic for
the process of ionization leading to the limit ionic structure
C ([(LNCN)Bu2Sn]+) as a consequence of strengthening of
Sn–N interaction and five- or better [3 + 2] coordinated
tin centre. With further decrease of temperature to 200 K
the only detectable signal was d(119Sn) = 48.8 ppm which
is due to further increase of Sn–N bond strength and an
extrusion of methanol molecule from tin coordination
sphere as shown in the limit structure C. In 19F NMR spec-
tra at 260 K, two broad signals, are at ꢀ149.0 ppm with
1J(19F, 119Sn) = 2398 Hz, corresponding to structure A,
and the other at ꢀ130.0 ppm corresponding to values of
free F ion, were observed. Decreasing the temperature to
the limit 170 K, adjacent broad signals were detected
(ꢀ131.1; ꢀ137.8; ꢀ146.2; ꢀ147.9; ꢀ150.4 at 170 K). The
signal with the tin satellites observed at higher temperature
(ꢀ149.0 ppm; 260 K) was getting broader and at 200 K was
not detected which can be explained by Sn–F bond dissoci-
ation and ionic structure formation. The next signals at
lower temperature can be explained by an interaction of
‘naked’ fluorine ion with the solvent molecules.
Fig. 2. Molecular structure of 1c (ORTEP, 50% probability level).
Hydrogen atoms are omitted for clarity. The selected distances (A) and
˚
angles (°): Sn(1)–N(1) 2.417(3), Sn(1)–N(2) 2.428(3), Sn(1)–C(11) 2.092(3),
Sn(1)–C(21) 2.122(3), Sn(1)–C(31) 2.121(3), I(1)–I(2) 2.8918(4), I(2)–I(3)
2.9388(4), C(11)–Sn(1)–C(31) 118.17(13), C(11)–Sn(1)–C(21) 122.93(13),
C(31)–Sn(1)–C(21) 118.86(13), C(11)–Sn(1)–N(1) 75.47(12), C(31)–Sn(1)–
N(1) 97.19(12), C(21)–Sn(1)–N(1) 99.28(12), C(11)–Sn(1)–N(2)-75.66(12),
C(31)–Sn(1)–N(2) 98.71(12), C(21)–Sn(1)–N(2) 94.04(12), N(1)–Sn(1)–
N(2) 151.00(10), C(12)–C(11)–Sn(1) 118.9(2), C(16)–C(11)–Sn(1) 119.5(3),
I(1)–I(2)–I(3) 178.087(13).
During the preparation of fluoride derivatives of diorg-
anotin [21], a more complicated situation than triorganotin
fluorides containing LCN ligand was observed. Similar to
Dakternieks [11], the phenyl group migration in the case
of reactivity of diorganotin LCNSnPhCl2 was observed.
This fact was assisted by the presence of LC2 NSnF2,
LCNSnPh2F in the crude product and Ph2SnF2 and Ph3SnF
in the insoluble part of the product detected by the solid
state 19F CP/MAS NMR spectra. The previously published
products of fluorination of LCNSnPhCl2 were only slightly
soluble in methanol. The structural investigation was based
on 1H, 119Sn and low temperature 19F NMR spectral data.
Very complicated multiplets in the 119Sn spectra and very
broad signals in the 19F NMR spectra at room temperature
were found. The similar structural behaviour was assigned
to the derivative 4a by means of multinuclear NMR spec-
troscopy in the chloroform solution. In contrast to analogs
of 4 containing LCN ligand, all fluoroderivatives of 4
(190 K)). In proton NMR spectrum measured at 290 K,
only one set of broad signals for –CH2N and NMe2 were
observed, which decoalesce with the decrease in tempera-
ture (–CH2N at 280 K and N(CH3)2 at 260 K). Only negli-
gible shift of these signals to the higher field is caused by
strengthening Sn–N interaction. One sharp signal at
ꢀ186.0 ppm with satellites (1J(19F, 119Sn) = 2150 Hz) in
19F NMR spectrum gave further evidence of monomeric
structure with covalent and terminal Sn–F bond. This
structural arrangement retained in the whole temperature
range (300–210 K) and only a few hertz decrease in the
1
value of J(19F, 119Sn) is caused by shortening of interac-
tion between the Sn and donor atoms and consequent elon-
gation of the tin–fluorine bond. On the other hand, in
methanol solution, a similar dynamic equilibrium as found
for LNCNnBu2SnCl or Br with the Sn–X bond ionization
+
+
N(CH3)2
N(CH3)2
N(CH3)2
Bu
T<260K
Bu
Sn
Bu
Sn
F-
Sn
F-
Bu
Bu
Bu
Y
Y
F
N(CH3)2
(CH3)2N
(CH3)2N
A
B
C
Fig. 3. Structural behaviour of 3a in the methanol solution; Y – molecule of solvent.

4290
P. Nova´k et al. / Journal of Organometallic Chemistry 692 (2007) 4287–4296
i)
[(LNCN)PhSnF3]- NH4+ (4a)
ii)
(LNCN)PhSnCl2 (4)
iii)
iv)
4a + [(LNCN)SnF4]- NH4+ (5a)
v)
[(LNCN.H+)SnF4]- (5c)
[(LNCN)SnF2(μ-F)2]3 (5b)
Fig. 4. The reactivity of 4 with: (i) 2 equiv. of NH4F; (ii) excess of NH4F; (iii) 20 equiv. of NH4F; (iv) 2 equiv. of LCNnBu2SnF; (v) CH2Cl2/hexane.
revealed very good solubility in methanol and even in
CDCl3 and CD2Cl2.
are identical to spectra of 5c (vide infra). Insoluble prod-
ucts formed by this reaction were identified to be identical
with Ph2SnF2 and Ph3SnF previously detected in the reac-
tivity of LCNPhSnCl2 by 19F CP/MAS NMR spectroscopy
[21].
Compound 5 is very reactive towards the moisture and
its molecular structure can be described as a distorted octa-
hedron with nearly equivalent Sn–Br and Sn–N bonds
(Fig. 5). In the case of reactivity of 5 (LNCN)SnBr3 two syn-
thetic pathways were used (Fig. 6).
Firstly, 2 equiv. of NH4F in CH2Cl2 were added to 4
(Fig. 4) which led, according to 19F and 119Sn NMR spec-
tra, to the dominant formation of 4a. This compound
reveals characteristic broadened doublet of triplet (dt) in
119Sn NMR spectrum measured in methanol (d(119Sn) =
ꢀ486.6 ppm with 1J(119Sn, 19F) = 2770 and 2635 Hz). Sim-
ilar spectral pattern and chemical shift have been observed
in 119Sn NMR spectrum of [Bu4N+][Ph2SnF3
]
ꢀ
(ꢀ402 ppm; 1J(119Sn, 19F) = 2310 (d) and 2250 (t) Hz)
[11] and for [LCNPhSnF3ꢀ] moiety (ꢀ484.8 ppm with
1J(119Sn, 19F) = 2626 and 2706 Hz). A triplet (ꢀ143.0
When only 3 equiv. of NH4F were used for fluorination
of 5, poorly soluble products in non-coordinating solvents
were obtained. Although these species revealed relatively
higher solubility in methanol, we were not able to identify
1
2
ppm; J(19F, 119Sn) = 2581 Hz and J(19F, 19F) = 32 Hz)
1
and a doublet (ꢀ159.9 ppm; J(19F, 119Sn) = 2745 Hz and
their structures even from low temperature proton and 19
F
2J(19F, 19F) = 32 Hz) with integral ratio 1:2 were found
in 19F NMR spectrum at 250 K. Further addition of
NH4F into the sample of 4a did not lead to changes in
NMR spectral patterns.
NMR spectra. We can suggest the presence of partially
fluorinated products making various types of oligomers
through halide bridges with the increase of temperature.
As depicted in Fig. 4, some reactions of 4 led to the for-
mation of monoorganotin derivatives identical to those
found in the case of reactivity of 5 (vide infra) as a result
of previously described phenyl group migration process
[21]. The reaction of 4 with 20 molar equivalents of ammo-
nium fluoride gave the described 4a in an equilibria with 5a
[(LNCN)SnF4]ꢀNH4+ which are sparingly soluble in CDCl3.
119Sn NMR spectrum in this solvent shows the major dou-
blet of triplet for 4a ꢀ488.3 ppm with two comparable Sn–
F couplings 2792 and 2577 Hz and the second quite com-
plex multiplet (Fig. 7a, ꢀ601.3 ppm (ddt) 1J(119Sn,
19F) ꢁ 2430 Hz) which corresponds to 5a. 19F NMR spec-
trum at 295 K contained a couple of very broad signals and
one broadened triplet at ꢀ138.6 ppm with 1J(19F,
119Sn) = 2745 Hz and 2J(19F, 19F) = 32 Hz. In the same
spectrum at 220 K, some signals are sharper (ꢀ136.9 ppm
with 1J(19F, 119Sn) = 2752 Hz and ꢀ165.6 ppm with
1J(19F, 119Sn) = 2606 Hz (4a)) but remaining signals which
belonging to 5a remained unchanged (vide infra).
After the reaction of 4 with 2 equiv. of LCNnBu2SnF, the
toluene insoluble residue was analyzed by ESI/MS. The
highest intensity isotopic peak with the highest m/z value
was 1161 [M+H]+ in positive ion mode which can be
assigned to compound [(LNCN)SnF2(l-F)2]3 (5b). In the
negative ion mode, there is the main peak m/z = 387 which
belongs to anion [(LNCN)SnF4]ꢀ. The trimeric organization
of 5b comes apart owing to solvent leading to the com-
pound 5c that will be discussed later and also 1H, 19F
and 119Sn NMR spectra of 5b measured in chloroform
Fig. 5. Molecular structure of
5 (ORTEP, 50% probability level)
Hydrogen atoms are omitted for clarity. Sn(1)–C(1) 2.034(14), Sn(1)–
N(2) 2.387(13), Sn(1)–N(1) 2.400(14), Sn(1)–Br(1) 2.4977(17), Sn(1)–Br(2)
2.6488(17), Sn(1)–Br(3) 2.6589(17), C(1)–Sn(1)–N(2) 77.7(5), C(1)–Sn(1)–
N(1) 77.1(5), N(2)–Sn(1)–N(1) 154.7(4), C(1)–Sn(1)–Br(1) 177.5(4), N(2)–
Sn(1)–Br(1) 102.3(3), N(1)–Sn(1)–Br(1) 103.0(3), C(1)–Sn(1)–Br(2)
94.6(4), N(2)–Sn(1)–Br(2) 86.7(3), N(1)–Sn(1)–Br(2) 93.7(3), Br(1)–
Sn(1)–Br(2) 87.83(6), C(1)–Sn(1)–Br(3) 89.9(4), N(2)–Sn(1)–Br(3)
95.7(3), N(1)–Sn(1)–Br(3) 85.9(3), Br(1)–Sn(1)–Br(3) 87.64(6), Br(2)–
Sn(1)–Br(3) 175.25(6).

P. Nova´k et al. / Journal of Organometallic Chemistry 692 (2007) 4287–4296
4291
i)
[(LNCN)SnF4]- NH4+ (5a)
(LNCN)SnBr3
(5)
ii)
[(LNCN)SnF2(μ−F)2]3 (5b)
iii)
[(LNCN.H+)SnF4]- (5c)
[(LNCN)SnF2(μ−F)2]2 (5d)
iv)
Fig. 6. The reactivity of 5: (i) 3 equiv. of NH4F and subsequent excess of
NH4F; (ii) 3 equiv. of LCNnBu2SnF; (iii) CH2Cl2/hexane; (iv) methanol.
This suggestion can be supported mainly by study of 19F
NMR spectra. At 290 K, a sharp singlet at ꢀ131.86 ppm
1
with satellites J(19F, 119Sn) = 2561 Hz, which belongs to
a terminal fluorine bonded to tin atom, but without any
further coupling to fluorine atoms, and very broad signal
in the range of ꢀ142 to ꢀ154 ppm. In this area of spectrum
at 220 K eight new quite broad signals without any cou-
plings were visible. Earlier sharp signal is getting very
broad with the loss of satellites at the same conditions.
At the same time, two new signals appeared at ꢀ163.6
and ꢀ167.4 ppm with 1J(19F, 119Sn) ꢁ 1785 Hz as is typical
for bridging fluorine atoms and which is in good agreement
with an oligomeric structure.
In the next reaction, an excess of NH4F was applied
which led to formation of 5a characterized by 119Sn
(Fig. 7) and 19F NMR spectra in methanol. 19F NMR spec-
trum at 290 K reveals two broad signals at ꢀ143.6 and
ꢀ153.2 ppm. With a decrease in temperature to 250 K,
the original signal at ꢀ143.6 ppm became sharper, the tin
couplings were observed (1J(19F, 119Sn) = 2529 Hz) and
the second signal disappeared. Further decrease of temper-
ature did not change the spectral pattern (220 K:
ꢀ142.9 ppm; 1J(19F, 119Sn) = 2531 Hz). The long time
measurement of 119Sn NMR spectrum gave an additional
structural information;
a
unsymmetrical quintet
(d(119Sn) = ꢀ603.5 ppm; 1J(119Sn, 19F) ꢁ 2300 Hz) was
observed supporting thus the description of 5a as hyperco-
ordinated (six-coordinated tin) ionic species where there
are four nearly equivalent terminal fluorine atoms and
one ligand with dynamically exchanging donor atoms.
In order to exclude ammonium fluoride from the reac-
tion systems, previously successful LCNBu2SnF was used
as a fluorinating agent. In toluene insoluble fraction (tolu-
ene filtrate contained only LCNBu2SnBr) was analyzed by
ESI/MS measurements. The same spectral patterns as in
the case of formation of 5b were observed. This product
is insoluble in inert solvents such as toluene but dramati-
cally reactive with, for example, CDCl3 and methanol, giv-
ing 5c as a zwiterionic product of acidic proton abstraction
and further amine quarternization. The monomeric stan-
nate structure (Fig. 8), where, one LNCN ligand is bonded
in bidentate fashion to the tin atom and the second arm
is protonized is observed. The tin coordination octahedron
is formed next by four non-equivalent Sn–F (for F1
Fig. 7. 119Sn ꢀNMR spectra of 5a: (a) in chloroform, (b) simulated for
] by gNMR 5.0 software (IVORYSOFT) using couplings from
[L NCNSnF
4
19F NMR spectrum in chloroform; (c) in methanol; (d) simulated
spectrum in methanol.
The distance Sn–F1 is somewhat shorter in comparison
with Sn–F2 and F4, respectively, as a product of
trans-effect of donor amino group. Much longer elongation
can be seen in the case of Sn–F3 bond due to the existence
˚
˚
˚
1.983(4) A, for F2 (trans to N1) 1.961(2) A, for F3
of hydrogen bonding (N2–H2ꢂ ꢂ ꢂF3 (2.757(3) A)). Similar
˚
˚
2.030(2) A, for F4 1.952(4) A) bonds.
bondlengths were found in the sole published mono-

4292
P. Nova´k et al. / Journal of Organometallic Chemistry 692 (2007) 4287–4296
Fig. 8. Molecular structure of 5c (ORTEP, 50% probability level).
˚
Hydrogen atoms are omitted for clarity. The selected distances (A) and
Fig. 9. 119Sn NMR spectra of 5c: (a) in chloroform; (b) simulated for
[LNCN(H)+SnꢀF4] by gNMR 5.0 software (IVORYSOFT) using couplings
from 19F NMR spectrum in chloroform.
angles (°): Sn(1)–N(1) 2.325(2), Sn(1)–F(1) 1.9522(14), Sn(1)–F(2)
1.9613(14), Sn(1)–F(3) 2.0302(13), Sn(1)–F(4) 1.9835(14), Sn(1)–C(1)
2.150(2), F(1)–Sn(1)–F(2) 93.64(6), F(1)–Sn(1)–F(4) 89.24(6), F(2)–
Sn(1)–F(4) 91.30(6), F(1)–Sn(1)–F(3) 85.29(6), F(2)–Sn(1)–F(3) 87.50(6),
F(4)–Sn(1)–F(3) 174.31(5), F(1)–Sn(1)–C(1) 161.08(8), F(2)–Sn(1)–C(1)
103.82(8), F(4)–Sn(1)–C(1) 97.49(7), F(3)–Sn(1)–C(1) 88.19(7), F(1)–
Sn(1)–N(1) 85.04(7), F(2)–Sn(1)–N(1) 174.35(7), F(4)–Sn(1)–N(1)
83.20(7), F(3)–Sn(1)–N(1) 97.84(6), C(1)–Sn(1)–N(1) 78.27(8).
NMR spectrum at 290 K gave no additional information
about the structure, because only one major signal at
ꢀ141 ppm and two minor very broad signals at ꢀ148.5
and ꢀ161.7 ppm were found. With the lowering of the tem-
perature to 250 K, the major signal (ꢀ141 ppm) goes
broader and the remaining two signals are sharpened
(ꢀ148.2 ppm with 1J(19F, 119Sn) = 2267 Hz and
ꢀ161.8 ppm) with 1J(19F, 119Sn) = 1593 Hz. Further
decrease in temperature led to broadening of these signals
again.
A different NMR spectral pattern was found directly
after dissolution of 5b in methanol-d4. We proposed the
equilibrium of a couple of species (Fig. 10) which led after
some minutes to the formation of 5c. In 119Sn NMR spec-
trum (295 K) two doublets of triplets at ꢀ576.8 ppm with
1J(119Sn, 19F) = 2485 Hz and ꢀ579.3 ppm with 1J(119Sn,
19F) = 2670 Hz which could be assigned to two different
isomers (Fig. 10) of [(LNCN)SnF3.O(H)Me] type are
observed. The third signal is split into a pseudoquartet of
organotin fluoride with terminal fluorine atoms (Sn–F:
˚
1.956; 1.948 aand 1.975 A) [19]. The main deviation from
the octahedral shape are the values of N1–Sn–F1 angle
(174.36(1)°, ideally 180°) and C1–Sn–F2 (103.83(3)°, ide-
ally 90°). Very close to this arrangement are also the hydro-
lysis products of chlorine and bromine analogs [25,28].
Although the hydrolysis product of 5 is dimeric the torsion
angle defined by C1–C2–C7–N1 (37.01° (5a), 34.52° (5))
˚
are similar. The distance Sn–N1 (2.325(2) A) is the stron-
gest reported contact Sn–N in this type of compounds;
˚
˚
(2.386(4) and 2.400(1) A for 5 and 2.3700(3)A for its hydro-
lysis product [25c]). This structure retained in CDCl3,
1
which is supported by H, 119Sn a 19F NMR spectra. In
the proton spectrum of 5c at 295 K, there is signal at
9.78 ppm assigned to R3NH+ group. In aliphatic part of
the spectrum, two broad signals (4.58 and 3.83 ppm)
belonging to two different –CH2N groups were found, as
well as another two (2.89 and 2.64 ppm) for methyl of
NMe2 groups, and these signals are not changed with low-
ering of the temperature. Complex multiplet (doublet of
doublets of triplets – ddt (Fig. 9)) with the centre of gravity
at ꢀ601.2 ppm and coupling 1J(119Sn, 19F) ꢁ 2520 Hz were
visible in 119Sn NMR spectrum, and this supports the non-
equivalency of terminal fluorine atoms. Measured 19F
triplets (or better, doublet of triplets
–
dtt) at
ꢀ604.9 ppm with 1J(119Sn, 19F) = 2560 and 1595 Hz, which
could be assigned to a dinuclear 5d [(LNCN)SnF2(l-F)2]2,
with two terminal and two bridging fluorine atoms.
19F NMR spectrum at 295 K gave no useful informa-
tion, because very broad and unresolved signals were
obtained. These signals are much sharper at 250 K, but
they are not consistent with the proposed monomeric struc-
ture of two isomers of [(LNCN)SnF3 Æ O(H)Me] type. With

P. Nova´k et al. / Journal of Organometallic Chemistry 692 (2007) 4287–4296
4293
NMe2
NMe2
F
Sn
Me
H
F
MeOH
[(LNCN)SnF2(μ-F)2]2
(5d)
+
F
[(LNCN)SnF2(μ-F)2]3
(5b)
+
Sn
F
O
F
F
HOMe
Me2N
Me2N
Δ T
[(LNCNSnF2)2(μ-F)]n
Fig. 10. Influence of solvent (CD3OD) to structure of 5b.
respect to the existence of two new signals at ꢀ150.7 ppm
been prepared by procedures reported in Refs.
[20,25a,25b]. Compound 5 was prepared similarly as in
ref. [25c] but very strict vacuo conditions were applied.
Yield: 62%; 1H NMR (500.13 MHz, Toluene-d8, 300 K,
ppm): 7.06 (t, 1H, Hð40Þ); 6.65 (d, 2H, Hð30Þ, 3J(119Sn,
1H) = 62.7 Hz); 3.32 (bs, 4H, NCH2); 2.39 (bs, 12H,
N(CH3)2). 13C NMR (Toluene-d8, 30 0K, ppm): 60.66,
NCH2; 46.84, NCH3. 119Sn{1H} NMR (Toluene-d8,
300 K, ppm): ꢀ601.4 (brs). The same conditions as
described in Ref. [26] for preparation of 1b yielded 1c only
with the same spectral data.
1
2
(d) with J(119Sn, 19F) = 2770 Hz, J(19F, 19F) = 19.8 Hz
and ꢀ168.5 ppm (t) with 1J(119Sn, 19F) = 1536 Hz and
2J(19F, 19F) = 19.8 Hz with integral ratio 4:1 which signal-
ize a formation of new oligomeric species of [(LNCN)-
SnF2(l-F)]n type.
3. Conclusions
The set of tri-, di- and monoorganotin(IV) halides con-
taining N,C,N-chelating ligand has been prepared and
structurally characterized (1c, 5). These compounds were
reacted with different fluorinating agents to give derivatives
containing fluorine atom(s).
4.2. NMR spectroscopy
Triorganotin(IV) fluorides 2a and 3a revealed the mono-
meric structural arrangement with covalent Sn–F bond
both in the coordinating and noncoordianting solvents,
except the behaviour of 3a which was ionized in the meth-
anol solution at low temperature.
The NMR spectra were recorded as solutions in metha-
nol-D4, C6D6, CDCl3 on a Bruker Avance 500 spectrome-
ter (equipped with Z-gradient 5mm probe) at 300, 250, 220
1
or 170 K, H (500.13 MHz), 119Sn{1H} (186.50 MHz) and
1
19F{1H} (470.53 MHz). The assignments of signals in H
Good solubility in more solvents as a consequence of
two chelating arms of ligand LNCN in the case of fluorides
originated from the compounds 4 and 5 was observed. The
compounds 4a and 5a were described in solution as the
ionic hypervalent fluorostannates. On the other hand,
the oligomeric compound 5b dissolved in chloroform or
methanol providing the zwitterionic monomeric stannate
5c. This structural arrangement was confirmed by XRD
analysis in the solid state.
spectra were made from standard 2D measurements. The
solutions were obtained by dissolving of 5–40 mg of each
compound in 0.5 ml of deuterated solvents. The H chem-
1
ical shifts were calibrated relative to the signal of residual
CHCl3 (d = 7.27) and benzene (7.16), methanol (d =
3.31), respectively, and the 19F chemical shifts are referred
to external Cl3FC (d = 0.0). The 119Sn chemical shifts are
referred to external neat tetramethylstannane (d = 0.0).
Positive chemical shifts values denote shifts to the higher
frequencies relative to the standards. 119Sn NMR spectra
were measured using the inverse gated-decoupling mode.
19F MAS NMR spectra were measured using Bruker
Avance 500 WB/US NMR spectrometer (Karlsruhe, Ger-
many, 2003) in 2.5 ZrO2 rotors. Magic angle spinning
(MAS) frequency was 30 kHz. Intensity of excitation
B1(19F) field corresponds to x1/2p = 113.6 kHz (length of
90° pulse is 2.2 ls). All experiments were performed at
room temperature (296 K). 19F chemical shift scale was cal-
ibrated using external standard KF (ꢀ130.0 ppm).
4. Experimental
4.1. General remarks
All experiments were carried out in an argon atmo-
sphere or in vacuo. (N,N-dimethylaminomethyl)benzene,
n-butyllithium, phenyltin(IV) trichloride, dibutyltin(IV)
dichloride, dimethyltin(IV) dichloride, tin(IV) bromide,
potassium fluoride, ammonium fluoride (dried in vacuo),
18-crown-6-ether were obtained from commercial sources
(Sigma–Aldrich). Toluene, benzene, n-hexane, n-pentane
were dried over and distilled from potassium alloy,
degassed and stored over potassium mirror. Chloroform
and dichloromethane were dried over and distilled from
P2O5 and CaH2. Compounds 1–4 and LCNnBu2SnF have
4.3. Mass spectrometry
Electrospray ionization (ESI) mass spectra (MS) were
measured on the ion trap analyser Esquire3000 (Bruker
Daltonics, Bremen, Germany) in the range m/z 50–2000.

4294
P. Nova´k et al. / Journal of Organometallic Chemistry 692 (2007) 4287–4296
The sample was dissolved in dried acetonitrile or methanol
and analysed by direct infusion at the flow rate 5 ll/min
both in the negative- and positive-ion modes. The ion
source temperature was 300 °C, the flow rate and the pres-
sure of nitrogen were 4 l/min and 10 psi, respectively. The
isolation width for MS/MS experiments was F[x] m/z = 8,
and the collision amplitude was 0.9 V.
4.5. {[Bis-2,6-(N,N-
dimethylaminomethyl)]phenyl}dimethyltin(IV) fluoride
(2a)
To a benzene solution of 2 (0.1 g, 0.27 mmol) in a
Schlenk tube was added KF (0.27 mmol) and 18-crown-6-
ether (0.02 mmol) and the reaction mixture was stirred
for one week. Afterwards a white solid was formed. The fil-
trate was concentrated and pentane was added to give an
oily product. Yield: 66 mg (68%). 1H NMR (C6D6,
300 K, ppm): 6.87 (bs, 2H, Hð30Þ), 7.31 (m, 1H, Hð40Þ);
3.5 (bs, 4H, NCH2); 1.76 (d, 6H, N(CH3)2); 1.34 (d, 6H,
N(CH3)2); 0.49 (s, 6H, H(1)), 2J(119Sn, 1H) = 65.1 Hz,
3J(19F, 1H(1)) = 7 Hz. 19F{1H} NMR (C6D6, 300 K,
ppm): ꢀ173.2 (s); 1J(19F, 119Sn) = 2116 Hz, 119Sn{1H}
NMR (C6D6, 300 K, ppm): ꢀ83.5 (d); 1J(119Sn,
19F) = 2160 Hz.
4.4. X-ray crystallography
The single crystals of 1c, 5 and 5b were obtained from
toluene (5) or dichlormethane solution.
Data for colorless crystals were collected at 150(1) K on
a Nonius KappaCCD diffractometer using Mo Ka radia-
˚
tion (k = 0.71073 A), and graphite monochromator. The
structures were solved by direct methods (SIR92 [29]). All
reflections were used in the structure refinement based on
F2 by full-matrix least-squares technique (SHELXL97 [30]).
Hydrogen atoms were mostly localized on a difference Fou-
rier map, however to ensure uniformity of treatment of
crystal, all hydrogen atoms were recalculated into idealized
positions (riding model) and assigned temperature factors
Hiso(H) = 1.2Ueq(pivot atom) or of 1.5Ueq for the methyl
moiety. Absorption corrections were carried on, using
either multi-scans procedure (PLATON [31] or SORTAV [32])
or Gaussian integration from crystal shape (Coppens
[33]). A twinned crystal of 5 reveals after solving of struc-
ture, rather high residual electron density maxima but
has no chemical significance; one of atoms (C1) was refined
isotropically.
4.6. {[Bis-2,6-(N,N-dimethylaminomethyl)]phenyl}di(1-
butyl)tin(IV) fluoride (3a)
To a solution of 0.2 g of 3 (0.44 mmol) in diethylether
(10 ml) was added an aqueous solution of KF (20 eq.
excess). The reaction mixture was stirred for one week.
Then, both phases were separated and the water phase
was extracted twice with diethylether. The organic phases
were brought together and dried over magnesium sulphate.
After removing of volatiles, the filtrate was evaporated to
dryness in vacuo to obtain the oily product. Yield:
0.164 g (82%). 1H NMR (500.13 MHz, CDCl3, 300 K,
ppm): 7.16 (bs, 1H, Hð40Þ); 7.02 (bs, 2H, Hð30Þ); 3.55 (bs,
4H, NCH2); 2.14 (bs, 12H, N(CH3)2); 1.66 (m, 4H, H(1));
1.34 (m, 4H, H(2)); 1.20 (m, 4H, H(3)); 0.86 (t, 6H,
H(4)). 13C NMR (CDCl3, 300 K, ppm): 143.1, Cð20; 60Þ;
140.2, 2J(19F, 13C) = 38.6 Hz, Cð10Þ; 125.9, Cð30; 50Þ;
128.3, Cð40Þ; 64.2, NCH2; 44.8, NCH3; 17.5, 1J(119Sn,
13C) = 526.3 Hz, 2J(19F, 13C) = 11.3 Hz, C(1); 28.1,
Crystallographic
data
for
1c:
C24H29N2I3Sn,
M = 844.88, monoclinic, P21/c, a = 10.4230(2), b =
˚
17.3750(3), c = 15.7690(3) A, b = 97.9620(13)°, Z = 4,
3
V = 2828.23(9) A , Dcalc = 1.984 g cmꢀ3, l = 4.191 mmꢀ1
,
˚
Tmin = 0.418, Tmax = 0.545; 128617 reflections measured
(hmax = 27.5°), 10134 independent (Rint = 0.0706), 5736
with I > 2r(I), 276 parameters, S = 1.097, R1(obs.
data) = 0.0306, wR2(all data) = 0.0741; max., min. residual
2J(119Sn,
13C) = 26.3 Hz,
C(2);
27.2,
3J(119Sn,
ꢀ3
electron density = 0.888, ꢀ0.959 e A
.
13C) = 87.8 Hz, C(3); 13.6, C(4). 19F{1H} NMR (CDCl3,
300 K, ppm): ꢀ186 (s); 1J(19F, 119Sn) = 2150 Hz,
119Sn{1H} NMR (CDCl3, 300 K, ppm): ꢀ96.0 (d);
1J(119Sn, 19F) = 2195 Hz. ESI-MS: MW = 444. m/z (%).
Positive ion mode MS: [MꢀF]+, 425 (100). Elemental
Anal. Calc. for C20H37N2FSn (443.22): C, 54.2; H, 8.41;
N, 6.32. Found: C, 54.18; H, 8.39; N, 6.35%.
˚
Crystallographic data for 5: C12H19N2Br3Sn,
M = 549.71, monoclinic, P21/n, a = 14.1760(4), b =
˚
8.4830(2), c = 14.7100(4) A, b = 108.7860(14)°, Z = 4,
V = 1674.72(8) A , Dcalc = 2.180 g cmꢀ3, l = 8.670 mmꢀ1
,
3
˚
Tmin = 0.152, Tmax = 0.699; 27954 reflections measured
(hmax = 27.5°), 10134 independent (Rint = 0.1498), 3781
with I > 2r(I), 163 parameters, S = 1.085, R1(obs.
data) = 0.0829, wR2(all data) = 0.2596; max., min. residual
4.7. Products of fluorination of (LNCN)PhSnCl2 (4) and
(LNCN)SnBr3 (5)
ꢀ3
˚
electron density = 4.515, ꢀ2.591 e A
.
Crystallographic data for 5c: C12H20N2F4Sn,
M = 386.99, monoclinic, P21/n, a = 15.1340(4), b =
Method A. The compound 4 (100 mg, 0.21 mmol) was
dissolved in 10 ml of dichloromethane and NH4F (20 eq.
excess) was added. The reaction mixture was stirred for five
days. Afterwards, the soluble part was filtered off and the
volatiles were vacuo removed. The product was dissolved
˚
7.3050(2), c = 15.5510(4) A, b = 116.0381(14)°, Z = 4,
V = 1544.73(7) A , Dcalc = 1.664 g cmꢀ3, l = 1.685 mmꢀ1
,
3
˚
Tmin = 0.813, Tmax = 0.885; 15798 reflections measured
(hmax = 27.5°), 10134 independent (Rint = 0.0393), 3086
with I > 2r(I), 180 parameters, S = 1.092, R1(obs.
data) = 0.0250, wR2(all data) = 0.0563; max., min. residual
1
in CDCl3. H NMR (CDCl3, 300 K, ppm): 7.92 (d, 2H),
3
0
0
Jð Hð4 Þ,1Hð3 ÞÞ ¼ 6:5Hz, 3J(119Sn, 1H) = 102.84 Hz,
1
ꢀ3
˚
electron density = 1.064, ꢀ0.775 e A
.
7.31–7.02 (m, 8H), 4.08 (bs, 4H, NCH2), 3.72 (bs, 4H,

P. Nova´k et al. / Journal of Organometallic Chemistry 692 (2007) 4287–4296
4295
NCH2), 2.74–2.65 (m, 12H, NCH3), 2.34–2.17 (m, 12H,
NCH3).19F{1H} NMR (CDCl3, 300 K, ppm): ꢀ138.6 (s),
1J(19F, 119Sn) = 2734 Hz, ꢀ145 (bs), ꢀ152 (bs), ꢀ155 (s),
ꢀ160 (bs). 119Sn{1H} NMR (CDCl3, 300 K, ppm):
ꢀ488.3 (dt), 1J(119Sn, 19F) = 2792 and 2577 Hz, ꢀ601.3
NCH3). 19F{1H} NMR (CDCl3, 300 K, ppm): ꢀ141 (bs),
ꢀ146.8 (bs), ꢀ161.7 (s). 119Sn{1H} NMR: (CDCl3,
300 K, ppm): ꢀ601.2 (ddt), 1J(119Sn, 19F) ꢁ 2520 Hz.
ESI-MS: MW = 388; m/z (%). Positive ion mode:
[M+K]+, 427 (49), [M+KꢀHF]+, 407 (75), [M-F]+, 369
(93), [MꢀFꢀHF]+, 349 (100), [MꢀFꢀ2*HFꢀCH2@
N(CH3)2], 271 (32), [LNCN+H]+, 193 (90). Negative ion
mode: [LNCNSnF4]ꢀ, 387 (100).
1
(ddt), J(119Sn, 19F) ꢁ 2430 Hz.
Method B. To a toluene solution of 4 (0.145 g,
0.31 mmol) was added LCNnBu2SnF (0.104 g, 0.63 mmol)
and the reaction mixture was stirred and heated at 80 °C
for 5 days. Afterwards, toluene was removed by filtration
and the remaining insoluble solid was washed several times
with toluene. The toluene extract was evaporated to dry-
ness in vacuo and a residuum was identified by NMR spec-
troscopy as the chloride analogue of LCNnBu2SnF. The
solid was investigated by ESI/MS: MW = 1161; m/z (%):
Positive ion mode: [(LNCNSnF4)3 + K]+, 1200 (10);
[(LNCNSnF4)3 + Na]+, 1184 (49); [(LNCNSnF4)3 + H]+,
5. Supplementary material
CCDC 636307, 636308 and 636309 contain the supple-
mentary crystallographic data for 1c, 5 and 5c. These data
can be obtained free of charge via http://www.ccdc.cam.a-
c.uk/conts/retrieving.html, or from the Cambridge Crystal-
lographic Data Centre, 12 Union Road, Cambridge CB2
1EZ, UK; fax: (+44) 1223-336-033; or e-mail:
deposit@ccdc.cam.ac.uk.
1162
(11);
[Mꢀ(LNCNSnF4)+Na]+,
797
(100);
[Mꢀ(LNCNSnF4) + H]+, 775 (35); [LNCNSnF3 + K]+, 407
(61); Negative ion mode: [LNCNSnF4]ꢀ, 387 (100). After-
wards, the solid was dissolved in CDCl3 to give. 1H
NMR (CDCl3, 300 K, ppm): 9.78 (bs, NH+), 7.42–7.11
(m), 4.58 (bs, 2H, CH2N), 3.83 (bs, 2H, CH2N), 2.89 (bs,
6H, NCH3), 2.65 (bs, 6H, NCH3). 19F{1H} NMR (CDCl3,
300 K, ppm): ꢀ139 (bs), ꢀ148.6 (bs), ꢀ163.4 (bs).
119Sn{1H} NMR: (CDCl3, 300 K, ppm): ꢀ604.0 (ddt),
1J(119Sn, 19F) ꢁ 2520 Hz.
Acknowledgement
´
The authors thank Dr. Jirˇı Brus for CP-MAS NMR
spectra measurements. The financial support of the Science
Foundation of the Czech Republic (Grant No. 203/07/
0468) and the Ministry of Education of the Czech Republic
(Project VZ0021627501) is acknowledged.
References
For 5: Method A. The compound 5 (0.2 g, 0.36 mmol)
was dissolved in 10 ml of dichloromethane and NH4F (20
eq. excess) was added. The reaction mixture was stirred
for five days. Afterwards the soluble part was filtrated off
and the volatiles were vacuo removed. The product was
dissolved in CD3OD. 1H NMR (500.13 MHz, CD3OD,
300 K, ppm): 7.44 (bs, 1H), 7.27 (m, 2H), 5.16 (bs, NH4
+), 4.2 (bs, 4H, NCH2), 2.74 (bs, 12H, NCH3).19F{1H}
NMR (CD3OD, 300 K, ppm): ꢀ140 to ꢀ155 (vbs).
119Sn{1H} NMR (CD3OD, 300 K, ppm): ꢀ600.9 (pseudo-
quintet), 1J(119Sn, 19F) = 2308 Hz. ESI-MS: MW = 405.
Positive ion mode: m/z (%): [MꢀNH4F+H]+, 369 (100),
[LNCNSnF2]+, 349 (60), [MꢀFꢀ2*HFꢀCH2@N(CH3)2],
271 (68), [LNCN]+, 193 (57). Negative ion mode:
[LNCNSnF4]ꢀ, 387 (100).
[1] (a) For reviews see: E.F. Murphy, R. Murugavel, H.W. Roesky,
Chem. Rev. 97 (1997) 3425–3460;
(b) B. Jagirdar, E.F. Murphy, H.W. Roesky, Prog. Inorg. Chem. 48
(1999) 351–455;
(c) H. Dorn, E.F. Murphy, H.W. Roesky, J. Fluorine Chem. 86
(1997) 121.
[2] M. Makosza, R. Bujok, J. Fluorine Chem. 126 (2005) 209.
[3] M. Makosza, R. Bujok, Tetrahedron Lett. 45 (2004) 1385.
[4] N. Chaniotakis, K. Jurkschat, D. Muller, K. Perdikaki, G. Reeske,
¨
Eur. J. Inorg. Chem. (2004) 2283.
[5] J.L. Wardell, G.M. Spenser, in: R.B. King (Ed.), Encyclopedia of
Inorganic Chemistry, vol. 8, Wiley, New York, 1994, p. 4172.
[6] S.S. Al-Juaid, S.M. Dhaher, C. Eaborn, P.B. Hitchcock, J. Organo-
met. Chem. 325 (1987) 117.
[7] H. Reuter, H. Puff, J. Organomet. Chem. 379 (1989) 223.
[8] J. Beckmann, D. Horn, K. Jurkschat, F. Rosche, M. Schurmann, U.
¨
Zachwieja, D. Dakternieks, A. Duthie, E.K.L. Lim, Eur. J. Inorg.
Chem. (2003) 164.
[9] U. Kolb, M. Dra¨ger, B. Jousseaume, Organometallics 10 (1991) 2737.
[10] D. Tudela, R. Fernandez, V.K. Belsky, V.E. Zavodnik, J. Chem.
Soc., Dalton Trans. (1996) 2123.
[11] D. Dakternieks, H. Zhu, Organometallics 11 (1992) 3820.
[12] W.-P. Leung, W.-H. Kwok, Z.-Y. Zhou, T.C.W. Mak, Organomet-
allics 22 (2003) 1751.
Method B. To a toluene solution of 5 (90 mg,
0.16 mmol) was added LCNnBu2SnF (190 mg, 0.48 mmol)
and the reaction mixture was stirred and heated at 80 °C
for 5 days. Afterwards toluene was removed by filtration
and the remaining insoluble solid was washed several times
with toluene. The solid was investigated by ESI/MS:
MW = 1161; m/z (%): Positive ion mode: [(LNCN
-
[13] N. Pieper, C. Klaus-Mrestani, M. Schurmann, K. Jurkschat, M.
¨
SnF4)3+K]+, 1200 (10); [(LNCNSnF4)3+Na]+, 1184 (49);
Biesemans, I. Verbruggen, J.C. Martins, R. Willem, Organometallics
16 (1997) 1043.
[14] M. Mehring, I. Vrasidas, D. Horn, M. Schurmann, K. Jurkschat,
¨
[(LNCNSnF4)3+H]+, 1162 (11); [Mꢀ(LNCNSnF4)+ Na]+,
797
(100);
[Mꢀ(LNCNSnF4)+H]+,
775
(35);
[LNCNSnF3+K]+, 407 (61). Negative ion mode:
[LNCNSnF4]ꢀ, 387 (100). Afterwards the solid was dis-
Organometallics 20 (2001) 4647.
[15] N. Pieper, C. Klaus-Mrestani, M. Schurmann, K. Jurkschat, M.
Biesemans, I. Verbruggen, R. Willem, Organometallics 11 (1992) 3820.
[16] N. Pieper, C. Ludwig, M. Schurmann, K. Jurkschat, M. Biesemans,
I. Verbruggen, R. Willem, Phosphorus Sulfur Silicon Relat. Elem.
151 (1999) 305.
1
solved in CDCl3 to give: H NMR (CDCl3, 300 K, ppm):
9.78 (bs, NH+), 7.42–7.11 (m), 4.58 (bs, 2H, CH2N), 3.83
(bs, 2H, CH2N), 2.89 (bs, 6H, NCH3), 2.65 (bs, 6H,

4296
P. Nova´k et al. / Journal of Organometallic Chemistry 692 (2007) 4287–4296
˚
´
´
[17] J. Beckmann, D. Dakternieks, A. Duthie, E.R.T. Tiekink, J.
Organomet. Chem. 648 (2002) 204.
(c) R. Jambor, A. Ruzˇicˇka, J. Brus, I. Cısarˇova, J. Holecˇek, Inorg.
Chem. Commun. 4 (2001) 257.
´
´
´ˇ
´
´
ˇ
´
[18] D. Dakternieks, K. Jurkschat, H. Zhu, E.R.T. Tiekink, Organomet-
allics 14 (1995) 2512.
[26] B. Kasˇna, R. Jambor, L. Dostal, L. Kolarova, I. Cısarova, J.
Holecˇek, Organometallics 25 (2006) 148.
´
ˇ
´
˚
ˇ
ˇ
[19] S. Dostal, J. Stoudt, P. Fanwick, W.F. Sereatan, B. Kahr, J.E.
Jackson, Organometallics 12 (1993) 2284.
[27] (a) R. Jambor, I. Cısarova, A. Ruzˇicka, J. Holecek, Acta Crystallogr.
373 (2001) C57;
´
´
´
´
´
ˇ
´
˚
´
(b) A. Ruzˇicka, L. Dostal, R. Jambor, V. Buchta, J. Brus, I.
ˇ
[20] J. Baresˇ, P. Novak, M. Nadvornık, T. Lebl, R. Jambor, I. Cısarova,
˚
´
´
A. Ruzˇicˇka, J. Holecˇek, Organometallics 23 (2004) 2967.
Cısarˇova, M. Holcˇapek, J. Holecˇek, Appl. Organomet. Chem. 315
´
´
ˇ
´
˚
ˇ
ˇ
[21] P. Novak, J. Brus, I. Cısarova, A. Ruzˇicka, J. Holecek, J. Fluorine
(2002) 16.
Chem. 126 (2005) 1531.
[28] S.H.L. Thoonen, H. van Hock, E. de Wolf, M. Lutz, A.L. Spek, B.J.
Deelman, G. van Koten, J. Organomet. Chem. 691 (2006) 1544.
[29] A. Altomare, G. Cascarone, C. Giacovazzo, A. Guagliardi, M.C.
Burla, G. Polidori, M. Camalli, J. Appl. Crystallogr. 27 (1994) 1045–
1050.
´
ˇ
´
´
ˇ
´
´ˇ
´
˚
ˇ
[22] P. Novak, Z. Padelkova, I. Cısarova, L. Kolarova, A. Ruzˇicka, J.
Holecˇek, Appl. Organomet. Chem. 20 (2006) 226.
ˇ
˚
[23] S. Chandra, A. Ruzˇicˇka, P. Svec, H. Lang, Anal. Chim. Acta 577
(2006) 91.
ˇ
´
´
´
ˇ
´
´
ˇ
´
[24] P. Svec, P. Novak, M. Nadvornık, Z. Padelkova, I. Cısarova, L.
[30] G.M. Sheldrick, SHELXL-97, A Program for Crystal Structure Refine-
ment, University of Go¨ttingen, Germany, 1997.
´ˇ
´
˚
ˇ
ˇ
Kolarova, A. Ruzˇicka, J. Holecek, J. Fluorine Chem. (in press).
˚
´
´
´
[25] (a) A. Ruzˇicˇka, R. Jambor, L. Dostal, I. Cısarˇova, J. Holecˇek,
[31] A.L. Spek, J. Appl. Cryst. 36 (2003) 7–13.
Chem. Eur. J. 9 (2003) 2411;
[32] R.H. Blessing, J. Appl. Crystallogr. 30 (1997) 421–426.
[33] P. Coppens, in: F.R. Ahmed, S.R. Hall, C.P. Huber (Eds.), Crystal-
lographic Computing, Munksgaard, Copenhagen, 1970, pp. 255–270.
˚
´
´
(b) A. Ruzˇicˇka, R. Jambor, J. Brus, I. Cısarˇova, J. Holecˇek, Inorg.
Chim. Acta 323 (2001) 163;