C,N-chelated hexaorganodistannanes, and triorganotin(IV) hydrides and cyclopentadienides

Article abstract of DOI:10.1016/j.jorganchem.2009.04.043

Triorganotin(IV) hydrides and cyclopentadienides as well as hexaorganodistannanes containing the moiety L^CN (2-(N,N-dimethylaminomethyl)phenyl-) as chelating ligand and phenyl, n-butyl or t-butyl substituents were prepared and characterized by NMR and XRD. The compounds reveal trigonal bipyramidal geometry around the central tin atom except for the distannanes in which the tin atom has tetrahedral configuration. The di-n-butyl distannane cannot be oxidized by oxygen or heavier chalcogens and give no tin radical when irradiated by UV light or treated with the TEMPO - free radical at room temperature. L^CN(t-Bu)₂SnH undergoes reaction in solution toward the corresponding distannane. The hydrostannation reaction of L^CN(n-Bu)₂SnH with ferrocenylacetylene was investigated. The CO₂ activation by L^CN(n-Bu)₂SnH was also examined.

Full text of DOI:10.1016/j.jorganchem.2009.04.043

Journal of Organometallic Chemistry 694 (2009) 3000–3007
Contents lists available at ScienceDirect
Journal of Organometallic Chemistry
journal homepage: www.elsevier.com/locate/jorganchem
C,N-chelated hexaorganodistannanes, and triorganotin(IV) hydrides
and cyclopentadienides
a
a
a
a
b
c
ˇ
ˇ
ˇ
ˇ
ˇ
Jan Turek , Zdenka Padelková , Zdenek Cernošek , Milan Erben , Antonín Lycka , Mikhail S. Nechaev ,
d
a,
*
ˇ
ˇ ˇ
Ivana Císarová , Aleš Ru˚ zicka
a
ˇ
Department of General and Inorganic Chemistry, Faculty of Chemical Technology, University of Pardubice, Nám. Cs. Legií 565, CZ-532 10 Pardubice, Czech Republic
b Research Institute for Organic Syntheses (VUOS), Rybitví 296, 532 18 Pardubice 20, Czech Republic
c Department of Chemistry, Moscow State University, Leninskie Gory, 1 (3), GSP-2, 119992 Moscow, Russia
d Charles University in Prague, Faculty of Science, Hlavova 2030, 128 40 Praha 2, Czech Republic
a r t i c l e i n f o
a b s t r a c t
Article history:
Triorganotin(IV) hydrides and cyclopentadienides as well as hexaorganodistannanes containing the moi-
ety LCN (2-(N,N-dimethylaminomethyl)phenyl-) as chelating ligand and phenyl, n-butyl or t-butyl substit-
uents were prepared and characterized by NMR and XRD. The compounds reveal trigonal bipyramidal
geometry around the central tin atom except for the distannanes in which the tin atom has tetrahedral
configuration. The di-n-butyl distannane cannot be oxidized by oxygen or heavier chalcogens and give no
tin radical when irradiated by UV light or treated with the TEMPO – free radical at room temperature.
Received 2 March 2009
Received in revised form 29 April 2009
Accepted 30 April 2009
Available online 7 May 2009
Keywords:
Organotin(IV) compounds
Hydride
Cyclopentadienide
C,N-ligand
L
CN(t-Bu)2SnH undergoes reaction in solution toward the corresponding distannane. The hydrostannation
reaction of LCN(n-Bu)2SnH with ferrocenylacetylene was investigated. The CO2 activation by LCN(n-
Bu)2SnH was also examined.
Ó 2009 Elsevier B.V. All rights reserved.
Distannane
1. Introduction
C,N-chelating ligand(s). In a recent paper, we described the unu-
sual reactivity of bis{2-[(dimethylamino)methyl]phenyl} tin(IV)
In recent years, the organotin(IV) hydrides have found exten-
sive applications in organic syntheses that involve radical chain
reactions in which the stannyl radical R3SnÅ is a chain carrying
intermediate [1].
Distannanes of general formula R3SnSnR3 can be taken as being
the source of above mentioned radical R3SnÅ as well, and are also
frequently studied. The chemistry of organotin(IV) compounds
dibromide [8–13] with two equivalents of cyclopentadienyl- or flu-
orenyllithium in THF [14].
In the present paper, the structure, properties and preliminary
reactivity studies of hydrides, cyclopentadienides and distannanes
containing LCNR2Sn moiety, where R is Ph, n-Bu and t-Bu are
reported.
where the tin atom is
r-bonded to a cyclopentadienyl moiety is
2. Results and discussion
also well established including, for example, studies of mixed va-
lence tin(II) and tin(IV) compounds or stability and properties of ti-
n(III) radicals generated by irradiation of Bu4ꢀnCpnSn. Recent
studies targeted mainly onto the synthesis of tin substituted ferro-
cenes [2] or ferrocenophanes [3], and the use of these compounds
as cyclopentadienyl group transfer agents to the transition metal
center [4].
Our interest is mainly focused on the family of organotin(IV)
compounds containing 2-[(dimethylamino)methyl]phenyl-group
(LCN) or related ligands which reveal interesting structural proper-
ties [5,6] and potential use [7]. The aim of our previous studies was
to prepare tin(IV) bridged ansa metallocenes containing mentioned
Reactions of starting chlorides 1a–c with NaCp, K(BEt3)HꢁTHF
and an excess of potassium provided the desired products in high
yield as shown in Scheme 1. The only problematic seems to be the
reaction of t-butyl derivative 1c towards NaCp giving a mixture of
starting material and inseparable products.
The reactions of starting chlorides 1a and 1b with sodium cyclo-
pentadienide in diethyl ether gave the desired cyclopentadienides
in 81% (for 2a) and 72% (for 2b) yield. The reaction of di-t-butyl
derivative (1c) gave the mixture of inseparable products at the
same conditions. In 1H NMR spectra of 2a and 2b, a signal at
6.42 ppm (2J(119Sn, 1H) = 14 Hz) for 2a and 6.29 ppm (2J(119Sn,
1H) = 19 Hz) for 2b, respectively, typical for a monohapto bonded
cyclopentadienyl ring, was observed [18]. Compounds 2a and 2b
display 119Sn resonances at ꢀ73.6 and ꢀ144.9 ppm, respectively,
* Corresponding author. Tel.: +420 466037151; fax: +420 466037068.
ˇ ˇ
E-mail address: ales.ruzicka@upce.cz (A. Ru˚ zicka).
0022-328X/$ - see front matter Ó 2009 Elsevier B.V. All rights reserved.
doi:10.1016/j.jorganchem.2009.04.043

J. Turek et al. / Journal of Organometallic Chemistry 694 (2009) 3000–3007
3001
NaCp
LCNR2SnCp
LCNR2SnCl
(1a - c)
-30°C
(2a - b)
K(BEt3)H.THF
-20°C
N(CH3)2
LCNR2SnH
(3a - c)
3
5
2
1
4
= LCN
3 equiv. K
-30°C
[LCNR2Sn]2
(4a - c)
6
a; R=n-Bu, b; R=Ph, c; R=t-Bu
Scheme 1.
Table 1
Selected NMR spectra parameters
Compound type/R d(119Sn) [ppm]/1J(119Sn, X), X = 1H for 3; X = 117Sn for 4; X = 19
F
for LCNR2SnF [Hz]
n-Bu
Ph
t-Bu
L
L
CNR2SnCpa
ꢀ73.6 (2a)
ꢀ144.9 (2b)
–
Fig. 1. ORTEP plot of molecule 2b showing 50% probability displacement ellipsoid
CNR2SnHa
ꢀ113.2 (3a)/1668
ꢀ105.7 (4a)/3416
ꢀ77.1 [6]/2114
ꢀ51.7 (1a) [6]
ꢀ76.9 [17]
ꢀ180.9 (3b)/2128
ꢀ145.1 (4b)/5158
ꢀ198.6 [6]/2148
ꢀ177.1 (1b) [15]
ꢀ187.6 [17]
ꢀ90.0 (3c)/1638
and the atom numbering scheme. Hydrogen atoms were omitted for clarity.
0
(LCNR2Sn)2
LCNR2SnFb
(4c)c
a
Selected bonding lengths (ÅA) and angles (°): Sn1–N1 2.7288(17), Sn1–C1
2.1427(18), Sn1–C10 2.292 (2), Sn1–C15 2.144(2), Sn1–C21 2.129(2), Sn1–C10–Cg
108.9(1), C21–Sn1–C1 116.06(7), C21–Sn1–C15 116.24(8), C1–Sn1–C15 117.39(7),
C21–Sn1–C10 102.80(7), C1–Sn1–C10 100.25(8), C15–Sn1–C10 99.42(8).
ꢀ92.1 [6]/2197
17.5 (1c) [16]
ꢀ46.3 [17]
ꢀ35.6 [17]
L
L
CNR2SnClb
CNR2SnOHa
(LCNR2Sn)2Oa
ꢀ59.3 [17]
ꢀ173.2 (5b) [17]
a
Measured in C6D6.
Measured in CDCl3.
See Section 3.
b
c
hydride (4.78 ppm) [23,24]. Another parameter characteristic for
monomeric triorganotin hydrides is 1J(119Sn, 1H) coupling constant,
found here to be 1627 Hz for 3a, 2128 Hz for 3b to be compared to
1576 Hz for n-Bu3SnH and 1950 Hz for Ph3SnH [25]. The 119Sn
chemical shift of compound 3a (ꢀ113.2 ppm, Table 1) is strongly
shifted to low frequency field when compared to its closest analog
without intramolecular donor, Bu2PhSnH, 82 ppm [26]. In contrast,
the change observed for the 119Sn chemical shift of the diphenyl
substituted compound 3b, ꢀ180.9 ppm, when compared to the va-
lue for Ph3SnH, ꢀ162.1 ppm, is rather limited. These results sug-
gest a strong intramolecular Sn–N coordination in 3a, but only a
limited one, at most very weak, for the triaryl compound 3b. This
discrepancy can be tentatively ascribed to the larger steric strain
induced by the phenyl groups. An alternative explanation could
be that, since the n-butyl groups of 3a are inductive releasing
groups, while the phenyl groups of 3b are inductive electron with-
drawing, the hydride ligand should be much more apicophile in 3a
than in 3b, explaining why the former tends more to five-coordina-
tion, while the latter would be rather tetrahedral. Unfortunately no
crystals could be obtained for any of these hydrides, so that corrob-
orating any of this explanation with an X-ray structure determina-
tion of 3a and/or 3b turned out impossible.
Further reactivity of the starting chlorides was investigated as
reductors using a slight excess of potassium mirror, which yielded
the corresponding hexaorganodistannanes. In the case of the n-bu-
tyl substituted organotin, the only product was the distannane 4a.
Compound 4a reveals similar 119Sn NMR shift value change as 3a
(ꢀ105.7 ppm), indicating relatively strong Sn–N intramolecular
coordination leading to five-coordinated tin atom in this com-
pound, unfortunately the direct proof as the 119Sn NMR shift value
for (Phn-Bu2Sn)2 is not available in the literature. The 1J(119Sn,
117Sn) coupling constant of 4a is 3416 Hz, but in hexaorganodist-
annanes in general, this coupling constant can display a wide range
of values from 624 to 16870 Hz [27]. The reduction of 1b by potas-
sium mirror was performed in a similar way as for 1a. Even though
all the processes were performed in strict moisture- and air-free
conditions, two 119Sn resonances (ꢀ145.1 and ꢀ172.6 ppm in inte-
gral ratio 15:1) were observed for the target compound 4b. The
high frequency resonance is assigned to the distannane because
of its coupling satellites (1J(119Sn,117Sn) = 5158 Hz), while the low
frequency resonance arises from the distannoxane 5b [17], which
in good agreement with a distorted trigonal bipyramidal configura-
tion at the tin atom. These values are of the same order of magni-
tude as for the starting chlorides and related compounds (see Table
1).
Single crystals of 2b were obtained from diethyl ether at ꢀ30 °C.
The geometry of the tin atom is in agreement with the solution
NMR data, with a relatively weak Sn–N intramolecular interaction
0
(2.7288(17) ÅA) and a trigonal bipyramidal coordination geometry.
The sum of the equatorial C–Sn–C angles is 349.69°, which demon-
strates a deviation towards the tetrahedral geometry. There is a
0
notable elongation of Sn1–C10 (2.2922(19) ÅA) bond, being about
0
0
0.06–0.10 ÅA longer than usual Sn–CCp bonds (2.19–2.23 ÅA) [19],
likely related to the trans effect of the weakly tin coordinating
Me2N moiety. Also the Sn1–C10–Cg (as centroid of Cp ring) angle
(108.95°) is smaller than expected for a non-distorted structure
(ideally 125°) [19], for example for (1-(CH3)3Sn)(3-
(C6H5)3C)C5H4(118.0(1)°) [20].
The sigmatropic migration of the tin atom around the cyclopen-
tadienyl ring, rapid on the proton NMR time scale, focused much
attention in the past [21]. This phenomenon was also observed
for 2a and 2b, with only some signal broadening in toluene at
low temperature. At 180 K, the onset to a decoalescence, evidenced
by a saddle point in the resonance, was observed at 6.81 ppm for
2a. An estimation of the Gibbs free energy for this sigmatropic
migration in 2a, based on these data, provides 37 1 kJ/mol, which
is higher than for Me3Sn(g
1-C5H5), 29.7 2.9 kJ/mol [19]. One
might expect that the coordination of Me2N-group to tin would in-
crease the ionic character of Sn–Cp bond (trans effect), thus leading
to the decrease in energy barrier. We assume that the observed in-
crease is due to steric repulsion of Cp ring and phenyl group of LCN
ligand (Fig. 1).
The reactions yielding hydrides 3a–c were carried out in THF
solution at ꢀ40 °C. The yield in the obtained hydrides, using
K(BEt3)HꢁTHF, is much better than reported by Vedejs, using LiAlH4
[22]. All hydrides reveal the typical hydride 1H NMR signal, albeit
shifted to higher frequency (5.83 ppm for 3a, 6.98 ppm for 3b,
and 6.01 ppm for 3c) when compared, for example, to tributyltin

3002
J. Turek et al. / Journal of Organometallic Chemistry 694 (2009) 3000–3007
though this distance is much smaller than the sum of the Van
der Waals radii. In the co-crystal of 4bꢁ(5b)2 there are comparable
interatomic distances for the 5b fragment as found for the struc-
ture of 5bꢁC6D6 [17]. The only difference is the wider Sn–O–Sn an-
gle in the case of co-crystal 4bꢁ(5b)2 caused probably by crystal
packing.
2.1. Reactivity of selected compounds
In order to investigate the potential chemistry of the prepared
compounds, the following reactions have been performed. Com-
pounds 3a, 4a and 3b were treated with one molar equivalent of
the TEMPO – free radical at room temperature in benzene for
5 min in order to prepare the appropriate organotin radical. Similar
results were obtained for the reaction of 2a and 2b under UV-light
irradiation for 1 h under the same conditions. Unfortunately no re-
sults were obtained, in particular no tin radical could be observed
using ESR.
In order to prepare chalcogen derivatives of the compounds
studied, 4a was treated with an excess of oxygen in benzene solu-
tion at room temperature for 10 min, and with one equivalent of
sulfur, selenium and tellurium in benzene solution at 80 °C for
6 h. No product was observed in all reaction attempts. Under
slightly more drastic conditions, the reaction of neat 4a in molten
sulfur gave exclusively (LCNn-Bu2Sn)2S, which displays a single
119Sn signal at ꢀ7.7 ppm with 2J(119Sn, 117Sn) satellites of 162 Hz.
This indicates tetrahedrally coordinated tin atom (about 70 ppm
difference in comparison to an oxide analog (LCNn-Bu2Sn)2O, see
Table 1) and is also comparable to previously found values for tri-
organotin sulfides [30a,b].
To examine the possibilities of hydrostannation reactions, 3a
was heated with ferrocenylacetylene at 90 °C in a sealed NMR tube
for 6 h, giving a mixture of stannylated ferrocenyl derivatives in
overall 47.2% yield. For comparison, the reaction of Bu3SnH with
ferrocenylacetylene gave no desired product under the same con-
ditions. The same reaction was also conducted in the presence of
a catalytic amount (1 mol.%) of Pd(PPh3)4 at ꢀ30 °C for 30 min.
Compound 3a gave the same product as in the previous case in
23.6% yield and Bu3SnH gave virtually no reaction. The yield in fi-
nal stannylated vinylferrocene compound was deduced from the
integral ratio of the new and well-separated doublet at 6.28 ppm,
tentatively assigned to one of the vinylic protons, and the hydride
signal of unreacted 3a,b.
Fig. 2. ORTEP plot of molecule 4b showing 50% probability displacement ellipsoid
and the atom numbering scheme. Hydrogen atoms and the stannoxane molecule
0
were omitted for clarity. The selected bonding lengths (ÅA) and angles (°): for 4b:
Sn1–Sn1a 2.8014(13), Sn1–N11 3.106(13), C21–Sn1–C11 110.53(12), C21–Sn1–C31
103.54(12), C11–Sn1–C31 103.99(12), C21–Sn1–Sn1a 122.94(9), C11–Sn1–Sn1a
111.52(8), C31–Sn1–Sn1a 101.78(8); for 5b: Sn2–O1 1.958(3), Sn3–O1 1.976(3),
Sn3–N71 2.723(3), Sn2–N41 2.789(3), O1–Sn2–C41 96.01(12), O1–Sn2–C61
98.16(13), C41–Sn2–C61 123.84(13),O1–Sn2–C51 108.75(11), C41–Sn2–C51
112.32(13), C61–Sn2–C51 113.64(13), O1–Sn3–C71 94.47(11), O1–Sn3–C91
99.90(12), C71–Sn3–C91 131.37(12), O1–Sn3–C81 101.82(12), C71–Sn3–C81
111.85(12), C91–Sn3–C81 110.16(13), Sn2–O1–Sn3 142.69(14).
is the oxidation product of 4b. The value of 119Sn NMR chemical
shift of ꢀ145.1 ppm, to be compared with that of hexaphenylditin,
ꢀ144 ppm [30c,d], indicates a four-coordinate tin atom without
any Sn–N interaction. This matches the high reactivity of 4b to-
wards oxygen. A couple of crystals suitable for X-ray diffraction
measurements were obtained in the NMR tube of crude product.
These crystals are formed by one equivalent of distannane 4b
and two equivalents of distannoxane 5b (Figs. 2 and 3).
The structure of 4b consists of two symmetry equivalent tin
moieties, where the tin atoms are tetrahedrally coordinated by
the three phenyl carbon atoms and the adjacent tin atom. The
sum of the interatomic angles C–Sn–C (318.1°), is extremely small,
being 328.5° for an ideal tetrahedral configuration of the tin atom.
The Sn–Sn bond distance of 2.8014(13) Å is relatively short and of
the same order as the Sn–Sn distance in Me6Sn2 (2.78 Å) in the va-
por phase, as found by gas electron diffraction, 2.763(2) Å for
Ph6Sn2 [28] and the Sn–Sn distance (2.804(4) Å) recently observed
in our group for a distannane coordinated by zirconocene [29]. The
nitrogen atom is primarily not involved in the tin atom coordina-
tion sphere, given the long Sn1–N11 bond (3.106(13) Å), even
Activation of small molecules such as CO2 is presently the object
of major investigation. CO2 activation by organotin(IV) species to
give linear and/or cyclic organic organotin [17,31] carbonates
was reported previously [32]. The use of both tin(II) and tin(IV) hy-
drides to produce formates as reactive species is also mentioned in
the literature [33]. The reaction of 3a with CO2 gave formate LCN(n-
Bu)2SnOC(@O)H (Scheme 2) in almost quantitative yield when the
Fig. 3. View of the unit cell of 4bꢁ(5b)2.

J. Turek et al. / Journal of Organometallic Chemistry 694 (2009) 3000–3007
3003
reaction was carried out in hexane. In the case of the same reaction
in benzene, but with moistened CO2, formaldehyde was obtained
as a by-product, as identified by NMR and IR. LCN(n-Bu)2S-
nOC(@O)H reveals, for the SnOC(@O)H moiety, a characteristic 1H
lium tetrakis(pentafluorophenyl)borate [38] both for three-coordi-
nated tin atom and N,C,N- or O,C,O-chelating ligands derivatives for
five-coordinated tin atoms [39]. The determined crystal structure of
[LCN(n-Bu)2Sn]+[Ti2Cl9]ꢀ revealed the same geometry for the tin
atom as proposed from the solution NMR studies. Three carbon
atoms are localized in the basement of the square pyramid which
resonance at 8.78 ppm and
a
characteristic 13C NMR at
168.3 ppm, in good agreement with data of Jana et al. [33a]. The
single 119Sn NMR resonance at ꢀ75.4 ppm indicates a monomeric,
monodentate bonding mode for the formate ligand to the five-
coordinated tin center as observed for analogous carboxylates
[34]. Infrared spectra of the isolated product showed strong
absorption bands at 1591, 1367 and 761 cmꢀ1 that are assigned
is capped by the nitrogen donor atom (Fig. 4). The sum of the three
0
C–Sn–C angles is 356.5(2)°, and the Sn1–N1 distance is 2.258(4) ÅA,
the shortest one found for a donor–acceptor Sn–N connection.
[LCN(n-Bu)2Sn]+[Ti2Cl9]ꢀ is the first four-coordinate triorganotin(IV)
ionic compound. Attempts to prepare analogous ionic species by
reaction of 1a with AgPF6, AgBF4, and AgSbF6 failed [40]. The dis-
to the ma, ms and scissoring modes of the formate moiety, respec-
tively. A similar IR pattern has been reported for related com-
pounds R3SnOC(@O)H (R = Me, Et, n-Pr) [35,36].
tance between the Sn1 atom of a molecule and the Cl2a atom from
0
symmetry related Ti2Clꢀ anion (3.1872(14) ÅA) is smaller than the
9
0
Based on 1H, 13C and 119Sn NMR spectra LCN(n-Bu)2SnOC(@O)Me
(see Fig. 6) and LCN(n-Bu)2SnOMe [17] are most probably the prod-
ucts of reaction of 3a with CO2 in methanol. The 119Sn NMR spec-
trum displays two signals in ratio 100 (ꢀ46.8 ppm) to 37
(ꢀ65.8 ppm), the minor signal being assigned to the methoxide.
The 13C NMR spectrum of the solid product washed with benzene
displays a broad resonance at 161.5 ppm assigned to the carbonate
function [17,31]. The IR spectrum of isolated solid shows a broad ma
band centered at 1672 cmꢀ1 indicating the presence of carboxylic
ester. The strong band at 1342 cmꢀ1 is assigned to the ms mode of
the OCO moiety. The absorption band gap between ma and ms of
330 cmꢀ1 indicates a contribution of ionic form that could be ex-
plained by the presence of the asymmetric methylcarbonate unit
O-bonded to the tin atom, in agreement with earlier observations
for oligomeric compounds of the type [Bu3SnOC(@O)OR]n
(R = Me, i-Pr) [33a].
Another reaction at room temperature, between cyclohexene
oxide and CO2 at atmospheric pressure, in the presence of 3a, gave,
after 30 min, the cyclic carbonate, hexahydro-benzo[1,3]dioxol-2-
one, with 7% yield calculated from the starting oxide amount.
The 119Sn NMR spectrum of the reaction mixture revealed two sig-
nals, a major one at ꢀ69.7 ppm and a minor one at ꢀ48.5 ppm
which do not raise from the starting hydride 3a but rather from
the corresponding tin alcoholate [17] and the above mentioned
carbonate.
sum of van der Waals radii (3.92 ÅA) (Fig. 5), indicating a contact. This
anion is a common moiety stabilizing various unstable cations, as
the oxonium [41], iminium [42], phosphonium [43] or thiophenium
[44] ones. When 3a is reacted with only one mole equivalent of
TiCl4, 1a and CpTiCl3 are detected by 1H and 119Sn NMR. In the case
of the reaction of 3a with a half equivalent of FeBr2 in THF at room
temperature, ferrocene and LCN(n-Bu)2SnBr [12] were found as
products.
Since [LCN(n-Bu)2Sn]+[Ti2Cl9]ꢀ is the first four-coordinated trior-
ganotin(IV) ionic compound it was of interest to study stabilization
factors by DFT methods. As can be seen from Fig. 6, in all cases,
abstraction of Clꢀ from triorganotin compounds using two mole-
cules of TiCl4 with formation of isolated ions is an energetically
unfavorable process. Free Gibbs energies of the reactions show
highly positive values. However, the presence of coordination
groups at tin assist ionization. The presence of one-coordination
group lowers the Gibbs free energy by 125.6 kJ/mol. The coopera-
tive effect of two-coordination groups is even higher,
DDG0 = 205.2 kJ/mol. Thus in the absence of coordination groups
at tin, the isolation of stannylium ions is achieved with the use
ꢀ
of weakly coordinating anions [Bu3Sn]+[CB11Me12
]
[37], and/or
by introduction of steric bulk [(2,4,6-iPrC6H2)3Sn]+[B(C6F5)4]ꢀ
[38]. Further, the use of O,C,O and N,C,N monoanionic tridentate li-
gands allows the isolation of stannylium ions in presence of nucle-
ophilic anions such as halogenides [39].
To examine the possible transfer of the Cp ring from 2a to a moi-
ety with a transition metal atom, the reaction of 2a in benzene with
neat TiCl4 in excess was investigated. In the reaction mixture,
It should be noted that not only steric and electronic factors are
responsible for the formation of ionic species. Thus, optimization of
the isolated structure of [LCN(n-Bu)2Sn]+[Ti2Cl9]ꢀ reveals that the
Sn–Cl bond distance is significantly shorter in the isolated struc-
ture (2.756 Å), than in the crystal state (3.187 Å), while it is longer
CpTiCl3, [LCN(n-Bu)2Sn]+[Ti2Cl9]ꢀ and
a minor amount of (n-
Bu)2SnCl2 were detected in various NMR spectra. The 1H NMR spec-
trum of [LCN(n-Bu)2Sn]+[Ti2Cl9]ꢀ gave a single set of broad signals,
while the 119Sn NMR signal at 185.6 ppm indicated a four-coordi-
nate tin atom. This chemical shift value is about 240 ppm to higher
frequency with respect to starting compound 3a or chloride 1a, as
similarly found for tributylstannylium [37]. Such an increase is
most probably caused by the ionic character of [LCN(n-Bu)2-
Sn]+[Ti2Cl9]ꢀ in benzene solution. The structure of the organotin
fragment is thus composed of three carbon atoms and one intramo-
lecularly coordinated nitrogen atom. The ionization of triorganotin
compounds was observed in the case of tributyltin dodecamethyl-
1-carba-closo-dodecaborate [37], tris(triisopropylphenyl)stanny-
O
MeOH
LCN(n-Bu)2Sn
LCN(n-Bu)2Sn
O
OMe
H
LCN(n-Bu)2SnH + CO2
hexane
O
O
Fig. 4. ORTEP plot of the molecule [LCN(n-Bu)2Sn]+[Ti2Cl9]ꢀ showing 50% probability
displacement ellipsoids and the atom numbering scheme. Hydrogen0 atoms, C6D6
and [Ti2Cl9]ꢀ were omitted for clarity. The selected bonding lengths (AÅ) and angles
(°): Sn1–N1 2.258(4), Sn1–C1 2.121(5), Sn1–C10 2.129(5), Sn1–C14 2.152(5), C1–
Sn1–C10 123.56(19), C1–Sn1–C14 114.87(19), C10–Sn1–C14 118.1(2).
Scheme 2.

3004
J. Turek et al. / Journal of Organometallic Chemistry 694 (2009) 3000–3007
tional PBE [45,46]. Valence electrons were treated using TZ2P
basis set. Innermost electrons of Sn, Ti, Cl, C, N atoms were emu-
lated using effective core potentials ECP-SBKJC [47]. All calcula-
tions were made using the PRIRODA program [48].
3.3. ESR spectroscopy
The solution ESR spectra were recorded at ambient temperature
at X-band (
m
ꢂ 9.5 GHz) using an ERS 221 spectrometer (Magnet-
tech Berlin). A microwave power of 1 mW, sufficiently below the
saturation power, was used.
3.4. NMR spectroscopy
The NMR spectra were recorded from samples in C6D6 solution,
unless otherwise indicated, on a Bruker Avance 500 spectrometer
(equipped with Z-gradient 5 mm probe) at 300 K with resonance
frequencies of 500.13 MHz for 1H, 186.50 MHz for 119Sn{1H} and
125.67 MHz for 13C{1H} nuclei. The assignments of 1H resonances
were achieved from standard 2D spectra. The solutions were ob-
tained by dissolving 40 mg of each compound in 0.5 ml of C6D6
or CD3OD in vacuo sealed tubes. The 1H chemical shifts were cali-
brated relative to the signal of residual benzene (7.16 ppm) or
methanol (4.87 ppm). The 13C chemical shifts were calibrated rela-
tive to the residual benzene (128.44) or methanol (49.1 ppm) sig-
nal. The 119Sn chemical shifts are referred to external neat
tetramethylstannane (d = 0.0). 119Sn NMR spectra were measured
using the inverse gated proton broad band decoupling mode.
Fig. 5. View of the cationic and symmetry related anionic parts of [LCN(n-
0
Bu)2Sn]+[Ti2Cl9]ꢀ with Sn1–Cl2a interaction. Sn1–Cl2a 3.1872(14) AÅ, N1–Sn1–Cl2a
171.42(12)°; symmetry operator = x, y, ꢀ1 + z.
Bu
Bu
Bu
-
Sn Cl
Bu
Sn
+2TiCl4
+Ti2Cl9
G0 =456.4;
G 0 = 0.0
NMe2
NMe2
3.5. X-ray crystallography
Bu
Sn
Bu
Bu
-
Data for the colorless crystals were collected on a Nonius Kap-
Sn
Cl
+2TiCl 4
+Ti2Cl9
Bu
paCCD diffractometer using Mo K
a radiation (k = 0.71073 Å), and
a graphite monochromator. The structures were solved by direct
methods (SIR92 [49]). All reflections were used in the structure
refinement based on F2 by full-matrix least-squares technique
G 0 =330.8; G 0 = 125.6
(
SHELXL97 [50]). Heavy atoms were refined anisotropically. The high-
NMe2
Bu
NMe2
est residual maximum in the co-crystal of 4bꢁ(5b)2 is close to the
tin atoms. Hydrogen atoms were localized on a difference Fourier
map; however to ensure the uniformity of the treatment of the
crystal, they were all recalculated into idealized positions (riding
model) and were assigned temperature factors Hiso(H) of 1.2 Ueq
(pivot atom) or of 1.5 Ueq for the methyl group. Absorption correc-
tions were carried on, using Gaussian integration from crystal
shape [51].
Bu
Sn
-
Sn
Cl
+2TiCl 4
+Ti2Cl9
Bu
Bu
NMe2
Me2N
G 0 =251.2; G 0 = 205.2
Fig. 6. Calculated energies of Clꢀ abstraction from triorganotin compounds (free
Gibbs energies in kcal/mol).
3.5.1. Crystallographic data for 4bꢁ(5b)2
2(C42H44N2OSn2)ꢁC42H44N2Sn2, M = 2474.52, monoclinic, C 2/c,
a = 55.9238(5), b = 9.80601(10), c = 21.1252(2) Å, b = 105.4850
(6)°, Z = 4, V = 11164.23(18) Å3, Dc = 1.472 g cmꢀ3, 1.375 mmꢀ1
,
than the calculated Sn–Cl bond length in LCN(n-Bu)2SnCl (2.472 Å).
Thus, the crystal field effect is also of importance for the formation
of tetracoordinated LCN(n-Bu)2Sn+ stannylium cation.
Tmin = 0.785,
(hmax = 27.5°), 12 799 independent (Rint = 0.0537), 10 061 with
I > 2 (I), 637 parameters, S = 1.041, R1(obs. data) = 0.0363, wR2(all
Tmax = 0.910;
81 362
reflections
measured
r
data) = 0.0766; maximum, minimum residual electron den-
0
3. Experimental
sity = 2.806, ꢀ1.518 eÅAꢀ3
.
3.1. IR spectroscopy
3.5.2. Crystallographic data for 2b
26H27NSn, M = 472.18,
b = 11.1968(3), c = 12.1249 Å,
ꢀ
C
triclinic,
= 78.5558(13)°, b = 83.3013(16)°,
V = 1094.02 Å3, Dc = 1.433 g cmꢀ3
= 1.178 mmꢀ1, Tmin = 0.758, Tmax = 0.840; 20 385 reflections mea-
P1,
a = 8.2807(2),
Infrared spectra were recorded on a FTIR Nicolet Magna 550
spectrometer, the sample being placed between KBr windows dis-
persed in Nujol.
a
c
= 87.3236(16)°,
Z = 2,
,
l
sured (hmax = 27.5°), 5025 independent (Rint = 0.0361), 4598 with
3.2. Calculation procedure
I > 2 (I), 259 parameters, S = 1.052, R1(obs. data) = 248, wR2(all
r
data) = 0.0581; maximum, minimum residual electron den-
All molecules were studied at the DFT level. Molecular geome-
tries were optimized using generalized gradient-corrected func-
0
sity = 0.799, ꢀ0.788 eAÅꢀ3
.

J. Turek et al. / Journal of Organometallic Chemistry 694 (2009) 3000–3007
3005
3.5.3. Crystallographic data for [LCN(n-Bu)2Sn]+[Ti2Cl9]ꢀꢁC6D6
product was obtained when the mother liquor was evaporated in
vacuo. 1H NMR (C6D6, 300 K, ppm): 7.78 (d, 1H-6, 3J(119Sn,
1H) = 55 Hz); 7.20 (m, 2H-4, 5); 7.06 (m, 1H-3); 5.83 (s, 1H-SnH,
1J(119Sn, 1H) = 1627 Hz); 3.25 (s, 2H-NCH2); 1.99 (s, 6H-N(CH3)2);
ꢀ
C23H36Cl9NSnTi2, M = 860.07, triclinic, P1, a = 9.6642(8),
b = 10.0831(6), c = 10.2396(4) Å,
a = 92.325(4)°, b = 101.151(4)°,
c
= 115.512(6)°,
Z = 1,
V = 874.83(10) Å3,
Dc = 1.633 g cmꢀ3
,
1.856 mmꢀ1, Tmin = 0.519, Tmax = 0.650; 16 514 reflections mea-
sured (hmax = 27.49°), 7427 independent (Rint = 0.0564), 6671 with
1.73 (m, 4H-a); 1.47 (m, 4H-b); 1.18 (m, 4H-c); 0.98 (t, 6H-d).
119Sn{1H} NMR (C6D6, 300 K, ppm): ꢀ113.2 (s, 1J(1H, 119Sn) =
1668 Hz). 13C{1H} (C6D6, 300 K, ppm): 146.0 (C-2, 2J(119/117Sn,
13C) = 24 Hz); 142.0 (C-1, 1J(119Sn, 13C) = 500 Hz, 1J(117Sn,
13C) = 477 Hz); 138.7 (C-3, 3J(119/117Sn, 13C) = 40 Hz); 128.8 (C-5,
3J(119/117Sn, 13C) = 40 Hz); 128.7 (C-4, 4J(119/117Sn, 13C) = 11 Hz);
127.5 (C-6, 2J(119/117Sn, 13C) = 51 Hz; 66.5 (C-NCH2, nJ(119/117Sn,
13C) = 19 Hz); 44.8 (C-N(CH3)2); 30.8 (C-b, 2J(119/117Sn,
I > 2r(I), 325 parameters, S = 1.118, R1(obs. data) = 0.0385, wR2
(all data) = 0.0849; maximum, minimum residual electron
0
P
P
density = 0.679,
ꢀ0.979 eAÅꢀ3
.
Rint
¼
jF2o ꢀ F2o;meanj=
F2o;
1
ꢄ
ꢂ
ꢃ
ꢅ
ꢀ
ꢁ
2
2
P
S ¼
w F2o ꢀ F2c
=ðNdiffrs
ꢀ
Nparams
Þ
,
weighting scheme:
h
iꢀ1
h
ꢀ
ꢁ
i
13C) = 20 Hz); 27.9 (C-
c,
3J(119/117Sn, 13C) = 61 Hz); 14.3 (C-d);
2
w¼ r2ðFo2Þþðw1PÞ þw2P
,
where P¼ max F2o þ2Fc2 ;RðFÞ¼
11.3 (C-
a
, 1J(119Sn, 13C) = 384 Hz, 1J(117Sn, 13C) = 367 Hz). Anal. Calc.
ꢄ
ꢂ
ꢃꢆ
ꢀ
ꢁ
ꢀ
ꢁ
2
P
P
P
P
1
2
2
kFojꢀjFck= jFoj;wRðF2Þ ¼
w F2o ꢀF2c
wðF2oÞ ꢃ .
for C17H31NSn (368.13): C, 55.47; H, 8.49; N, 3.80. Found: C, 55.5;
H, 8.5; N, 3.8%.
3.6. GC/MS
3.7.3. Bis{[2-(N,N-dimethylaminomethyl)phenyl]di-n-butyltin(IV)}
(4a)
The samples were analysed using a gas chromatograph GC 17A
coupled with a mass spectrometry detector QP 5050A (EI, NCI, both
Shimadzu) and a GC/MS solution data system (Shimadzu). The he-
lium (grade 5.0, Linde) was used as carrier gas. Separations were
The K-mirror (0.65 g, 16.6 mmol) was prepared and poured over
with hexane. Afterwards, the solution of (LCN)(n-Bu)2SnCl (4.5 g,
11.0 mmol) in hexane was added during 15 min at ꢀ30 °C. The
reaction mixture was stirred for 5 days. Afterwards, the solvent
was evaporated in vacuo. A white oily product was obtained. Yield
3.72 g (92%). 1H NMR (C6D6, 300 K, ppm): 7.74 (d, 2H-6, 3J(119Sn,
1H) = 48 Hz); 7.30 (m, 4H-4, 5); 7.15 (m, 2H-3); 3.34 (s, 4H-
performed on a capillary column (30 m, 25
lm i.d.) coated with a
0.25 m film of polymethylsiloxane (HP-5 MS). Split injection
l
1:200 was used. The column oven was isothermally maintained
at 45 °C for 1 min and, subsequently, a temperature increase for
20 °C/min to 300 °C (kept for 6.5 min) was applied. The tempera-
ture of the injector was 220 °C and the temperature of the interface
was 230 °C. The identification of the compounds was based on the
comparison of their mass spectrum with the library spectrum
(NIST 107 and NIST 21, Shimadzu).
NCH2); 2.01 (s, 12H-N(CH3)2); 1.71 (m, 8H-a); 1.44 (br m, 16H-b,
c
); 0.95 (t, 12H-d). 119Sn{1H} NMR (C6D6, 300 K, ppm): ꢀ105.7
(s, 1J(119Sn, 117Sn) = 3416 Hz). Anal. Calc. for C34H60N2Sn2
(734.25): C, 55.62; H, 8.24; N, 3.82. Found: C, 55.6; H, 8.2; N, 3.8%.
3.7.4. [2-(N,N-dimethylaminomethyl)phenyl]diphenyltin (IV)
cyclopentadienide (2b)
3.7. Synthesis
Compound 1b (0.80 g, 1.8 mmol) was dissolved in diethyl ether
and a solution of NaCp (0.16 g, 1.8 mmol) in diethyl ether was
added dropwise during 10 min at ꢀ30 °C. The reaction mixture
was stirred for 5 days. Afterwards, the reaction mixture was fil-
tered off and the solvent was evaporated in vacuo. A yellow crystal-
line product was obtained. The solid was recrystallized at ꢀ30 °C
from diethyl ether to give white crystals. Yield 0.61 g (72%), m.p.
217–220 °C. 1H NMR (C6D6, 295 K, ppm): 8.18 (d, 1H-6, 3J(119Sn,
1H) = 64 Hz); 7.46 (m, 12H-4, 5, o, m, p); 7.14 (m, 2H-3); 6.29 (s,
5H-Cp, 2J(119Sn, 1H) = 19 Hz); 2.99 (s, 2H-NCH2); 1.27 (s, 6H-
N(CH3)2). 119Sn{1H} NMR (C6D6, 295 K, ppm): ꢀ144.9 (s). Anal. Calc.
for C26H27NSn (472.20): C, 66.13; H, 5.76; N, 2.97. Found: C, 66.2;
H, 5.8; N, 3.0%.
All experiments were carried out under argon atmosphere.
(N,N-dimethylaminomethyl)benzene, sodium cyclopentadienide
(NaCp), K(BEt3)HꢁTHF and potassium were purchased (Sigma–Al-
drich). Diethyl ether, THF and n-hexane were dried over and dis-
tilled from potassium-sodium alloy, degassed and stored under
argon over a potassium mirror. Compounds 1a–c were obtained
by published methods [12,15,16].
3.7.1. [2-(N,N-dimethylaminomethyl)phenyl]di-n-butyltin (IV)
cyclopentadienide (2a)
Compound 1a (2.6 g, 6.5 mmol) was dissolved in diethyl ether
and a solution of NaCp (0.57 g, 6.5 mmol) in diethyl ether was
added dropwise during 10 min at ꢀ30 °C. The reaction mixture
was stirred for 5 days. Afterwards, the reaction mixture was fil-
tered off and the solvent was evaporated in vacuo. A brown oily
product was obtained in 81% yield (2.3 g). 1H NMR (C6D6, 295 K,
ppm): 8.00 (d, 1H-6, 3J(119Sn, 1H) = 50 Hz); 7.24 (m, 2H-4, 5);
7.03 (d, 1H-3); 6.42 (s, 5H-Cp, 2J(119Sn, 1H) = 14 Hz); 3.19 (s, 2H-
3.7.5. [2-(N,N-dimethylaminomethyl)phenyl]diphenyltin (IV) hydride
(3b)
Compound 1b (0.54 g, 1.2 mmol) was dissolved in THF at
ꢀ20 °C and 1.22 ml of K(BEt3)HꢁTHF (c = 1 mol dmꢀ3, 1.2 mmol)
were added. The reaction mixture was stirred up to room temper-
ature. Subsequently, the solvent was evaporated in vacuo, diethyl
ether was then added and the soluble part was isolated by filtra-
tion. A colorless solution of the desired product was obtained. 1H
NMR (C6D6, 295 K, ppm): 7.60 (d, 1H-6, 3J(119Sn, 1H) = 58 Hz);
7.14 (br m, 13H-3, 4, 5, o, m, p); 6.98 (s, 1H-SnH, 1J(119Sn,
1H) = 2128 Hz); 3.15 (s, 2H-NCH2); 1.66 (s, 6H-N(CH3)2). 119Sn{1H}
NMR (C6D6, 295 K, ppm): ꢀ180.9 (s). Anal. Calc. for C21H23NSn
(408.11): C, 61.80; H, 5.68; N, 3.43. Found: C, 61.8; H, 5.7; N, 3.4%.
NCH2); 1.92 (s, 6H-N(CH3)2); 1.62 (m, 4H-
1.40 (m, 4H-
a); 1.52 (m, 4H-b);
c
); 0.96 (t, 6H-d). 119Sn{1H} NMR (C6D6, 295 K, ppm):
ꢀ73.6 (s). Anal. Calc. for C22H35NSn (432.22): C, 61.14; H, 8.16; N,
3.24. Found: C, 61.1; H, 8.2; N, 3.3%.
3.7.2. [2-(N,N-dimethylaminomethyl)phenyl]di-n-butyltin (IV)
hydride (3a)
Compound 1a (1.3 g, 3.2 mmol) was dissolved in THF at ꢀ20 °C
and 3.22 ml of K(BEt3)HꢁTHF (c = 1 mol dmꢀ3, 3.2 mmol) were
added. The reaction mixture was stirred up to room temperature.
Subsequently, the solvent was evaporated in vacuo, hexane was
then added and the soluble part was filtered off. A colorless oily
3.7.6. Bis{[2-(N,N-dimethylaminomethyl)phenyl]diphenyltin(IV)} (4b)
The K-mirror (0.65 g, 16.6 mmol) was prepared and poured over
with hexane. Afterwards, the solution of 1b (4.9 g, 11.0 mmol) in
hexane was added during 15 min at ꢀ30 °C. The reaction mixture
was stirred for 5 days. Afterwards, the solvent was evaporated in

3006
J. Turek et al. / Journal of Organometallic Chemistry 694 (2009) 3000–3007
vacuo. The white solid product was crystallized from toluene. Yield
3.95 g (88%), m.p. 178–180 °C. 1H NMR (C6D6, 300 K, ppm): 9.00 (d,
2H-6, 3J(119Sn, 1H) = 72 Hz); 7.67 (m, 24H-4, 5, o, m, p); 7.05 (d, 2H-
3); 2.95 (s, 4H-NCH2); 1.34 (s, 12H-N(CH3)2). 119Sn{1H} NMR (C6D6,
300 K, ppm): ꢀ145.1 (s, 1J(119Sn, 117Sn) = 5158 Hz). Anal. Calc. for
C42H44N2Sn2 (814.21): C, 61.96; H, 5.45; N, 3.44. Found: C, 62.0;
H, 5.5; N, 3.4%.
orated and the white waxy material obtained was washed by
benzene and crystallized from methanol. The obtained single crys-
tals were destroyed during the XRD measurement. 119Sn{1H} NMR
(C6D6, 300 K, ppm): ꢀ46.6 (s). 13C{1H} (CD3OD 300 K, ppm):
161.50 (C(@O)O–); 147.05 (C-2); 142.94 (C-1); 138.22 (C-3);
130.82 (C-5); 130.24 (C-6); 127.51 (C-4); 67.82 (C-NCH2); 49.67
(OMe); 45.92 (C-N(CH3)2); 30.59 (C-b); 28.71 (C-c); 14.23 (C-d);
11.14 (C- ).
a
3.7.7. [2-(N,N-dimethylaminomethyl)phenyl]di-t-butyltin (IV) hydride
(3c)
3.7.12. 3a + CO2 + cyclohexene oxide
Compound 1c (0.40 g, 1.0 mmol) was dissolved in THF and tol-
The reaction of 10 ml of cyclohexene oxide (98.8 mmol) with
CO2 in presence of 3a (0.72 g, 1.88 mmol, 1.9 mol% to cyclohexene
oxide) was carried out by bubbling CO2 at nearly atmospheric pres-
sure for 30 min at room temperature through the mixture. Color-
less solution was obtained. 1H NMR spectrum of reaction mixture
is very complex and was not analyzed. 119Sn{1H} NMR (C6D6,
300 K, ppm): ꢀ48.5 (s), ꢀ69.7 (s). GC/MS measurement was per-
formed at declared conditions using starting material and product
as standards to proof the course of the reaction.
uene at ꢀ20 °C and 989
ll
of K(BEt3)HꢁTHF (c = 1 mol dmꢀ3
,
1.0 mmol) were added. The reaction mixture was stirred up to
room temperature. Subsequently, the solvent was evaporated in
vacuo, hexane was added and the soluble part was isolated by fil-
tration. A pale yellow solution of the product was obtained. 1H
NMR (C6D6, 300 K, ppm): 7.19 (m, 4H-3, 4, 5, 6); 6.01 (s, 1H-SnH,
1J(119Sn, 1H) = 1638 Hz); 3.28 (s, 2H-NCH2); 2.06 (s, 6H-N(CH3)2);
1.40 (s, 18H-t-Bu, 3J(119Sn, 1H) = 63 Hz). 119Sn{1H} NMR (C6D6,
300 K, ppm): ꢀ90 (s). After 3 days, decomposition of product and
formation of a mixture of new products, probably including dist-
annane, were observed. 119Sn{1H} NMR (C6D6, 300 K, ppm):
ꢀ145.5 (major, s); ꢀ4.8 (major, s); ꢀ64.0 (s); ꢀ70.0 (s); ꢀ80.0 (s).
Acknowledgements
The financial support of the Science Foundation of the Czech
Republic (Grant No. 104/09/0829), the Ministry of Education of
the Czech Republic (Project VZ0021627501) and Academy of
3.7.8. [2-(N,N-dimethylaminomethyl)phenyl]di-n-butyltin(IV) sulfide
Oily 4a (0.44 g, 0.59 mmol) was transferred into a Schlenk tube
and 0.019 g of sulfur (0.59 mmol) was added in one portion. The
mixture was stirred at 140 °C for 4.5 h. A part of the yellow oily
product was dissolved in C6D6 and NMR spectra were recorded.
1H NMR (C6D6, 300 K, ppm): 8.83 (d, 2H-6, 3J(119Sn, 1H) = 58 Hz,
3J(1H, 1H) = 7.2 Hz); 7.27 (m, 4H-4, 5); 7.01 (d, 2H-3, 3J(1H,
1H) = 7.2 Hz); 2.98 (s, 4H-NCH2); 1.94 (s, 12H-N(CH3)2); 1.78 (m,
Sciences
of
the
Czech
Republic
(KJB401550802)
is
acknowledged.
Appendix A. Supplementary material
CCDC 702855, 702854 and 720158 contain the supplementary
crystallographic data for 4bꢁ(5b)2, 2b and [LCN(n-Bu)2Sn]+
[Ti2Cl9]ꢀꢁC6D6. These data can be obtained free of charge from
The Cambridge Crystallographic Data Center via <http://
www.ccdc.cam.ac.uk/data_request/cif>.
8H-a); 1.36 (m, 16H-b, c
); 0.93 (t, 12H-d). 119Sn{1H} NMR (C6D6,
300 K, ppm): ꢀ7.7 (s, 2J(119Sn, 117Sn) = 162 Hz).
3.7.9. [LCN(n-Bu)2Sn]+[Ti2Cl9]ꢀ
Supplementary data associated with this article can be found, in
the online version, at doi:10.1016/j.jorganchem.2009.04.043.
Oily 2a (0.05 g, 0.11 mmol) was transferred into an NMR tube,
dissolved in C6D6 and 50 ll of TiCl4 (0.45 mmol) was added in
one portion. The NMR spectra were recorded. In the 119Sn NMR
spectrum a minor signal from (n-Bu)2SnCl2 was observed. 1H
NMR (C6D6, 300 K, ppm): 7.87 (d, 1H-6, 3J(119Sn, 1H) = 49 Hz);
7.31 (m, 4H-4, 5); 7.15 (d, 2H-3); 2.62 (s, 2H-NCH2); 2.21 (s, 6H-
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