Preparation and structure of tin(IV) catecholates by reactions of C,N-chelated tin(IV) compounds with a catechol or lithium catecholate, and various stannylenes with a quinone

Article abstract of DOI:10.1016/j.jorganchem.2013.07.025

Various tri-, di- and monoorganotin(IV) catecholates were prepared independently by three different reaction pathways, e.g. elimination of a small molecule (lithium halide) from the conversion of organotin(IV) halide with lithium catecholate, condensation or protonolytic reactions of organotin(IV) oxide or hydride with catechol and reduction of a quinone by distannane, organotin(IV) hydride or stannylene. C,N-chelating 2-[(CH₃) ₂NCH₂]C₆H₄- = L^CN, bulky amido ([2,6-(ⁱPr)C₆H₃](SiMe₃)N- = L^N and amido-amino chelating ({2-[(CH₃) ₂NCH₂]C₆H₄}(SiMe₃ or GePh₃)N- = L^NN1 or L^NN2 ligands were used in this study. All tin(IV) catecholates reveal dimeric structures with six-coordinated tin atoms except for (L^CN)₂Sn{(3,5-(t-Bu) ₂C₆H₂]-1,2-(O)₂)} which is monomeric due to the presence of two C,N-chelating ligands. All compounds, including two hydrolysis products, were characterized by a multinuclear NMR approach and X-ray diffraction techniques.

Full text of DOI:10.1016/j.jorganchem.2013.07.025

Journal of Organometallic Chemistry 745-746 (2013) 25e33
Contents lists available at ScienceDirect
Journal of Organometallic Chemistry
journal homepage: www.elsevier.com/locate/jorganchem
Preparation and structure of tin(IV) catecholates by reactions of
C,N-chelated tin(IV) compounds with a catechol or lithium
catecholate, and various stannylenes with a quinone
*
ꢀ
ꢀ
ꢀ ꢁꢀ ꢀ
Jan Turek, Hana Kampová, Zdenka Padelková, Ales Ruzicka
Department of General and Inorganic Chemistry, Faculty of Chemical Technology, University of Pardubice, Studentská 573, CZ-532 10 Pardubice, Czech
Republic
a r t i c l e i n f o
a b s t r a c t
Article history:
Various tri-, di- and monoorganotin(IV) catecholates were prepared independently by three different
reaction pathways, e.g. elimination of a small molecule (lithium halide) from the conversion of orga-
notin(IV) halide with lithium catecholate, condensation or protonolytic reactions of organotin(IV) oxide
or hydride with catechol and reduction of a quinone by distannane, organotin(IV) hydride or stannylene.
C,N-chelating 2-[(CH3)2NCH2]C6H4e ¼ LCN, bulky amido ([2,6-(iPr)C6H3](SiMe3)Ne ¼ LN and amido-
amino chelating ({2-[(CH3)2NCH2]C6H4}(SiMe3 or GePh3)Ne ¼ LNN1 or LNN2 ligands were used in this
study. All tin(IV) catecholates reveal dimeric structures with six-coordinated tin atoms except for
(LCN)2Sn{(3,5-(t-Bu)2C6H2]-1,2-(O)2)} which is monomeric due to the presence of two C,N-chelating li-
gands. All compounds, including two hydrolysis products, were characterized by a multinuclear NMR
approach and X-ray diffraction techniques.
Received 22 May 2013
Received in revised form
9 July 2013
Accepted 9 July 2013
Keywords:
Organotin(IV) compounds
C,N-ligand
Catecholate
NMR
Ó 2013 Elsevier B.V. All rights reserved.
XRD
1. Introduction
polymerization processes [13]. This was proved by polymerization
of styrene and methylmetacrylate in presence of bis(catecholate)
After the first successful tries consisting of trapping unstable
analogs of carbenes [1] e germylenes and stannylenes or dis-
tannynes performed by Neumann [2] and Weidenbruch [3], plenty
of similar reactions of o-benzoquinones [4] and other diones [5]
with these unstable molecules were carried out. Such reactivity
leads usually to five-membered 1,3-dioxametallacycles as demon-
strated for example by Barrau [6], Edelmann [7] and Eaborn and
Smith [8]. The resulting organotin(IV) compounds, formally 1,3-
diols, were recently extensively studied by means of 119Sn NMR
spectroscopy [9] in order to investigate the influence of mainly
glycolic or catecholic ligands to the isomerism of these compounds.
Another promising field of tin(IV) catecholate chemistry are one
electron oxidation reactions investigated first in the 1980s [10],
now followed by Piskunov [11] and others [12] by EPR spectroscopy
techniques.
tin(IV) complex [14]. In addition, these complexes play an impor-
tant role in regulating the chain length and they also provide a
linear growth of the molecular weight of the product with a
growing conversion ratio of the reaction.
In this paper, we report on the reactivity of organotin(IV) halides
or hydride with lithium catecholate or catechol, respectively. The
preparation of the same type of products, tin(IV) catecholates, from
stannylenes containing various ligands (Scheme 1) and 3,5-di-t-
butylquinone was tested.
2. Results and discussion
In our opinion there are three different pathways leading to
tin(IV) catecholates that are synthetically feasible. The first is the
elimination of a small molecule from the conversion of organo-
tin(IV) halide with lithium catecholate, then the condensation or
protonolytic reactions of organotin(IV) oxide or hydride with
catechol and the last is the reduction of a quinone by distannane,
organotin(IV) hydride or stannylene. All these types of reactions
were tested for the preparation of target compounds applicable in
polymer science. They were also tested in order to compare their
structural motifs and to evaluate possible reverse photolytic
reactions.
These days, tin catecholates are thoroughly investigated in many
fields of applications, mainly for their possible catalytic properties.
Thanks to their unique ability of accepting various radicals,
including carbon ones, they can be for example used in radical
* Corresponding author. Fax: þ420 466037068.
ꢁꢀ ꢀ
E-mail address: ales.ruzicka@upce.cz (A. Ruzicka).
0022-328X/$ e see front matter Ó 2013 Elsevier B.V. All rights reserved.
http://dx.doi.org/10.1016/j.jorganchem.2013.07.025

26
J. Turek et al. / Journal of Organometallic Chemistry 745-746 (2013) 25e33
Scheme 1. Schematic view of the studied ligands and the ligand and substituents numbering.
2.1. Condensation and protonolytic reactions
unresolved broad signals. In 119Sn NMR spectrum, the signal at
15.2 ppm is detected. The chemical shift value is indicative to the
proposed structure of the ionic form of LCN(n-Bu)2Snþ similarly to
previously reported cases of ionic stannanes (185.6 ppm for [LCN(n-
Bu)2Sn]þ[Ti2Cl9]ꢀ e extreme case of separated ions [16]; e 1.0 ppm
for [LCN(n-Bu)2Sn]þOTfꢀ [21] and 36 ppm for [LCN(n-
Bu)2Sn]þCB11H1ꢀ2 [22] e weakly interacting ions). The 7Li NMR
spectra reveal the presence of one broad signal at 1.3 ppm. When 5
reacts with an excess of LCN(n-Bu)2SnCl, only signals attributable to
6 along with signals of the starting chloride are detected in both 1H
and 119Sn NMR spectra.
In order to prepare the target tin(IV) catecholates, reactions of
catechol 1 (Scheme 2) (condensation and protonolysis) with oxide
((LCN)2SnO)n [15] and hydride LCN(Bu)2SnH [16], respectively, were
performed. As expected, the products 2 and 3 were obtained in
both cases in moderate yields. No reaction of 3 with an excess of
hydride LCN(Bu)2SnH (even at elevated temperature) has been
observed. This particular compound is characterized by multinu-
clear NMR spectroscopy, where in the 1H spectrum in C6D6, the
signal at 7.34 ppm is assigned to the OH group of the catechol. The
119Sn chemical shift value (ꢀ82.9 ppm) indicates the formation of a
pentacoordinated tin species with a relatively narrow signal.
The non-equivalency of the dimethylaminomethyl groups is
clearly seen from the 1H NMR spectra of 2 where the AX spin
pattern is visible. This indicates the presence of both ligands with a
weak coordination to the tin center in a trans fashion even in so-
lution of the coordinating solvents. The 119Sn NMR shift values of
diorganotin(IV) compound 2 (ꢀ258 ppm) could be attributed to the
pseudo six-coordinated ([4 þ 2]) tin species which are comparable
with values for (LCN)2SnX2 (ꢀ254.6 ppm for X ¼ Cl; ꢀ271.2 ppm for
X ¼ Br) [17,18a].
Reactions of compound 5 with the rest of the diorganotin(IV)
halides in the series (Scheme 4) which contain one or two LCN li-
gands led to the formation of 2 (for alternative preparation see
above) and dimeric products 7 and 8, respectively. As for 2, the non-
equivalency of the dimethylaminomethyl groups is seen from the
1H NMR spectra based on the presence of AX spin patterns (broad
signals for 7 in THF-d8). Here, in contrast to 2, the non-equivalency
is explained by the formation of dimers persistent even in solution
of the coordinating solvents. The 119Sn NMR shift values of 7
(ꢀ270 ppm in toluene-d8 and ꢀ247 ppm in THF-d8) could be again
attributed to the pseudo six-coordinated tin species which are
comparable to values for (LCN)2SnX2 (ꢀ254.6 ppm for
X ¼ Cl; ꢀ271.2 ppm for X ¼ Br) [17,18a], while the value for the five-
coordinated tin in LCN(n-Bu)SnCl2 is from ꢀ98 to ꢀ103 ppm [18].
Compound 2 (Fig. 1) crystallizes as a monomer in the triclinic
crystal system with a six-coordinated tin atom whose coordination
neighborhood can be described as distorted C,C-transoidal pseudo
octahedron or rather tetragonal bipyramid similarly to the already
described (LCN)2SnX2 (X ¼ F, Cl, Br, I or OH) [17,19,20]. Nitrogen
donor atoms N1 and N2 are located in the equatorial plane together
with pivot atoms of the 3,5-di-t-butylcatecholate O1 and O2 with
The
d
(
119Sn) value for 8 (ꢀ448.6 ppm) evidently indicates the six-
coordinated neighborhood of the tin atom in this compound and
is also similar to the value for starting LCNSnBr3 (ꢀ408 ppm)
[18a,19].
ꢁ
the SneN separations (Sn1eN1 2.514(7), Sn1eN2 2.534(8) A) being
In compound 7 (Fig. 2) all tin, oxygen and nitrogen donor atoms,
as well as phenyl rings of 3,5-di-t-butylcatecholate lie nearly in one
plane. The butyl groups lie above this plane and the phenyl rings of
the LCN ligand lie beneath the plane. Compound 7 reveals a dimeric
structure where a connection is established by Sn1/O1A and
Sn2/O1B interactions, respectively. The coordination vicinity of
the tin atom is pseudo octahedral, oxygen atoms O1A, O1B, O2A and
the intramolecularly coordinated nitrogen atom N1A lie in the
equatorial plane; axial positions are occupied by carbon atoms of
the LCN ligand and the butyl group. The dimeric structural pattern of
this type is relatively rare in the literature, with only few structures
comparable to that of the compound 7, the 2,2-di-t-butyl-1,2,3-
dioxastannolane [23], methyl 4,6-O-benzylidene-2,3-O-dibutyl-
slightly nonequivalent. Axial positions are occupied by carbon
atoms C22 and C15. The comparable monomeric compound formed
by the oxidation of SnCl2 with 3,5-di-t-butyl-1,2-benzoquinone was
published by Piskunov [11a]. The tin(IV) ion in the described
structure has similarly the distorted octahedral coordination and
the bidentate catecholate ligand in the equatorial plane with the
ꢁ
ꢁ
SneO distances of 2.011(2) A and 2.013(2) A which, in the case of
ꢁ
compound 2, are slightly elongated (Sn1eO2 2.050(2) A; Sn1eO1
ꢁ
2.054(2) A) due to the presence of relatively strong intramolecular
coordination of the donating nitrogen atom.
2.2. Salt elimination reactions
stannylene-a-D-glucopyranoside [24] and the product of the re-
Compound 3 is also a product of the reaction of monolithiated
catechol 4 with 1 M equivalent of LCN(n-Bu)2SnCl [18] (Scheme 3).
When the catechol is dilithiated (5) it reacts with only one equiv-
alent of LCN(n-Bu)2SnCl to produce compound 6, which is struc-
turally characterized in solution on the basis of multinuclear NMR
spectra measurements. The 1H NMR spectrum of 6 reveals only
action between 1,2,4-butanetriol and di-t-butyltin oxide [25].
The dimeric structure of compound 8 (Fig. 3) is similar to that of
7, revealing a similar coordination polyhedra pattern. The equato-
rial plane is occupied by a carbon atom of LCN ligand which in case
of compound 7 is located in an axial position. In compound 8, the
bromine atom Br1 and the nitrogen atom N1 lie in axial positions.

J. Turek et al. / Journal of Organometallic Chemistry 745-746 (2013) 25e33
27
Scheme 2. Reactions of 3,5-di-t-butylcatechol (1) with organotin(IV) oxide and hydride.
Both bromine atoms are in mutual anti positions which is different
from the syn positions of butyl groups in compound 7. The short-
ening of the coordination bond Sn1eN1 in comparison to com-
pound 7 was also observed, the angle O1eSn1eO2, on the other
hand, is comparable with the corresponding one in compound 7.
of dilithiated 3,5-di-t-butylcatecholate with LCN(n-Bu)SnCl2 (see
above).
Accordingly to Eaborn and Smith [8] and Barrau [6], a very clean
route to the target compounds are oxidation reactions of both
homo- and heteroleptic stannylenes by a quinone, therefore the
3,5-di-t-butyl-1,2-benzoquinone (9) was selected for this study in
order to prepare the same compounds by alternative reactions.
Selected stannylenes (Scheme 6) were the C,N-chelated homoleptic
stannylene (LCN)2Sn [26], homoleptic LN2Sn [27] stannylene con-
taining bulky amido group, two hybrid amino-amido stannylenes
LNN12Sn [28], and LNN22Sn [28], and heteroleptic stannylenes LNSnCl
[29] and LNN1SnCl [28], where only LN ligand (Scheme 1) is mon-
odentate and the remaining are hemilabile bidentate ligands. These
reactions (Scheme 6) produce nearly quantitative yields of pure
compounds 2, 11 and 12 at very short reaction times.
2.3. Reduction of quinone
Another possible pathway is the reduction of a quinone pre-
cursor by low valent or reduced tin(IV) species leading to the
appropriate tin(IV) catecholate. Reactions of the quinone 9 with
known tin(IV) based reducing agents (hydride or distannane) were
investigated as well (Scheme 5). The monosubstituted catechol 3
(see above) is obtained in good yield from 9 and triorganotin(IV)
hydride LCN(n-Bu)2SnH [16]. The reaction of an excess (up to 2
molar equivalents) of LCN(n-Bu)2SnH with 9 led to the formation of
3 as the only product. On the other hand, the reaction of 9 with
distannane (LCN(n-Bu)2Sn)2 [16] yields the bis(stannane)
substituted catechol 10. Signals in 1H NMR spectrum of 10 are
broadened, an AX pattern is found for benzylic protons and the
broad signal at ꢀ273.0 ppm is found in the 119Sn NMR spectrum in
C6D6 which indicates a slight nonequivalence of dangling tin spe-
cies on the catecholate moiety and higher coordination number of
the tin atoms than found in 3.
On the other hand, the reaction of 9 with LN2Sn gave mixture of
unidentified products (see Experimental part), which are charac-
terized by six signals of different intensity in 119Sn NMR spectrum.
Two signals are present in both of 119Sn NMR spectra of the
remaining two reaction mixtures of LNN12Sn and LNSnCl with 9 (see
Experimental part), respectively. In the latter two cases we can only
speculate about an isomerization of the proposed products by Berry
pseudorotation similarly as described for analogous compounds by
Jurkschat et al. [9a].
In both 1H NMR spectra of the compounds 11 and 12, one
broader signal is found for benzylic protons instead of an AX
pattern in the spectra of reactants. In contrast to 1H NMR spectra,
high differences of chemical shift values were observed in 119Sn
NMR spectra of all starting compounds and relevant products.
Signals of oxidized products 2 (an alternative preparation), 11 and
12 (see Experimental part) compared to the starting stannylenes
((LCN)2Sn w 144 [26], LN2Sn w 440 [27], LNN12Sn w ꢀ118 [28],
LNN22Sn w ꢀ129 [28], LNSnCl w 14 [29], LNN1SnCl w ꢀ65 [28] ppm)
are from about 200 ppm to 950 ppm upfield shifted. These rela-
tively high values of 119Sn chemical shifts indicate a rather high
coordination number of the central atom and/or its bonding with
highly electronegative groups. In the case of 12, a speculation about
the dimeric structure with a six-coordinated tin atom could be
made. On the other hand, the structures of compounds 2 and 11
should be monomeric in solution, incorporating two pendant ni-
trogen donor groups to the coordination neighborhood of the tin
atom. This is indicated by relatively higher chemical shifts values of
these compounds (2 w ꢀ258.2, 11 w ꢀ355.0 ppm), and also by the
fact that both described C,N- and N,N-chelating ligands produce
typically pseudo octahedral transoidal [17,19,20] geometry of the tin
atom with strongly coordinated dimethylamino groups.
According to the 119Sn NMR spectrum, the reaction of dio-
rganotin(IV) distannane (LCN(n-Bu)SnCl)2 with 9 leads to the for-
mation of two products. One of them (
d
(
119Sn) w ꢀ98.5 ppm) is
assigned to the known LCN(n-Bu)SnCl2 [18] and the second one
(characterized by
d(
119Sn) w ꢀ267.4 ppm) belongs to the dimeric
compound 7. Compound 7 could also be obtained from the reaction
The isolation and the molecular structure determination of
oxidation products of heteroleptic stannylenes were complicated
because of the lower stability of those products. From this series the
only fully characterized minor compounds from the same reaction
sequence were the hydrolytic product isolated from the reaction of
LNN1SnCl with 3,5-di-t-butylcatechol (12a) and an adduct of the
oxidized LNN1SnCl with SnCl2 (12b) (Scheme 7). The hydrolysis of
the former was probably caused by traces of water from the 3,5-di-
t-butylquinone. In the case of the latter, the molar excess of SnCl2
comes most likely from one of the steps of an in situ performed
Fig. 1. The molecular structure (ORTEP 30% probability level) of 2,ꢁhydrogen atoms are
ꢁ
omitted for clarity. Selected interatomic distances [A] and angles [ ]: Sn1eO2 2.050(2),
Sn1eO1 2.054(2), Sn1eC22 2.121(3), Sn1eC15 2.126(4), Sn1eN1 2.514(7), Sn1eN2
2.534(8), O2eSn1eO1 81.75(9), O2eSn1eC22 102.78(12), O1eSn1eC22 100.81(12),
O2eSn1eC15 100.24(12), O1eSn1eC15 99.87(12), C22eSn1eC15 150.92(14), O2e
Sn1eN1 160.89(16), O1eSn1eN1 80.80(17), O2eSn1eN2 89.40(18), O1eSn1eN2
168.45(19), N1eSn1eN2 108.9(2).

28
J. Turek et al. / Journal of Organometallic Chemistry 745-746 (2013) 25e33
Scheme 3. Reactions of mono- (4) and dilithiated (5) 3,5-di-t-butylcatecholate with triorganotin(IV) chloride.
reaction sequence, where a slight excess of SnCl2 is necessary for
the exclusive formation of the heteroleptic stannylene (LNN1SnCl).
That was also the reason for the presence of the lithium atom in the
structure of the hydrolytic product 12a. The discussion of the solid
state structures of 12a (Fig. S1) and 12b (Fig. S2) is available in
Supporting information.
is explored giving the products of the quinone to tin catecholates
reduction. Structures of the studied compounds are predominantly
dimeric with a strong coordination of hemilabile chelating ligands
to the tin centers which are thus six-coordinated. The only mono-
meric compound is 2 which can be prepared by almost all pathways
and reveal a reversible photolytic reaction when irradiated by UV-
light. Two minor hydrolysis products were also characterized by X-
ray techniques as tetranuclear and trinuclear cluster-like com-
pounds, respectively.
2.4. Additional properties of selected compounds
Compound 2 as the most stable and easily available was also
tested for its light sensitivity (Scheme 8). Under UV-light irradiation
in a quartz tube, a gradual and immediate darkening of the solution
was observed. The 1H and 119Sn NMR spectra measured approxi-
mately 3 min after the irradiation revealed a minor presence of the
stannylene (LCN)2Sn and quinone 9. After additional minutes these
signals completely disappeared and only signals belonging to 2
were detected, indicating the reversibility of the reaction. The
stannylene (LCN)2Sn can be trapped as (LCN)2SnCl2 when the irra-
diation of 2 is performed in the dichloromethane solution.
Considering the rich electrochemistry of catecholates and their
complexes [30], compound 8 as a representative and as the most
promising candidate was studied by cyclic voltammetry at plat-
inum disc electrode in dry THF. Within the accessible potential
range, compound 8 undergoes a single redox change (Supporting
information, Fig. S3). This redox process is electrochemically
reversible [31] and occurs at ꢀ0.20 V vs. ferrocene/ferrocenium
reference (see Supporting information).
4. Experimental
4.1. NMR spectroscopy
NMR spectra were recorded from solutions in benzene-d6, THF-
d8, toluene-d8 and CDCl3 on Bruker Avance II and on Bruker AMX
360 spectrometers (equipped with Z-gradient 5 mm probe) at
frequencies for 1H (500.13 MHz; 400.13 MHz; 360.13 MHz), 119Sn
{1H} (186.50 MHz; 149.21 MHz; 134.28 MHz), 13C{1H} (125.76 MHz;
100.61 MHz; 90.55 MHz) and 7Li{1H} (194.37 MHz) at 295 K (in the
3. Conclusions
Various organotin(IV) halides react with lithium catecholates to
give appropriate organotin(IV) catecholates. Similar compounds
were obtained from reactions of the catechol 1 or the quinone 9
with triorganotin(IV) hydride and various distannanes, respec-
tively. The reactivity of various stannylenes towards the quinone 9
tBu
LCN
Sn
LCN
O
LCN2SnBr2
toluene; RT
tBu
O
tBu
LCN
X
O
2
tBu
OLi
OLi
LCNBuSnCl2
toluene; RT
O
tBu
Sn
tBu
5
LCNSnBr3
O
X
tBu
Sn
toluene; RT
Fig. 2. The molecular structure (ORTEP 30% probability level) of 7$3C7H8, hydrogen
O
LCN
atoms, solvent molecules and parts ofꢁthe tBu moiety are omitted for clarity. Selected
tBu
ꢁ
X = Bu for 7
interatomic distances [A] and angles [ ]: Sn1eO1A 2.108(4), Sn1eO2A 2.066(4), Sn1e
8
X = Br for
C24A 2.122(6), Sn1eC1A 2.148(6), Sn1eO1B 2.388(4), Sn1eN1A 2.558(6), O1AeSn2
2.404(4), Sn2eO2B 2.072(4), Sn2eO1B 2.095(4), Sn2eC1B 2.119(7), Sn2eC24B
2.129(8), Sn2eN2B 2.576(6), Sn1eO1AeSn2 113.14(18), Sn2eO1BeSn1 114.23(17).
Scheme 4. Substitution reactions of dilithiated 3,5-di-t-butylcatecholate (5).

J. Turek et al. / Journal of Organometallic Chemistry 745-746 (2013) 25e33
29
tBu
tBu
tBu
O
O
L2Sn
LSnCl
L
Sn
L
L
O
O
O
Sn
O
THF; RT
THF; RT
tBu
tBu
tBu
Cl
9
L = LCN for 2
L = LNN1 for 12
L = LNN2 for 11
Scheme 6. Oxidation reactions of stannylenes with 3,5-di-t-butyl-1,2-benzoquinone
(9).
4.2. Cyclic voltammetry
Electrochemical measurements were performed with a multi-
purpose potentiostat mAUTOLAB III (Eco Chemie) at room temper-
ature using a standard Metrohm three-electrode cell equipped with
a platinum disc working electrode (2 mm diameter), platinum
sheet auxiliary electrode, and a double-junction Ag/AgCl (3 M KCl)
reference electrode. The compound was dissolved in dry THF to
give a solution containing ca. 1 mM of the analyzed compound and
0.1 M Bu4N[PF6] (Fluka, p.a. for electrochemistry). The solution was
prepared under argon, transferred to the electrochemical cell and
kept under an argon blanket. The redox potentials are given relative
to internal ferrocene/ferrocenium reference.
Fig. 3. The molecular structure of one independent molecule (ORTEP 40% probability
level) of 8$3C7H8, hydrogen atoms and solvent molecules are omitted for clarity.
ꢁ
ꢁ
Selected interatomic distances [A] and angles [ ]: Sn1eO2 2.022(2), Sn1eC1 2.144(3),
Sn1eO1a 2.148(2), Sn1eO1 2.166(2), Sn1eN1 2.352(3), Sn1eBr1 2.5707(4), O2eSn1e
C1 103.21(11), O2eSn1eO1a 144.27(9), C1eSn1eO1a 111.19(10), O2eSn1eO1 77.77(8),
C1eSn1eO1 168.95(10), O1eSn1eO1a 66.61(9), O2eSn1eN1 85.94(9), C1eSn1eN1
77.13(11), O1aeSn1eN1 92.35(9), O1eSn1eN1 92.02(9), O2eSn1eBr1 93.03(7), C1e
Sn1eBr1 94.30(9), O1aeSn1eBr1 93.75(6), O1eSn1eBr1 96.65(6), N1eSn1eBr1
170.86(7).
4.3. X-ray crystallography
case of 10 variable temperature measurement was used for 119Sn
NMR spectroscopy). All deuterated solvents were degassed and
then stored over K-mirror under an argon atmosphere. Solutions
were obtained by dissolving of approximately 40 mg of each
compound approximately in 0.5 mL of deuterated solvents. Values
of 1H chemical shifts were calibrated to internal standard e tetra-
The X-ray data (Tables S1 and S2, see Supporting information)
for single crystals of all compounds were obtained at 150 K using an
Oxford Cryostream low-temperature device on a Nonius KappaCCD
ꢁ
diffractometer with MoKa radiation (
monochromator, and the 4 and
l
¼ 0.71073 A), a graphite
c
scan mode. Data reductions were
performed with DENZO-SMN [32]. The absorption was corrected
using integration methods [33]. Structures were solved by direct
methods (Sir92) [34] and refined by full matrix least-square based
on F2 (SHELXL97) [35]. Hydrogen atoms were mostly localized on a
difference Fourier map, however, to ensure uniformity of the
treatment of the crystal, all hydrogen atoms were recalculated into
idealized positions (riding model) and assigned temperature fac-
tors Hiso(H) ¼ 1.2 Ueq(pivot atom) or of 1.5 Ueq for the methyl
methylsilane (
d
(1H) ¼ 0.00) or to residual signals of benzene
(
d
(1H) ¼ 7.16), THF (
d
(1H) ¼ 1.73), toluene (
d
(1H) ¼ 2.09 or 6.98) or
chloroform (
brated to signals of THF (
toluene-d8
d
(1H) ¼ 7.27). Values of 13C chemical shifts were cali-
d(
13C) ¼ 67.2), CDCl3
(d(
13C) ¼ 77.2) or
(
d(
13C) ¼ 20.4). The 119Sn chemical shift values are
referred to external neat tetramethylstannane (
d
(
119Sn) ¼ 0.0) and
7Li to external 1 M LiCl in D2O (
quency ratio
d
(7Li) ¼ 0.0; recalculated to fre-
X
for 500.13 MHz spectrometer e 194.369507
ꢁ
moiety with CeH ¼ 0.96, 0.97, and 0.93 A for methyl, methylene
9361 MHz). The 13C NMR spectra were only recorded in cases of
sparingly soluble compounds in CDCl3, toluene-d8 or THF-d8. A
quite problematic feature of 13C NMR spectra measured is the high
broadening of signals which disabled its proper interpretation.
and hydrogen atoms in aromatic rings or allyl moiety, respectively.
4.4. Elemental analysis
The compositional analyses were determined under an inert
atmosphere of argon on the automatic analyzer EA 1108 by FISONS
Instruments.
tBu
LCNBu2SnH
Et2O; RT
OH
4.5. Synthesis
tBu
tBu
tBu
OSnBu2LCN
3
All experiments were carried out under an argon atmosphere
using the standard Schlenk techniques. 3,5-di-t-butylcatecholate,
3,5-di-t-butyl-1,2-benzoquinone and n-butyllithium were obtained
from commercial sources (SigmaeAldrich). Toluene, n-hexane,
diethyl ether and THF were dried over and distilled from potas-
siumesodium alloy, degassed and stored under argon over potas-
sium or sodium mirror.
Bis[2-(N,N-dimethylaminomethyl)phenyl]stannylene [26], bis(N-
trimethylsilyl-N-2,6-diisopropylphenylamido)stannylene [27], bis(N-
trimethylsilyl-N-2-(dimethylaminomethyl)phenylamido)stannylene
[28], bis(N-triphenylgermyl-N-2-(dimethylaminomethyl)phenylami
do)stannylene [28], bis[(N-trimethylsilyl-N-2,6-diisopropylpheny
lamido)tin(II) chloride] [29], (N-trimethylsilyl-N-2-(dimethylamino-
methyl)phenylamido)tin(II) chloride [28], [2-(N,N-dimethylamino-
methyl)phenyl]di-n-butyltin(IV) hydride [16], bis{[2-(N,N-dimethy
tBu
tBu
tBu
OSnBu2LCN
OSnBu2LCN
O
O
(LCNBu2Sn)2
THF; RT
tBu
10
9
LCN
O
(LCNBuSnCl)2
Bu
Sn
tBu
THF; RT
- LCNBuSnCl2
O
O
7
Sn
Bu
O
LCN
tBu
Scheme 5. Oxidation of organotin(IV) hydride and distannanes with 3,5-di-t-butyl-
1,2-benzoquinone (9).

30
J. Turek et al. / Journal of Organometallic Chemistry 745-746 (2013) 25e33
O
Li
Cl
tBu
tBu
O
H
Cl
O
Me
2N
N
O
Sn
O
tBu
Sn
Sn
tBu
O
O
tBu
O
tBu
Sn
O
N
NMe2
O
H
Cl
O
tBu
Li
LNN1Li + ex. SnCl2
12a
tBu
Cl
tBu
in situ
O
O
O
air
LNN1SnCl +
tBu
+
moisture
Cl
Cl
Me
2N
Sn
tBu
tBu
O
O
O
O
N
Sn
Sn
Cl
12b
N
Cl
Me2N
tBu
tBu
Scheme 7. Oxidation of LNN1SnCl with 3,5-di-t-butyl-1,2-benzoquinone (9) and subsequent reaction/degradation of its products.
laminomethyl)phenyl]di-n-butyltin(IV)} [16], bis{[2-(N,N-dimethy-
laminomethyl)phenyl]n-butylchloro}distannane [36], [2-(N,N-dime-
thylaminomethyl)phenyl]di-n-butyltin(IV) chloride [18], (N,N-dimet
hylaminomethyl)phenyl-n-butyltin(IV) dichloride [18], bis(N,N-dim
ethylaminomethyl)phenyltin(IV) dibromide [18], (N,N-dimethylami-
nomethyl)phenyltin(IV) tribromide [18,19] and bis[(N,N-dimethyla-
minomethyl)phenyl]tin(IV) oxide [15] were obtained by published
methods.
d
: ꢀ258. Anal. found: C 63.1, H 7.0, N 4.5%; Calcd for C32H44N2O2Sn:
C 63.28, H 7.30, N 4.61%.
4.5.2. Preparation of 3
Compound 3 could be obtained from a reaction of LCN(n-
Bu)2SnH with 3,5-di-t-butylcatechol or from a reaction of mono-
lithiated 3,5-di-t-butylcatechol with LCN(n-Bu)2SnCl. But the most
convenient and straightforward way of preparation seemed to be
the reaction of 3,5-di-t-butyl-1,2-benzoquinone with LCN(n-
Bu)2SnH:
4.5.1. Preparation of 2
Compound 2 could be isolated from the condensation reaction
of bis[(N,N-dimethylaminomethyl)phenyl]tin(IV) oxide with 3,5-
di-t-butylcatechol (analogously with previously published results
[20a]) or from the reaction of dilithiated 3,5-di-t-butylcatechol
with (LCN)2SnBr2 (analogous to the preparation of 6, see below) or
from the reaction of 3,5-di-t-butyl-1,2-benzoquinone with stan-
nylene (LCN)2Sn. The latter reaction turned out to be the most
convenient one:
To a stirred solution of 0.702 g of LCN(n-Bu)2SnH (1.91 mmol) in
15 mL of diethyl ether 0.428gof 9(1.91mmol)in10mLofdiethylether
was added dropwise at room temperature. The reaction mixture was
stirred for one day. After evaporation, the oily residue was washed
with 10 mL of hexane, 0.706 g of 3 (1.20 mmol) were obtained (yield
63%).1H NMR (500 MHz, C6D6, 295 K)
d: 8.18 (d,1H, J ¼ 7.2 Hz, ArH(6));
7.34 (s, 1H, OH); 7.11 (t, 1H, J ¼ 7.4 Hz, ArH(4)); 7.06 (t, 1H, J ¼ 7.2 Hz,
ArH(5)); 6.97 (m, 1H, ArH(3)); 6.87 (m, 2H, ArH(40,60)); 3.01 (s, 2H,
A solution of 0.037 g of 9 (0.16 mmol) in 10 mL of Et2O was
added dropwise to a solution of 0.063 g of (LCN)2Sn (0.16 mmol) in
10 mL of Et2O at room temperature. The reaction mixture was
stirred for 2 h. After that, single crystals of product 2 started to
grow, 0.033 g of product (0.053 mmol) were obtained (yield 34%).
NCH2); 1.71 (s,18H, C(CH3)3); 1.63 (m, 4H,
1.30 (m, 4H, -CH2); 1.19 (m, 4H,
-CH2); 0.83 (t, 6H, J ¼ 7.4 Hz, CH3).
119Sn NMR (186 MHz, C6D6, 295 K)
a-CH2); 1.37 (s, 6H, N(CH3)2);
g
b
d
: ꢀ83. Anal. found: C 63.0, H 8.7, N
2.3%; Calcd for C31H51NO2Sn: C 63.28, H 8.74, N 2.38%.
M.p. 253 ꢁC. 1H NMR (360 MHz, CDCl3, 295 K)
d
: 7.95 (s, 2H, ArH(6));
4.5.3. Preparation of lithiated 3,5-di-t-butylcatecholates 4 and 5
n-BuLi (1.6 M solution in hexanes) in appropriate molar ratio
was added slowly to a stirred solution of 3,5-di-t-butylcatechol in
7.28 (m, 4H, ArH(4,5)); 7.12 (m, 2H, ArH(3)); 6.77 (s, 1H, ArH(40));
6.56 (s, 1H, ArH(60)); 3.64, 3.50 (anisochronous signals, AX spin
system, Dd ¼ 50 Hz, 2J ¼ 14 Hz, 4H, NCH2); 2.27 (br s, 12H, N(CH3)2);
1.48 (s, 9H, C(CH3)3); 1.28 (s, 9H, C(CH3)3). 13C NMR (91 MHz, CDCl3,
tBu
tBu
295 K)
d
: 152.98 (ArC(50)); 149.02 (ArC(2)); 141.18 (1J ¼ 29.35 Hz,
LCN
Sn
LCN
O
O
ArC(1)); 140.62 (ArC(30)); 137.20 (ArC(10)); 136.91 (ArC(6)); 133.61
(ArC(20)); 129.62 (ArC(4)); 127.88 (3J ¼ 42.9 Hz, ArC(5)); 127.21
(3J ¼ 42.7 Hz, ArC(3)); 110.96 (ArC(40)); 110.18 (ArC(60)); 64.63
(NCH2); 46.20 (N(CH3)2); 34.90 (C(CH3)3); 34.26 (C(CH3)3); 32.12
(C(CH3)3); 29.89 (C(CH3)3). 119Sn NMR (134 MHz, CDCl3, 295 K)
O
O
hν
hν
LCN2SnCl2
LCN2Sn +
tBu
CH2Cl2
tBu
2
9
Scheme 8. Further reactivity of product 2.

J. Turek et al. / Journal of Organometallic Chemistry 745-746 (2013) 25e33
31
40 mL of hexane at room temperature. After few minutes the so-
lution was filtered off and the solid product (4 or 5) was washed
with hexane and then dried in vacuo. Compounds 4 and 5 were
used in situ in all of the following reactions.
Dd ¼ 62 Hz, 4H, NCH2); 2.61, 2.19 (anisochronous signals, AX spin
system, Dd ¼ 169 Hz, 12H, N(CH3)2); 1.31 (s, 18H, C(CH3)3); 1.25 (s,
18H, C(CH3)3). 13C NMR (101 MHz, THF-d8, 295 K) : 149.19 (ArC(50));
d
148.45 (ArC(2)); 147.66 (ArC(10)); 139.35 (ArC(1)) þ ArC(30)); 136.57
(ArC(20)); 134.54 (2J ¼ 41.7 Hz, ArC(6)); 129.80 (ArC(4)); 128.32
(3J ¼ 60.7 Hz, ArC(5)); 127.34 (3J ¼ 53.4 Hz, ArC(3)); 112.77 (ArC(40));
108.27 (ArC(60)); 62.92 (3J ¼ 34.1 Hz, NCH2); 47.10, 46.38 (aniso-
chronous signals, Dd ¼ 73.5 Hz, N(CH3)2)); 35.28 (C(CH3)3); 34.52
(C(CH3)3); 32.25 (C(CH3)3); 30.00 (C(CH3)3). 119Sn NMR (149 MHz,
4.5.4. Reaction of [2-(N,N-dimethylaminomethyl)phenyl]di-n-
butyltin(IV) chloride with 5
0.330 g of LCN(n-Bu)2SnCl (0.82 mmol) in 20 mL of toluene were
slowly added to the solution of 0.096 g of 5 (0.41 mmol) in 10 mL of
toluene at room temperature. The reaction mixture was stirred
overnight and afterward evaporated in vacuo. A mixture of two
inseparable products was obtained. NMR spectra show the pres-
ence of the unreacted starting compound and one new product (6).
THF-d8, 294 K)
d
: ꢀ449. Anal. found: C 49.7, H 5.7, Br 14.5, N 2.4%;
Calcd for C46H66Br2N2O4Sn2: C 49.86, H 6.00, Br 14.42, N 2.53%.
4.5.7. Preparation of 10
1H NMR (500 MHz, C6D6, 295 K)
d
: 8.73 (m, 0.5H, ArH); 8.67 (m, 1H,
A solution of 0.164 g of 3,5-di-t-butylquinone (0.73 mmol) in
THF was added to a stirred solution of 0.537 g of (LCN(n-Bu)2Sn)2
(0.73 mmol) in 20 mL of THF at room temperature. White powder
started to precipitate in the orange reaction mixture after 4 h of
stirring. The solution was filtered off and the solid product was
washed three times with hexane. 0.328 g of compound 10
(0.34 mmol) was obtained (yield 47%). M.p. 127 ꢁC. 1H NMR
ArH); 7.19 (m, 6.5H, ArH); 7.05 (m, 5H, ArH); 6.91 (m, 2H, ArH); 3.16
(br s, 2H, NCH2); 3.04 (br s, 1.5H, NCH2); 2.16 (br s, 3.5H); 1.86 (m,
8.5H); 1.72 (m, 7H); 1.42 (m, 29H); 0.94 (m, 6H). 119Sn NMR
(500 MHz, C6D6, 295 K)
d
: 15; ꢀ49. 7Li NMR (C6D6, 194 MHz, 295 K)
d: 1.29 (s, 3Li); 1.2 (br s).
4.5.5. Preparation of 7
(500 MHz, C6D6, 295 K)
d
: 7.87 (d, 2H, J ¼ 7.3 Hz, ArH(6)); 7.29 (t, 2H,
0.396 g of LCN(n-Bu)SnCl2 (1.04 mmol) were dissolved in 20 mL
of toluene and a solution of 0.243 g of dilithiated 3,5-di-t-butyl-
catecholate 5 (1.04 mmol) in 20 mL of toluene was subsequently
added at room temperature. The reaction mixture was stirred for
1 h until the yellow solution of the product with insoluble pre-
cipitate of LiCl was formed. The reaction mixture was filtered off
and then reduced to its half volume in vacuo. From that solution,
0.474 g of colorless single crystals of product 7 (0.45 mmol) were
obtained at low temperature (yield 86%). M.p. 192 ꢁC. 1H NMR
J ¼ 7.4 Hz, ArH(4)); 7.18 (m, 4H, ArH(3,5)); 6.49 (s, 1H, ArH(40)); 6.43
(br s, 1H, ArH(60)); 4.13, 3.56 (anisochronous signals, AX spin sys-
tem, Dd ¼ 285 Hz, 4H, NCH2); 2.61 (br s, 12H, N(CH3)2); 1.58 (br s,
8H,
a
-CH2) 1.43 (s, 9H, C(CH3)3); 1.31 (m, 16H,
b-CH2 þ
g-CH2); 1.11
(t, 12H, J ¼ 8.8 Hz, CH3); 1.10 (s, 9H, C(CH3)3). 13C NMR (126 MHz,
THF-d8, 295 K) d: 137.32 (ArC(2)); 134.04 (ArC(1)); 130.51 (ArC(6));
128.44 (ArC(4)); 127.10 (ArC(3) þ ArC(5)); 111.95 (ArC(40)); 110.30
(ArC(60)); 64.47 (NCH2); 35.18 (C(CH3)3); 34.42(C(CH3)3); 32.36 (
b
a
-
-
CH2); 32.11 (C(CH3)3); 30.09 (C(CH3)3); 27.28 (
g-CH2); 23.35 (
(500 MHz, Tol-d8, 295 K)
d
: 8.10 (d, 2H, J ¼ 7.4 Hz, 3J(119,117Sn,
CH2); 13.83 (CH3). 119Sn NMR (186 MHz, C6D6, 295 K)
d
: ꢀ273. Anal.
1H) ¼ 61.2 Hz, ArH(6)); 6.98 (m, 8H, ArH(3,4,5,40)); 6.53 (br s, 2H,
ArH(60)); 4.50, 2.83 (anisochronous signals, AX spin system,
Dd ¼ 837 Hz, 2J ¼ 13 Hz, 4H, NCH2); 2.69 (br s, 12H, N(CH3)2); 1.89
found: C 60.5, H 8.4, N 2.9%; Calcd for C48H80N2O2Sn2: C 60.40, H
8.45, N 2.93%.
(m, 4H,
a
-CH2); 1.66 (s, 18H, C(CH3)3); 1.36 (m, 8H,
b-CH2 þ
g-CH2);
4.5.8. Reaction of bis(N-trimethylsilyl-N-2,6-
diisopropylphenylamido)stannylene with 9
1.23 (s, 18H, C(CH3)3); 0.85 (t, J ¼ 7.3 Hz, 6H, CH3). 1H NMR
(500 MHz, THF-d8, 295 K)
d
: 8.30 (d, 2H, J ¼ 7.4 Hz, 3J(119,117Sn,
A solution of 0.093 g of 9 (0.42 mmol) in THF was added dropwise
to a stirred solution of 0.258 g of (LN)2Sn (0.42 mmol) in 30 mL of THF.
The reaction mixturewas stirred atroom temperature for 2 h until the
color changed from dark green to yelloweorange. A mixture of
inseparable products was obtained after evaporation. 119Sn NMR
1H) ¼ 82.5 Hz, ArH(6)); 7.18 (m, 4H, ArH(3,4)); 7.06 (d, 2H, J ¼ 7.5 Hz,
ArH(5)); 6.52 (d, 2H, J ¼ 2.4 Hz, ArH(40)); 6.44 (d, 2H, J ¼ 2.4 Hz,
ArH(60)); 4.27, 3.31 (broad signals, Dd ¼ 383 Hz, 4H, NCH2); 2.50 (br
s, 12H, N(CH3)2); 1.79 (br m, 4H,
(br m, 8H,
-CH2 þ
6H, CH3). 13C NMR (101 MHz, THF-d8, 295 K)
a-CH2); 1.37 (s, 18H, C(CH3)3); 1.29
b
g-CH2); 1.19 (s, 18H, C(CH3)3); 0.85 (t, J ¼ 7.3 Hz,
(500 MHz, C6D6, 295 K)
d
: ꢀ145; ꢀ158; ꢀ334; ꢀ509; ꢀ510; ꢀ533.
d
: 151.42 (ArC(50));
150.59 (ArC(2)); 146.00 (ArC(10)); 142.81 (ArC(1)); 139.15 (ArC(30));
136.54 (ArC(20)); 133.93 (ArC(6)); 129.53 (ArC(4)); 127.62 (ArC(5));
127.27 (ArC(3)); 111.93 (ArC(40)); 109.69 (ArC(60)); 64.55 (NCH2);
45.21 (N(CH3)2); 35.38 (C(CH3)3); 34.66 (C(CH3)3); 32.50 (C(CH3)3);
4.5.9. Reaction of bis(N-trimethylsilyl-N-2-(dimethylaminomethyl)
phenylamido)stannylene with 9
To a solution of 0.199 g of (LNN1)2Sn (0.35 mmol) in 20 mL of THF
a solution of 0.078 g of 9 in 15 mL of THF was added dropwise at
room temperature. The reaction mixture was stirred for 1 h until
the color turned brown, then evaporated in vacuo and finally
washed with hexane. A mixture of two products in form of brown
foam was obtained (0.169 g; yield 62%). Both 1H and 119Sn NMR
spectra revealed the presence of two indistinguishable compounds
30.28 (C(CH3)3); 28.20 (
119Sn NMR (186 MHz, Tol-d8, 270 K)
THF-d8, 295 K)
g
-CH2); 27.20 (
a
-CH2 þ
b-CH2); 14.03 (CH3).
d
: ꢀ270; 119Sn NMR (149 MHz,
d
: ꢀ247 broad. Anal. found: C 61.3, H 7.9, N 2.5%;
Calcd for C54H84N2O4Sn2: C 61.04, H 7.97, N 2.64%.
Compound 7 could also be isolated from the reaction of dis-
tannane (LCN(n-Bu)SnCl)2 with 3,5-di-t-butyl-1,2-benzoquinone.
in approximate molar ratio 2:1. 1H NMR (500 MHz, C6D6, 295 K)
d:
7.20 (br s, 2H, ArH); 6.98 (m, 6H, ArH); 6.91 (m, 3H, ArH); 6.79 (br s,
2H, ArH); 6.24 (br s, 1H, ArH); 3.97, 2.87 (anisochronous signals, AX
spin system, Dd ¼ 550 Hz, 2H, NCH2); 3.64, 3.15 (anisochronous
signals, AX spin system, Dd ¼ 245 Hz, 4H, NCH2); 2.30 (s, 6H); 2.01
(s, 12H); 1.69 (m, 13H); 1.36 (m, 15 H); 0.13 (m, 27H, Si(CH3)3). 119Sn
4.5.6. Preparation of 8
To a solution of 2.219 g of LCNSnBr3 (4.50 mmol) in 50 mL of
toluene, a solution of 1.055 g of 5 (4.50 mmol) in 40 mL of toluene
was added dropwise at room temperature. The reaction mixturewas
stirred until the color turned green and then filtered off and evap-
orated in vacuo. 2.05 g of compound 8 (1.85 mmol) were obtained
NMR (500 MHz, C6D6, 295 K)
d: ꢀ351; ꢀ435.
(yield 82%). M.p. 110 ꢁC (dec.). 1H NMR (400 MHz, THF-d8, 294 K)
d:
4.5.10. Preparation of 11
8.01 (d, 2H, J ¼ 7.2 Hz, 3J(119,117Sn, 1H) ¼ 61.8 Hz, ArH(6)); 7.34 (t, 2H,
J ¼ 7.2 Hz, ArH(4)); 7.29 (t, 2H, J ¼ 7.2 Hz, ArH(5)); 7.10 (d, 2H,
J ¼ 6.9 Hz, 3J(119,117Sn,1H) ¼ 24 Hz, ArH(3)); 6.62 (s, 2H, ArH(40)); 6.59
(s, 2H, ArH(60)); 4.12, 3.96 (anisochronous signals, AX spin system,
A solution of 0.101 g of 9 (0.45 mmol) in 30 mL of THF was added
dropwise at room temperature to a solution of 0.4695 g of (LNN2)2Sn
(0.46 mmol) in 50 mL of THF. The color of the reaction mixture
turned from yellowegreen to dark brown during 2 h of stirring. The

32
J. Turek et al. / Journal of Organometallic Chemistry 745-746 (2013) 25e33
[3] M. Weidenbruch, H. Kilian, K. Peters, H.G. von Schnerig, H. Marsmann, Chem.
Ber. 128 (1995) 983e985.
[4] (a) T.A. Annan, R.K. Chadha, D.G. Tuck, K.D. Watson, Can. J. Chem. 65 (1987)
2670e2676;
product was washed with hexane and dried under vacuum. 0.352 g
of the product 11 (0.28 mmol) was obtained (yield 63%). The 1H
NMR spectra pattern confirms the presence of 11 with unclear
inconsistency in integral ratios of aromatic and aliphatic peaks. 1H
(b) D. Agustin, G. Rima, H. Gornitzka, J. Barrau, J. Organomet. Chem. 592 (1999)
1e10;
(c) A. Akkari, J.J. Byrne, I. Saur, G. Rima, H. Gornitzka, J. Barrau, J. Organomet.
Chem. 622 (2001) 190e198;
(d) J. Rouzaud, M. Joudat, A. Castel, F. Delpech, P. Riviere, H. Gornitzka,
J.M. Manriquez, I. Chavez, J. Organomet. Chem. 651 (2002) 44e51;
(e) A. Mcheik, N. Katir, A. Castel, H. Gornitzka, S. Massou, P. Riviere, T. Hamieh,
Eur. J. Inorg. Chem. (2008) 5397e5403.
NMR (500 MHz, C6D6, 295 K) d: 7.79 (m, 2H, ArH); 7.48 (m, 12H,
ArH); 7.03 (m, 18 H, ArH); 6.89 (m, 2H, ArH); 6.79 (m, 2H, ArH); 6.71
(s, 1H, ArH); 6.60 (m, 2H, ArH); 6.45 (s, 1H, ArH); 4.27, 2.97 (ani-
sochronous signals, AX spin system, Dd ¼ 650 Hz, 2H, NCH2); 1.75
(br s, 6H, N(CH3)2); 1.43 (m, 15H, C(CH3)3). 119Sn NMR (186 MHz,
C6D6, 295 K)
d
: ꢀ355. Anal. found: C 67.9, H 6.2, N 4.7%; Calcd for
[5] (a) T. Mukaiyama, N. Iwasawa, T. Yura, R.S.J. Clark, Tetrahedron 43 (1987)
5003e5017;
C
68H74GeN4O2SiSn: C 68.13, H 6.22, N 4.67%.
(b) D.S. Hays, G.C. Fu, J. Org. Chem. 63 (1998) 6375e6381;
(c) R.D. Sweeder, R.L. Gdula, B.J. Ludwig, M.M. Banaszak Holl, J.W. Kampf,
Organometallics 22 (2003) 3222e3229;
4.5.11. Reaction of bis[(N-trimethylsilyl-N-2,6-
(d) D. Ghereg, H. Ranaivonjatovo, N. Saffon, H. Gornitzka, J. Escudié, Organo-
metallics 28 (2009) 2294e2299;
(e) V. Barba, J. Zaragoza, H. Höpfl, N. Farfán, H.I. Beltrán, L.S. Zamudio-Rivera,
J. Organomet. Chem. 696 (2011) 1949e1956.
diisopropylphenylamido)tin(II) chloride] with 9
To a solution of 0.090 g of (LNSnCl)2 (0.11 mmol) in 15 mL of THF
a solution of 0.051 g of 9 (0.23 mmol) was added dropwise at room
temperature. During 18 h of stirring at room temperature the color
of the reaction mixture turned from green to brown, afterward it
was evaporated in vacuo. 0.032 g of mixture of two products were
[6] (a) J. Barrau, G. Rima, T. El Amraoui, J. Organomet. Chem. 561 (1998) 167e
174;
(b) J. Barrau, G. Rima, T. El Amraoui, J. Organomet. Chem. 570 (1998) 163e
174;
(c) J. Barrau, G. Rima, T. El Amraoui, Organometallics 17 (1998) 607e614;
(d) D. Agustin, G. Rima, H. Gornitzka, J. Barrau, Main Group Met. Chem. 22
(1999) 703e711.
obtained (yield 22%). 1H NMR (500 MHz, C6D6, 295 K)
d: 7.10 (m, 5H,
ArH); 3.91 (br s, 2H); 3.59 (br s, 10H); 3.46 (m, 2H, CH(CH3)2); 1.78
(br s, 4H); 1.41 (m, 18H, C(CH3)3); 1.21 (m, 14H, CH(CH3)2); 1.13 (m,
6H); 0.10 (s, 9H, Si(CH3)3). 119Sn NMR (186 MHz, C6D6, 295 K)
[7] F.T. Edelmann, M. Belay, J. Fluorine Chem. 84 (1997) 29e33.
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[9] (a) K. Jurkschat, N. Pieper, S. Seemeyer, M. Schürmann, Organometallics 20
(2001) 868e880;
d: ꢀ489; ꢀ509.
4.5.12. Preparation of 12
(b) S.N. Tandura, A.N. Shumsky, B.I. Ugrak, V.V. Negrebetsky, S.Y. Bylikin,
S.P. Kolesnikov, Organometallics 24 (2005) 5227e5240.
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A solution of 0.191 g of 9 (0.85 mmol) was added slowly to a
solution of 0.320 g of LNN1SnCl (0.85 mmol) in 30 mL of THF at room
temperature. The green reaction mixture was evaporated in vacuo,
washed with hexane and finally dried under vacuum. 0.340 g of 12
(b) G.A. Razuvaev, G.A. Abakumov, P.Y. Bayushkin, V.A. Tsaryapkin,
V.K. Cherkasov, Izv. Akad. Nauk SSSR, Ser. Khim. 9 (1984) 2098e2105;
(c) T.A. Annan, B.R. McGarvey, A. Ozarowski, D.G. Tuck, J. Chem. Soc. Dalton
Trans. (1989) 439e446.
(0.57 mmol) was obtained (yield 67%). The aliphatic part of the 1
H
NMR spectrum is rather complex with some signals being over-
[11] (a) A.V. Lado, A.I. Poddel’sky, A.V. Piskunov, G.K. Fukin, E.V. Baranov,
V.N. Ikorskii, V.K. Cherkasov, G.A. Abakumov, Inorg. Chim. Acta 358 (2005)
4443e4450;
lapped by signals of complexed THF. 1H NMR (500 MHz, C6D6,
295 K)
d
: 7.22 (t, 1H, J ¼ 7.6 Hz, ArH(4)); 7.14 (d, 1H, J ¼ 7.9 Hz,
(b) A.V. Lado, A.V. Piskunov, V.K. Cherkasov, G.K. Fukin, G.A. Abakumov, Russ.
J. Coord. Chem. 32 (2006) 173e179;
(c) A.V. Lado, A.V. Piskunov, O.V. Kuznetsova, M.I. Timoshenkov,
M.S. Piskunova, S.V. Maslennikov, Russ. J. Coord. Chem. 34 (2008) 329e333;
(d) A.V. Piskunov, O.Y. Sukhoshkina, I.V. Smolyaninov, Russ. J. Gen. Chem. 80
(2010) 790e799;
ArH(6)); 7.11 (br s, 1H, ArH(40)); 6.87 (m, 2H, ArH(3,60)); 6.74 (m, 1H,
ArH(5)); 3.67, 2.38 (anisochronous signals, AX spin system,
Dd ¼ 648 Hz, 2H, NCH2); 1.47 (br s, 6H, N(CH3)2); 1.33 (s, 18H,
C(CH3)3); 0.34 (s, 9H, Si(CH3)3). 119Sn NMR (134 MHz, C6D6, 295 K)
(e) E.V. Ilyakina, A.I. Poddel’sky, A.V. Piskunov, N.V. Somov, Inorg. Chem. Acta
380 (2012) 57e64.
[12] (a) B.R. McGarvey, A. Ozarowski, Z. Tian, D.G. Tuck, Can. J. Chem. 73 (1995)
1213e1222;
d
: ꢀ471. Anal. found: C 52.5, H 7.0, Cl 6.1, N 4.61%; Calcd for
C
26H41ClN2O2SiSn: C 52.41, H 6.94, Cl 5.59, N 4.70%.
(b) S. Bernadoni, M. Lucarini, G.F. Pedulli, L. Vlgimigli, V. Gevorgyan,
C. Chatgilialoglu, J. Org. Chem. 62 (1997) 8009e8014;
(c) N.Y. Kabarova, V.K. Cherkasov, L.N. Zakharov, G.A. Abakumov,
Y.T. Struchkov, L.G. Abakumova, Izv. Akad. Nauk, Ser. Khim. 12 (1992) 2798e
2804;
Acknowledgments
The financial support of the Czech Science Foundation (Project
no. 207/09/P092) is gratefully acknowledged. The authors are
grateful to prof. Petr Stepnicka of Charles University in Prague for
the performance of the CV experiment.
(d) A.S. Batsanov, J.A.K. Howard, M.A. Brown, B.R. McGarvey, D.G. Tuck, Chem.
Commun. (1997) 699e700.
ꢀ
ꢀ
ꢀ
[13] L.B. Vaganova, E.V. Kolyakina, A.V. Lado, A.V. Piskunov, V.K. Cherkasov,
D.F. Grishin, Polym. Sci. Ser. A 50 (2008) 153e159.
[14] L.B. Vaganova, E.V. Kolyakina, A.V. Lado, A.V. Piskunov, D.F. Grishin, Polym Sci.
Ser. B 51 (2009) 96e101.
Appendix A. Supplementary material
ꢀ
ꢀ
ꢀ
ꢁꢀ ꢀ
[15] Z. Padelková, M.S. Nechaev, Z. Cernosek, J. Brus, A. Ruzicka, Organometallics
27 (2008) 5303e5308.
[16] J. Turek, Z. Padelková, Z. Cernosek, M. Erben, A. Lycka, M.S. Nechaev,
CCDC 921163 (for 2), 921165 (for 12a), 921166 (for 12b), 921167
(for 12a0), 921168 (for 8), 921169 (for 7) contain the supplementary
crystallographic data for this paper. These data can be obtained free
of charge from The Cambridge Crystallographic Data Centre via
www.ccdc.cam.ac.uk/data_request/cif.
ꢀ
ꢀ
ꢀ
ꢀ
ꢀ
ꢁꢀ ꢀ
ꢀ
I. Císarová, A. Ruzicka, J. Organomet. Chem. 694 (2009) 3000e3007.
ꢀ
ꢀ
ꢁꢀ ꢀ
ꢀ
[17] P. Novák, Z. Padelková, L. Kolárová, I. Císarová, A. Ruzicka, J. Holecek, Appl.
Organomet. Chem. 19 (2005) 1101e1108.
ꢁꢀ ꢀ
ꢀ
ꢀ
[18] (a) A. Ruzicka, V. Pejchal, J. Holecek, A. Lycka, K. Jacob, Collect. Czech. Chem.
Commun. 63 (1998) 977e989;
ꢀ
ꢀ
ꢀ
ꢁꢀ ꢀ
ꢀ
(b) P. Svec, Z. Padelková, I. Císarová, A. Ruzicka, J. Holecek, Main Group Met.
Chem. 31 (2008) 305e309.
[19] P. Novák, Z. Padelková, I. Císarová, L. Kolárová, A. Ruzicka, J. Holecek, Appl.
Appendix B. Supplementary data
ꢀ
ꢀ
ꢀ
ꢁꢀ ꢀ
ꢀ
Organomet. Chem. 20 (2006) 226e232.
[20] (a) P. Svec, P. Novák, M. Nádvorník, Z. Padelková, I. Císarová, L. Kolárová,
Supplementary data related to this article can be found at http://
dx.doi.org/10.1016/j.jorganchem.2013.07.025.
ꢀ
ꢀ
ꢀ
ꢀ
ꢁꢀ ꢀ
ꢀ
A. Ruzicka, J. Holecek, J. Fluorine Chem. 128 (2007) 1390e1395;
ꢀ
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(b) P. Novák, J. Brus, I. Císarová, A. Ruzicka, J. Holecek, J. Fluorine Chem. 126
(2005) 1531e1538;
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