Quest for triorganotin(IV) compounds containing three C,N- and N,C,N-chelating ligands

Article abstract of DOI:10.1016/j.jorganchem.2013.02.018

Three novel tetraorganotin(IV) compounds of general formula L ₃SnR [where i) L is L^CN 2-(N,N-dimethylaminomethyl)phenyl- and R = n-Bu (1), Ph (2); and ii) L is L^NCN 2,6-bis-(N,N- dimethylaminomethyl)phenyl- with R = n-Bu (3)] were synthesized. These species were used as potential precursors for the target preparation of some triorganotin(IV) species of general formula L₃SnX [where i) L is L^NCN with X = OH (4), and ii) L is L^CN and X = Br (5), F (5b), Cl (5c)]. Several methods were applied to reach the target L ₃SnX molecules including the reactions of 1 or 2 with bromine, iodine or hydrohalic acids in various media, Kocheshkov reactions or transmetallation with HgCl₂, but the composition of all reaction mixtures was not satisfactory towards the target. Compound 4 has the monomeric structure with OH group interacting with one of the nitrogen atoms via H-bridge. Target compound 5 was prepared by the reaction of three equivalents L4CNSn with SnBr₄ followed by the isolation of 5 from the reaction mixture based on different solubility of 5 in various solvents. Surprisingly, the presumably air-stable 5 can easily ionize in the air to give a novel aqua-complex [L3CNSn(H ₂O)]⁺Br^- (5a). All prepared organotin(IV) compounds bearing both L^CN and L^NCN ligands were characterized by multinuclear NMR spectroscopy and, when eligible, by the elemental analysis. In addition, the solid-state structures of 1, 2, 4, 5a, 6, 8 and 9 were determined by the X-ray diffraction analysis.

Full text of DOI:10.1016/j.jorganchem.2013.02.018

Journal of Organometallic Chemistry 732 (2013) 47e57
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Journal of Organometallic Chemistry
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Quest for triorganotin(IV) compounds containing three C,N- and N,C,N-chelating
ligands
a,
a
a
b
c
a
ꢀ
ꢀ
*
ꢀ ꢁꢀ ꢀ
ꢀ
ꢀ
ꢀ
Ales Ruzicka , Zdenka Padelková , Petr Svec , Vladimír Pejchal , Lenka Ceslová , Jaroslav Holecek
a Department of General and Inorganic Chemistry, University of Pardubice, Studentská 573, CZ-532 10, Pardubice, Czech Republic
b Institute of Organic Chemistry and Technology, University of Pardubice, Studentská 573, CZ-532 10, Pardubice, Czech Republic
c Department of Analytical 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
Three novel tetraorganotin(IV) compounds of general formula L3SnR [where i) L is LCN 2-(N,N-dime-
thylaminomethyl)phenyl- and R ¼ n-Bu (1), Ph (2); and ii) L is LNCN 2,6-bis-(N,N-dimethylaminomethyl)
phenyl- with R ¼ n-Bu (3)] were synthesized. These species were used as potential precursors for the
target preparation of some triorganotin(IV) species of general formula L3SnX [where i) L is LNCN with
X ¼ OH (4), and ii) L is LCN and X ¼ Br (5), F (5b), Cl (5c)]. Several methods were applied to reach the
target L3SnX molecules including the reactions of 1 or 2 with bromine, iodine or hydrohalic acids in
various media, Kocheshkov reactions or transmetallation with HgCl2, but the composition of all reaction
mixtures was not satisfactory towards the target. Compound 4 has the monomeric structure with OH
group interacting with one of the nitrogen atoms via H-bridge. Target compound 5 was prepared by the
reaction of three equivalents LC4NSn with SnBr4 followed by the isolation of 5 from the reaction mixture
based on different solubility of 5 in various solvents. Surprisingly, the presumably air-stable 5 can easily
ionize in the air to give a novel aqua-complex [LC3NSn(H2O)]þBrꢀ (5a). All prepared organotin(IV) com-
pounds bearing both LCN and LNCN ligands were characterized by multinuclear NMR spectroscopy and,
when eligible, by the elemental analysis. In addition, the solid-state structures of 1, 2, 4, 5a, 6, 8 and 9
were determined by the X-ray diffraction analysis.
Article history:
Received 21 January 2013
Received in revised form
12 February 2013
Accepted 13 February 2013
Keywords:
Organotin(IV) compounds
C,N-ligand
NMR
XRD
Ó 2013 Elsevier B.V. All rights reserved.
1. Introduction
for Si and Sn compounds the strictly monodentate bonding of all
ꢁ
ligands was found (with shortest SneN distance 3.276 A). For the
C,N- and N,C,N-chelated metal complexes attracted much
attention of chemists directly after the development by van Koten
in 1970 [1]. Since that time, a plethora of papers dealing with this
part of chemistry appeared. The first and simple monoanionic bi-
(LCN) of terdentate LNCN) ligands (Fig. 1) underwent a number of
structural changes of their respective backbone which led in fact to
the constitution of self consistent field of chemistry covering nearly
all metals [2]. Although the amount of prepared and structurally
characterized compounds bearing only one or two simplest or
slightly modified ligands (Fig. 1) is really high (1226 structures in
the Cambridge Structural Data Base), the number of complexes
containing three or more ligands of this type per metal centre is
rather limited.
lanthanide compounds (LC2NM- 2-(LCN)2Li), two of the ligands are
m
bidentately bound but the remaining two act as bridging to the
lithium counter atom.
The familyof the compounds having three of these ligandsis from
the first view a bit broader but the major part of it are compounds of
groups 3, 13, 15 and lanthanides, where the stable oxidation state III
suggests the formation of such species [5,6]. In the case of phos-
phorus, these compounds (L3CNP) are successfully used as N,P-
chelating ligands for complexation of transition metal species [7].
On the other hand, for the rest of the metalloids and metals only
limited number of examples of compounds of the LC3NM type is
known. The tris-chelated chromium(III) complex with pseu-
dooctahedrally six-coordinated central metal atom is reported by
Cotton [8]. Two examples of ‘ate ZneLi complexes’ were reported
by van Koten [9], where one of the ligands acts as C,N-chelating to
the zinc atom, the second one is bridging between both metals and
the last one has CeZn covalent and LieN coordination bond. For the
central atom from the group 14 elements, where the rest of ex-
amples is found, compounds LC3NGeH [10] and L3CNSiF [11] were
Compounds with the central metal atom substituted by four
ligands were described for Si [3], Sn [4], Nd and Gd [5] only, where
* 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.2013.02.018

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A. Ruzicka et al. / Journal of Organometallic Chemistry 732 (2013) 47e57
48
benzene
- LiCl
N(CH3)2
N(CH3)2
3 LLi + RSnCl3
L3SnR (1 for LCN, R = n-Bu;
3
3
2
2
2 for LCN, R = Ph;
L= LCN, LNCN ; R = n-Bu, Ph
4
3 for LNCN, R = n -Bu)
4
1
1
5
6
air
LNCN3Sn(n-Bu) (3)
LNCN3SnOH (4) + n-BuH
LCN3SnBr (5)
N(CH3)2
LCN
LNCN
benzene
3 LCNLi + SnBr4
- LiBr
Fig. 1. Ligands used including the numbering of atoms.
direct workup
in the air
described by Corriu, and LC3NSiH [3] by Herdtweck having dynamic
behaviour in solution and only monodentately bound ligands in the
solid state with MeN distances about 3 A and thus the coordination
geometry of a distorted tetrahedron. Two very last examples came
from the private communication to the Cambridge Crystallographic
Data Base from the van Koten’s group [12], it seems these are
complexes of stannylene LC2NSn with LCNLi. In both cases the tin
atom is bonded to the three carbon atoms of ligands, nitrogen
donor groups are far from tin to speculate about coordination, and
one or two nitrogen donor group(s) being coordinated to the
[LCN2LCN(H)SnBr]+[Br.HBr]- (6)
ꢁ
Scheme 1. Preparation and reactivity of L3SnR (L ¼ LCN, LNCN; R ¼ n-Bu, Ph).
been studied by 13C and 15N NMR spectroscopy in solution and X-
ray diffraction techniques in the solid state. The preparation of 1
and 2 has been performed by addition of 3 equiv of LCNLi to the
stirred solution of RSnCl3 in benzene under an argon atmosphere at
approximately 10 ꢂC. The subsequent addition of chloroform in air,
led to the formation of yellowish precipitate of LiCl. Sufficiently
pure crystals of 1 and 2 were obtained after evaporation of solvents
and washing the solid residue by hexane in the case of 2, and long
time high dynamic vacuo evaporation in the case of 1. In order to
prepare LC3NSnBr, the direct reaction of 3 equiv of LCNLi and SnBr4
was conducted, the subsequent workup on the air gave a mixture of
different species from which the compound 6 as an adduct of 5 with
2 equiv of HBr was separated in about 20% yield. When the same
procedure is applied in the preparation of 3 which would contain
three potentially terdentate LNCN ligands, only compound 4 is ob-
tained as a product of a hydrolysis in a moderate yield (Scheme 1).
Such a hydrolysis and elimination of n-butane from the presumably
hydrolytically stable tetraorganotin(IV) compound, known for
metal-alkyl species of more electropositive metals, is for tin(IV)
compounds still elusive in the literature. Compounds 3 and 5 can be
obtained by described procedures under strictly inert conditions
only, where 5 is still isolated in a mixture together with LC2NSnBr2
[16a] and LC4NSn [4] (see below for more details).
ꢁ
lithium atom. There is rather short SneLi distance (w2.7e2.83 A)
completing the coordination polyhedra of the tin atom to a
deformed
position.
J-trigonal bipyramid with the lithium atom in an axial
Twenty years ago (w1994) we started some synthetic work in
the area of organotin(IV) compounds substituted by LCN ligand(s)
originally developed by van Koten and Jastrzebski [2b,13]. The main
idea was to develop a methodology for structure evaluation of these
hypercoordinated compounds based on various NMR spectroscopy
techniques in solution. For that reason we have developed the
chemistry of n-butyl [14] substituted compounds which enabled us
to measure the spectra of all nuclei present in the molecule and to
determine various coupling constants in high concentration sam-
ples. Since that time a plenty of LCN and LNCN substituted organo-
tin(IV) compounds were prepared and presented by us and others
[15], including the doubly [16] or quadruple [4] chelated ones.
These compounds also found a potential practical use as trans-
esterification or esterification catalysts [17], fluorinating agents
[18], parts of ion selective electrodes [19] or antimycotical agents
[20]. The particular use of some of these complexes in various types
of catalytically driven reactions such as CO2 activation to dimethyl
carbonate reactions has been developed, too [21].
The solution state 1H and 119Sn NMR spectra measurements of
precursors 1 and 2 in CDCl3 gave surprisingly well resolved signals
at room temperature, which indicate high degree of fluxionality of
all ligands and enabled us to measure also the 13C and 15N NMR
spectra at this temperature. The patterns typical for tetraorgano-
tin(IV) compounds containing LCN chelating ligands were observed
for room temperature 1H NMR spectra of 1 and 2. The temperature
As side products of this investigation, the compounds of the
types LC3NSnR and LN3CNSnR were prepared and investigated in order
to prepare highly coordinated species, L3Snꢁ radicals or ionic spe-
cies L3SnL and L3SnD which are of current interest not only as
chemical curiosities but also as heavier congeners of instable in-
termediates of organic compounds formation and reactivity in
various types of substitution reactions.
1
dependent H NMR spectra of 1 and 2 performed at ꢀ50 ꢂC show
only a broadening of all signals. In 119Sn NMR spectra of these
compounds, signals at ꢀ109.9 for 1 and ꢀ161.9 ppm for 2 were
observed which are similar to values found for comparable tin
compounds as for example ꢀ163.3 ppm for LCNSnPh3 [15g]
and ꢀ129.6 ppm for (2-i-Bu-C6H4)SnPh3 [14b], respectively. This
fact could be explained by very low effect of the potentially
chelating ligand or an increase of shielding by the presence of the
2. Results and discussion
2.1. Synthesis and structural characterization of tetraorganotin(IV)
compounds used as precursors for target triorganotin(IV) species.
Hydrolysis of LN3CNSn(n-Bu) (3)
LCN ligand instead of n-butyl group e the comparison of 119Sn)
d(
[14b] for
L
CNSn(n-Bu)3 being ꢀ50.7 ppm, for LC2NSn(n-
Bu)2 ꢀ85.3 ppm, and 1 (
d
(
119Sn) ¼ ꢀ109.9 ppm). On the other hand,
As precursors for target triorganotin(IV) compounds of the
L3SnX type, where X ¼ halogen, potentially trischelated complexes
L3SnR 1e3 (Scheme 1) were prepared by conversion of a slight
excess of appropriate lithium salt with n-butyl- or phenyltin(IV)
trichloride, respectively. All complexes were identified by 1H and
119Sn NMR spectroscopy in solution, ESI-MS spectrometry and
elemental analysis. In addition the structure and composition of
both 1 and 2 containing three potentially bidentate ligands, have
the 3J(119Sn,1H) (56.1 Hz for 1, and 60.3 Hz for 2) and 1J(119Sn,13C)
(484.9 and 480.1 Hz for 1; 594.8 and 557.4 Hz for 2) coupling
constants, which are highly indicative for the tin coordination
number value [22], are in line with previously found values for
related tetraorganotin(IV) compounds [14b]. Also the values found
in 15N NMR spectra are almost identical with values for LCNSn(n-
Bu)3 [14a] and other tetraorganotin(IV) compounds containing one
potentially chelating ligand.

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A. Ruzicka et al. / Journal of Organometallic Chemistry 732 (2013) 47e57
49
Both identity and purity of all stable compounds were
confirmed by ESI-MS spectrometry in the positive-ion mode. The
typical feature of ESI mass spectra of early studied organotin
compounds is the cleavage of the most labile bond present in the
molecule e for example Snehalogen or Sneoxygen. Completely
different behaviour is observed for samples where any labile bond
is present (1 and 2). In the case of 2, two series of ions are observed.
First, the phenyl is cleaved and then the subsequent losses of
CH3NHCH3 or LCN ligands are observed. The second series came
from protonated molecule of 2, the subsequent losses of CH3NHCH3
are observed in spectra. When n-butyl is bound to the tin atom
together with three LCN ligands (1), the butyl together with (CH3)3N
or LCN ligand together with (CH3)3N are primarily lost.
The solid state structures of 1 (Fig. 2) and 2 (Fig. 3) were
determined by crystallographic techniques. Both compounds reveal
tetrahedral vicinity of the tin central atoms with average CeSneC
angles being 109.3ꢂ, but with large discrepancies in angle values
from 102.54(9) to 121.56(9)ꢂ. These can be hardly described as
perfect tetrahedra. On the other hand, the influence of the pendant
arms containing the nitrogen donor atoms seems to be negligible in
the solid state from the point of view of observed SneN distances
Fig. 3. Molecular structure of 2 (ORTEP view, 40% probability level). Hydrogen atoms
ꢁ
ꢂ
around 3 A (as a minima). Although these distances are still in the
ꢁ
are omitted for clarity. Selected interatomic distances [A] and angles [ ]: Sn1 C1
2.146(3), Sn1 C10 2.149(2), Sn1 C19 2.173(3), Sn1 C28 2.135(3), Sn1 N1 2.992(3), Sn1 N2
4.787(3), Sn1 N3 4.705(3); C1 Sn1 C10 114.44(9), C1 Sn1 C19 106.38(10), C1 Sn1 C28
115.22(10), C28 Sn1 C19 103.05(10), C10 Sn1 C19 105.11(10), C28 Sn1 C10 111.30(10).
range determined by the sum of van der Waals radii of both atoms,
ꢁ
usually the distance over 2.8 A is not taken into the account as an
intramolecular connection.
In the case of NMR spectroscopic studies of 3, only broad set of
signals is observed in the 1H NMR spectrum at room temperature.
The broad signal at ꢀ135 ppm was detected in the 119Sn NMR
spectrum of 3 measured in C6D6. This value is slightly lower than for
1, but reasonable explanation pointer is available on the basis of
comparison with analogous lowering from LCNSnPh3 which reso-
nates at ꢀ163.9 ppm with LNCNSnPh3 resonating at ꢀ201.9 ppm
[15i]. A cooperative influence of more than one donor group in
chelating ligands could be the reason for this phenomenon. When 3
is exposed in solution to air, the loss of signals for n-butyl group is
observed in the 1H NMR spectrum in chloroform which is indicative
for the plausible formation of 4, but the OH resonance is not visible
and the rest of the signals remain broader. In the 119Sn NMR
spectrum of 4 in CDCl3, the broad signal at ꢀ158.1 ppm is detected
at room temperature. New broad set of signals was detected in 1H
NMR spectrum in THF-d8 which is not resolved in the whole tem-
perature range up to 220 K, but two new broad signals are visible in
the low field part of the spectrum at such a low temperature (13.5
and 12.3 ppm). Two broad signals of relative integral intensities
approximately 2:3 (ꢀ147.7 and ꢀ165.6 ppm e determined at 220 K)
and close to the chemical shift values observed in chloroform were
detected also in the 119Sn NMR spectrum. It seems, the structure of
4 is different in chloroform and THF solution, respectively, where
the formation of new species, presumably cationic one due to the
extrusion of the OHꢀ group from the tin coordination sphere, or the
formation of an isomer of 4 is observed. In the 119Sn NMR spectrum
of the same sample recorded in CDCl3 after the evaporation of THF-
d8 the same sole signal at ꢀ158.1 ppm is observed again thus
indicating the reversibility of the process.
The formation of [LN3CNSn]þ fragment e.g. loss of the hydroxyl
group is primarily observed in the positive mode of ESI-MS spec-
trum of 4.
Single crystals of pure 4 grew from the neat oily 4 after standing
for one week at room temperature. Its solid state structure (Fig. 4) is
composed of three LNCN ligands and one terminal OH moiety
covalently bound to the tin atom. Although the tin coordination
polyhedron could be described as even more distorted tetrahedron
than in 1 or 2, the nitrogen containing pendant arms which have
any contact with the central atom play important role in stabili-
zation of the terminal SneOH group by relatively strong connection
performed by hydrogen bridge to the N1 atom. The Sn1eO1 dis-
ꢁ
tance being 1.981(2) A lies in the range determined by values of
ꢁ
ꢁ
1.961 A and 2.005 A reported for only two correctly crystallo-
graphically determined structures of the tetrahedral monomeric
triorganotin(IV) hydroxides [23]. In comparison to 1, 2 and the rest
ꢁ
of SneC bonds in 4, the Sn1eC1 distance of 2.208(3) A is signifi-
cantly longer again probably due to the H-bond being situated in
the same part of the molecule. The literature comparison of the
structure of 4 to another SneOH fragment containing compounds
Fig. 2. Molecular structure of 1 (ORTEP view, 40% probability level). Hydrogen atoms
ꢂ
ꢁ
are omitted for clarity. Selected interatomic distances [A] and angles [ ]: Sn1 C1
2.157(2), Sn1 C10 2.179(2), Sn1 C19 2.177(2), Sn1 C28 2.145(2), Sn1 N1 3.059(2), Sn1 N2
3.173(2), Sn1 N3 4.785(2); C1 Sn1 C10 107.73(8), C1 Sn1 C19 110.26(8), C1 Sn1 C28
121.56(9), C28 Sn1 C19 105.87(9), C28 Sn1 C10 107.25(9), C10 Sn1 C19 102.54(9).
positioned
4 to the very limited group of monomeric tri-
organotin(IV) hydroxides. The rest of triorganotin(IV) hydroxides

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A. Ruzicka et al. / Journal of Organometallic Chemistry 732 (2013) 47e57
50
Fig. 5. Molecular structure of 6 (ORTEP view, 30% probability level). Some ofꢂhydrogen
ꢁ
atoms are omitted for clarity. Selected interatomic distances [A] and angles [ ]: Sn1 C1
Fig. 4. Molecular structure of 4 (ORTEP view, 50% probability level). Some of the
hydrogen atoms are omitted for clarity. Selected interatomic distances [A] and angles
ꢁ
2.155(9), Sn1 C10 2.151(10), Sn1 C19 2.146(10), Sn1 N1 2.474(8), Sn1 N2 3.310(11), Sn1
N3 4.748(7), Sn1 Br3 2.6887(12); C1 Sn1 C10 136.4(4), C1 Sn1 C19 108.5(4), C19 Sn1
C10 112.2(3), C1 Sn1 Br3 97.0(3), N1 Sn1 Br3 172.1(2). Hydrogen bonding: N3eH/Br1a
[ꢂ]: Sn1 O1 1.981(2), Sn1 C1 2.208(3), Sn1 C13 2.169(3), Sn1 C25 2.184(3), Sn1 N1
3.721(4), Sn1 N2 3.680(3), Sn1 N3 3.469(3), Sn1 N4 4.819(4), Sn1 N5 2.934(3), Sn1 N6
4.909(3); C1 Sn1 O1 97.40(10), O1 Sn1 C13 106.95(10), O1 Sn1 C25 102.66(10), C1 Sn1
C13 118.20(11), C1 Sn1 C25 ꢂ106.63(11), C13 Sn1 C25 121.15(10). Hydrogen bonding:
ꢂ
ꢂ
ꢁ
ꢁ
3.310(8) A, 158.5 ; Br1eH/Br2 4.107(8) A, 144.6(2) .
ꢁ
O1eH/N1 2.760(4) A, 168.6 .
was separated by crystallization of 8 from oily 7. The composition of
7 is deduced from 1H and 119Sn NMR spectra patterns similar to
LC2NSn(n-Bu)Cl [14a]. The 119Sn) of 7 and its chlorinated analogue
d(
usually condensate to oxides [24a] or crystallize as dimers or
polymers as in the cases of trimethyl- or triphenyltin(IV) hydrox-
ides [25]. The target synthesis and structural characterization of 5 is
described in detail in following Chapters 2.2. and 2.3.
differs only by ca. 7 ppm.
Except of the peak attributed to the protonated 7, the peak
corresponding to the loss of bromide anion is the most intense peak
observed in both positive mode ESI-MS spectra of 7 and 8,
respectively. Moreover the structure of 8 has been determined in
the solid state (see Supplementary material, Figs. S1 and S2).
The next possibility for the preparation of the L3SnX species is
the reaction of tetraaryltin(IV) species with bromine in benzene or
chloroform [27]. This procedure has been applied to 2 and half of
equivalent of bromine in the air taking into the account presumably
higher reactivity of the unsubstituted phenyl ring than the phenyl
with the pendant arm. The reaction is rather slow with yield of
about 30% after two days. When the same reaction is conducted at
elevated temperature the yield increased to approximately 45%, but
The composition and structure of [LC2NLCN(H)SnBr]þ[Br$HBr]ꢀ
(6), as a minor product of reaction of 3 equiv of LCNLi and SnBr4
(which should presumably produce 5) with a workup in the air,
were studied by NMR spectroscopy in solution as well as X-ray
diffraction in the solid state. Unfortunately, very low solubility (it
also did not melt below 270 ꢂC) of 6 in inert solvents such as
benzene or chloroform did not allow detailed NMR studies and only
broad signals at predictable positions were observed in the 1H NMR
spectrum in chloroform solution, no signal has been detected after
a whole day measurement in the 119Sn NMR spectrum.
The solid-state structure of 6 consists of tin containing fragment
[LC2NLCN(H)SnBr]þ interconnected by hydrogen bridge with
Brꢀ/HBr fragment (Fig. 5). The coordination behaviour of the tin
atom is trigonal bipyramidal with all three carbon atoms located in
equatorial plane and nitrogen donor atom and one of the bromine
atoms in axial positions revealing almost ideal flat interatomic
angle (N1 Sn1 Br3 ¼ 172.1(2)ꢂ).
DMF, air
R. T.
LCN3Sn(n-Bu) (1) + Br2
LCN2Sn(n-Bu)Br (7)
+ 2-(Me2NCH2)C6H4Br.HBr (8)
benzene, air
R. T.
-
LCN3SnPh (2) + Br2
LCN3SnPh (2) + I2
[LCN3Sn(H2O)]+Br (5a) + PhBr
Finally, having precursors 1e3, one could start the synthesis and
structural characterization of target triorganotin(IV) species
bearing three potentially chelating ligands.
benzene, air
reflux
LCN2SnI2 + Ph4Sn + LCNPh2SnI
benzene, air
R. T.
LCN3SnPh (2) + HI
LCN3SnPh (2) + HF
LCN2SnPhI.HI (9)
+ Me2NCH2C6H5 HI
.
2.2. Preparation and structural investigation of target compounds
of the LC3NSnX type (X ¼ halogen)
benzene, air
R. T.
LCN2SnPhF (5b) + LCN
H
We decided to use 1 and 2 for plausible formation of the target
species LC3NSnX (where X ¼ halogen, Scheme 2). The formation of
triorganotin(IV) bromides is described in the literature using re-
action of triarylalkyltin(IV) compounds with bromine or HBr [26].
Applying exactly the same protocol to the reaction of 1 yielded
(immediate decolourization of the bromine solution) surprisingly
the triorganotin(IV) compound 7 and an adduct of the ortho-
brominated ligand with HBr (8) (Scheme 2). The reaction mixture
benzene, air
R. T.
LCN4Sn + HgCl2
LCN2SnCl2 + LCN2Hg
THF, air
R. T.
2 LCN4Sn + HgCl2
LCN3SnCl (5c) + LCN2SnCl2
+ LCN2Hg
Scheme 2. Reactivity of LC3NSnR and L4CNSn.

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51
a mixture of products (LC3NSnBr, probably L2CNSnPhBr and L2CNSnBr2
[16a]) is obtained. The analogous procedure starting from LC4NSn [4]
led to the yield of about 10% of 5. From both reactions the crystalline
compound [LC3NSn(H2O)]þBrꢀ (5a) as an adduct of 5 with one water
molecule is isolated (see Scheme 2).
residue after the previous reaction is formed together with 5c
which could be identified by the help of NMR measurements and
similarity of the spectra with 5 as LC3NSnCl. Broad signals were
observed in 1H as well as in 119Sn NMR spectra where signal
at ꢀ190.2 ppm is attributed to 5c.
The structure of 5a (Fig. 6) consists of trigonal bipyramidal tin-
On the basis of above mentioned rather unsuccessful experi-
ments we decided to follow and reinvestigate the reaction of
3 equiv LCNLi with SnBr4 at various conditions.
containing cation which is made of three LCN ligands from which
ꢁ
one is bidentately coordinated (Sn1 N1 2.551(3) A) and the
remaining two have the hydrogen bonds to the water molecule
tightly connected to the tin atom in mutual trans positions to the
intramolecularly coordinated nitrogen atom.
2.3. Revisiting the synthesis and isolation of LC3NSnBr (5). Synthesis
of LC3NSnF (5b). Detailed structural characterization of 5, 5a and 5b
in solution
Other attempts to prepare LC3NSnI (Scheme 2) by reactions of 2
with HI and I2, respectively, were carried out. The reaction with
iodine yielded LC2NSnI2 [16a], LCNPh2SnI [16b], and tetraphenyl-
stannane, as identified by NMR spectroscopy [24b] and X-ray
diffraction analysis and a negligible amount of species having
similar broad signals in 1H NMR spectrum as 5a. The iodinated
analogue of 5a is probably the minor product. The second reaction
of 2 with HI yielded tin compound 9 and adduct of the free ligand
with HI which was identified by NMR spectroscopy revealing
similar spectrum as the protonated ligand with protic acids [28].
The structure of 9 is evaluated by ESI-MS and multinuclear NMR
spectroscopy showing similar spectral patterns as other stannates
bearing two LCN moieties [28] and X-ray techniques on single
crystalline material revealed similar structure to 6, unfortunately
the quality of crystals was not ideal and a disorder of the phenyl
ring together with only isotropical displacement of two nitrogen
atoms caused the publishing the data and figure in Supplementary
material (Figs. S3 and S4).
Surprisingly, all attempts for the direct synthesis of 5 from LCNLi
and SnBr4 (in a 3:1 ratio) in benzene at ambient temperature failed
and the only species which was isolated from the reaction mixture
was identified by 1H and 119Sn NMR spectroscopy as pure LC4NSn
(
d
(
119Sn) ¼ ꢀ145.8 ppm in THF-d8) [4]. Changing the reaction con-
ditions(e.g. the use of tolueneor THF instead of benzene as a solvent)
or varying the reaction temperature (e.g. reflux, ambient tempera-
ture or maintaining the temperature around 0 ꢂC) did not lead to the
expected exclusive formation of the desired product as well. Un-
fortunately, however, even reactions of LC2NSnBr2 [Ref. [16a]] and
L
CNSnBr3 [15f] with LCNLi (1 or 2 equiv, respectively) always resulted
only in the formation of mixture of products (identified as LC2NSnBr2,
L3CNSnBr, and L4CNSn [4] by 1H and 119Sn NMR spectroscopy) where
the desired compound 5 was present in less than 10% yield. Due to
these reasons we decided to synthesize the title compound by the
so-called Kocheshkov redistribution reaction [29].
The reaction of 2 with aqueous HF provided LC2NSnPhF [16c]
together with free ligand LCNH which was confirmed by multinu-
clear NMR spectroscopy.
Several possible reaction pathways were thus investigated (see
Scheme 3). Unfortunately, neither the reaction of LC4NSn [4] with
1 equiv of LC2NSnBr2 [16a] nor with LCNSnBr3 [15h] (in a 2:1 ratio) in
warm toluene gave exclusively the desired compound (reaction time
3 days). Nevertheless, we observed the presence of the desired
product in the reaction mixture as the major product (assay of 5 ca.
42, and 47 mol%, respectively) according to the 1H and 119Sn NMR
The attempt to prepare compound LC3NSnCl was based on the
reaction of LC4NSn with HgCl2 (Scheme 2), but only L2CNSnCl2 and
LC2NHg were detected by the help of 1H and 119Sn NMR spectra
measurement and comparison with the literature data [1c,16a,b].
When 2 equiv of LC4NSn was reacted with HgCl2 in THF at room
temperature, inseparable mixture of all compounds present in the
spectroscopy (
d
(
119Sn) ¼ ꢀ201.8 ppminTHF-d8). Themost promising
thus seemed to be the reaction of 3 equiv of LC4NSn (which can be
easily prepared on a large scale) with commercially available anhy-
drous SnBr4 in boiling toluene (mixed with ca. 25%THF by volume for
better solubility of reagents, reaction time 2 days). According to the
1H and 119Sn NMR spectroscopy, the reaction mixture contains both
starting reagent LC4NSn (
d(
119Sn) ¼ ꢀ145.8 ppm in THF-d8; ca. 32 mol
%) and desired compound 5 (
d(
119Sn) ¼ ꢀ201.8 ppm in THF-d8; ca.
64 mol%). In addition, LC2NSnBr2 was formed as well
(d(
119Sn) ¼ ꢀ271.4 ppm inTHF-d8; ca. 4 mol%). Target species 5 can be
then isolated in ca. 95% purity (with LC4NSn being the unreactive
toluene, 90°C
LCN4Sn + LCN2SnBr2
2 LCN4Sn + LCNSnBr3
3 LCN4Sn + SnBr4
LCN3SnBr + LCN4Sn + LCN2SnBr2
42% 29% 29%
inert at., 3 d
toluene, 90°C
inert at., 3 d
LCN3SnBr + LCN4Sn + LCN2SnBr2
47% 42% 11%
THF, R.T.
LCN3SnBr + LCN4Sn + LCN2SnBr2
41% 33% 26%
inert at., 3 d
Toluene/THF
3 LCN4Sn + SnBr4
LCN3SnBr + LCN4Sn + LCN2SnBr2
64% 32% 4%
Fig. 6. Molecular structure of 5a (ORTEP view, 50% probability level). Some of the
reflux,
inert at., 2 d
hydrogen atoms and the non-coordinated THF molecule are omitted for clarity.
ꢂ
ꢁ
Selected interatomic distances [A] and angles [ ]: Sn1 C1 2.125(4), Sn1 C10 2.140(4),
Sn1 C19 2.157(4), Sn1 N1 2.551(3), Sn1 N2 3.674(3), Sn1 N3 3.703(4), Sn1 O1 2.083(3);
C1 Sn1 C10 123.80(14), C1 Sn1 C19 114.65(15), C1 Sn1 O1 98.75(13), C1 Sn1 N1
Scheme 3. Various unsuccessful reactions studied for the plausible exclusive synthesis
of 5.
ꢁ
ꢁ
73.95(13). Hydrogen bonding: O1/N3 2.677(5) A and O1/N2 2.814(5) A.

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A. Ruzicka et al. / Journal of Organometallic Chemistry 732 (2013) 47e57
52
impurity) from this reaction mixture thanks to the different solubi-
lity in selected solvents (diethyl ether and chloroform) according to
the procedure which is described in the Experimental part in detail.
Preparation of 5 requires strictly anaerobic and anhydrous condi-
tions otherwise formation of its adduct with water (5a) will occur.
LC3NSnF (5b) was prepared from 5 by the simple reaction with
exhibited only one resonance at ꢀ196.9 (1J(119Sn, 19F) ¼ 2236 Hz,
measured in THF-d8) which is typical for monomeric tri-
organotin(IV) fluorides with terminal SneF bond [30]. This is the
direct and unambiguous evidence of the purely covalent nature of
the SneF bond in 5b in solution.
Unfortunately, however, single crystals of 5 were not obtained
despite several attempts to crystallize it were performed. But when
crystallized from wet THF in the air we were able to isolate again
single crystals of its aqua-derivative [LC3NSn(H2O)]þBrꢀ (5a) dis-
cussed above (see Fig. 6). 1H NMR spectra of this species recorded
both in CDCl3 and THF-d8 revealed nearly the same spectral pattern
L
CN(n-Bu)2SnF which proved to be a very effective and versatile
fluorinating agent [18]. 5b has been prepared in order to distinguish
between the presence of terminal or bridging fluorine atoms by the
help of multinuclear NMR spectroscopy. This can be done simply by
the comparison of coupling constants (1J(119Sn, 19F) found for 5b
with previously reported results (see below).
when compared to 1H NMR spectra of anhydrous
5 (see
Structure of 5 (95% purity) in solution was investigated by 1H
and 119Sn NMR spectroscopy. 1H NMR spectra of 5 recorded both in
THF-d8 and CDCl3 showed similar patterns at ambient temperature
revealing slightly broader resonances when measured in CDCl3.
According to the presence of only one set of signals that were
unambiguously attributed to all three ligands we assume the
bonding equality of these ligands. In general, the value of the
3J(119Sn, 1H) satellites of the doublet of the H(6) signal in the 1H
NMR spectra is a useful tool for characterizing all C,N-chelated
organotin compounds. Prepared 5 exhibits the coupling constant
3J(119Sn, 1H) being ca. 65 Hz which is in good agreement with
previously published results [14,22]. All other minor signals found
in the 1H NMR spectra were assigned to the LC4NSn [4] species being
the impurity (less than 5%). Almost pure 5b revealed similar
spectral pattern as in the case of 1H NMR spectrum of 5 but
exhibiting more narrow resonances, especially that one of the
doublet of the H(6) signal when recorded in THF-d8.
Experimental part). The only difference is caused by the presence of
the very broad resonance of the solvating water molecule
(d
(1H) ¼ 5.67 ppm) observed when measured in CDCl3. Surprisingly,
this signal disappeared when measuring the sample inTHF-d8. More
interesting structural data were gathered from 119Sn NMR spectra.
Only one broad signal was observed at ꢀ185 ppm (recorded in
CDCl3) which is a sign of the presence of five-coordinate tin species.
In general, according to our opinion, there are two possible struc-
tural motifs (presumably ionic) of this species in solution: i) ionic
form with only one intramolecularly coordinated ligand, two non-
coordinated ligands and coordinated solvating water molecule
(Fig. 7, structural motif C), and ii) ionic form bearing two intramo-
lecularly coordinated ligands, one non-coordinated ligand and the
water molecule interacting with the “naked” bromide anion (Fig. 7,
structural motif D). Unfortunately, we were not able to prove which
one of the two possible forms is really present in the chloroform
solution. The 119Sn NMR spectrum of 5a recorded in THF-d8 dis-
played only one broad resonance at ꢀ202.0 ppm which is very close
The most valuable data about the structure (i.e. the coordination
geometry of the central tin atom) of 5 in solution arose from the
119Sn NMR spectra. Surprisingly, according to the 119Sn NMR spec-
to the chemical shift value found for anhydrous
5
(d(
119Sn) ¼ ꢀ201.8 ppm in THF-d8). This could be explained by the
trum of
5
recorded in CDCl3 at ambient temperature
similar, presumably ionic, structure of these species in solution. As
described above in the discussion we suppose, in general, the
presence of two possible species with five-coordinate tin centres
(Fig. 7, structural motif C or D). In this particular case we favour the
presence of the species having the D ionic structural motif (e.g.
bearing two intramolecularly coordinated ligands, one non-
coordinated ligand and the water molecule interacting with the
“naked” bromide anion). All these conclusions were further sup-
ported by 1H and 119Sn VT-NMR spectroscopy measurements (vide
infra) and solid state investigation according tothe literature [31,32].
In addition, structural behaviour of anhydrous 5 (prepared under
an argon atmosphere and further dried over molecular sieves) in
solution was studied by VT-NMR spectroscopy in order to further
elucidate its structural behaviour in solution. Decreasing the tem-
perature to ꢀ40 ꢂC led to the differentiation of signals of ligands
forming thus quite complex spectral pattern (revealing several AX
spin systems attributable to the pendant arms of ligands) in the 1H
NMR spectra (recorded in CDCl3) as expected. Even more
(d
(
119Sn) ¼ ꢀ123.8 ppm, broad) we suggest no intramolecular
N / Sn interaction and thus only four-coordinate tin centre as
depicted in Fig. 7 (structural motif A). On the other hand, the 119Sn
NMR spectrum recorded at room temperature in THF-d8 clearly
shows significant upfield shift of the broad resonance up
to ꢀ201.8 ppm which corresponds with five-coordinate tin atom
(Fig. 7, structural motif B). So, based on structural data combined
from 1H and 119Sn NMR spectra recorded in THF-d8 at room tem-
perature we assume very fast equilibrium (at least on the NMR time
scale) between one coordinated and two non-coordinated pendant
arms of all three potentially chelating ligands. Contrary to the sit-
uation described for 5, we observed only one signal in each
deuterated solvent (doublets with coupling constants 1J(19F, 119Sn)
being 2162 Hz, and 2251 Hz, respectively) in the 119Sn NMR spectra
of 5b recorded in both CDCl3
(
d
(
119Sn) ¼ ꢀ207.8 ppm) and THF-d8
(d
(
119Sn) ¼ ꢀ204.8 ppm) which indicates that the central tin atom is
five-coordinated in both cases. The 19F NMR spectrum of 5b
+
+
NMe2
NMe2
Me2N
Me2
N
NMe2
NMe2
O
Br
Sn
Br
-
-
Br
Br
Sn
Sn
Me2N
Sn
Me2N
NMe2
NMe2
NMe2
NMe2
A
B
C
D
Fig. 7. Schematic drawings of four proposed structural motifs of 5 and its aqua complex 5a (O ¼ H2O or THF in the case of C).

ꢁꢀ ꢀ
A. Ruzicka et al. / Journal of Organometallic Chemistry 732 (2013) 47e57
53
complicated was interpretation of 1H VT-NMR spectra recorded in
THF-d8 at ꢀ60 ꢂC due to the complex equilibrium among three
structural motifs A, B and C or D depicted in Fig. 7 that was confirmed
by the 119Sn VT-NMR. Therefore, the complete assignment of all
signals was not carried out. Nevertheless, it is evident that at lower
temperatures the differentiation of signals of ligands (both intra-
molecularly coordinated and non-coordinated) occurs, too. The 119Sn
VT-NMR spectra measured in CDCl3 exhibited always only one nar-
row resonance shifted several ppm upfield (for example
of each compound approximately in 0.6 ml of deuterated solvents.
The values of 1H chemical shifts were calibrated to residual signals
of chloroform (
d
(1H) ¼ 7.27 ppm), benzene (
d
(1H) ¼ 7.16 ppm) or
THF (
d
(1H) ¼ 3.57 ppm). The values of 13C{1H} chemical shifts were
calibrated to signals of CDCl3 (
d
(
13C) ¼ 77.2ppm), 15N{1H} chemical
shifts to external neat nitromethane (
d
(1N) ¼ 0.0 ppm). Values of
19F{1H} chemical shifts were calibrated to external standard CCl3F
(
d
(
19F) ¼ 0.0 ppm). The 119Sn{1H} chemical shift values are referred
to external neat tetramethylstannane (
d
(
119Sn) ¼ 0.0 ppm). Positive
d
(
119Sn) ¼ ꢀ127.5 ppm at ꢀ40 ꢂC) relatively to the signal observed at
chemical shift values denote shifts to the higher frequencies rela-
tive to the standards. 119Sn{1H} NMR spectra were measured using
the inverse gated-decoupling mode. All 13C{1H} NMR spectra were
measured using standard proton-decoupled experiment and CH
and CH3 vs. C and CH2 were differentiated by the help of APT
method e in the cases of compounds with a dynamic behaviour in
solution or limited solubility no 13C NMR spectra were recorded.
ambient temperature (
d(
119Sn) ¼ ꢀ123.8 ppm) but still matching
with only four-coordinate tin atom (e.g. Fig. 7, structural motif A). As
stated vide supra we observed complex equilibrium among three tin-
containing species (structural motifs A, B and C or D depicted in
Fig. 7) in the 119Sn VT-NMR spectra measured in THF-d8. This hy-
pothesis is based on following chemical shift values found in the
spectrum (recorded at ꢀ60 ꢂC): i) minor signal at ꢀ125.7 ppm
(structural motif A) corresponds with non-ionic four-coordinate tin-
containing species; ii) first major narrow signal at ꢀ185.1 ppm
(structural motif C or D) matches to presumably ionic five-
coordinated tin-containing species; and iii) second major signal
at ꢀ221.5 ppm can be attributed tothe non-ionic form of 5 where the
central tin atom is five-coordinated (e.g. Fig. 7, structural motif B).
The mutual integral intensityof these two major resonances is nearly
in a 1:1 ratio.
4.1.3. Elemental analyses
The compositional analyses were determined on the automatic
analyzer EA 1108 by FISONS Instruments.
4.1.4. Crystallography
The X-ray data (Table 1) for colourless crystals of all compounds
were obtained at 150 K using Oxford Cryostream low-temperature
device on a Nonius KappaCCD diffractometer with MoKa radiation
ꢁ
(l
¼ 0.71073 A), a graphite monochromator, and the
f and c scan
3. Conclusion
mode. Data reductions were performed with DENZO-SMN [33]. The
absorption was corrected by integration methods [34]. Structures
were solved by direct methods (Sir92) [35] and refined by full matrix
least-square based on F2 (SHELXL97) [36]. 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 factors Hiso(H) ¼ 1.2Ueq(pivot atom) or of 1.5Ueq for the
Ten novel tri- or tetraorganotin(IV) compounds were prepared
and structurally characterized in the course of this work. Unfortu-
nately, in general, we were not able to discover any reaction which
would result in the exclusive formation of desired triorganotin(IV)
species bearing three C,N- or N,C,N-chelating ligands. Only mix-
tures of target LC3NSnX compounds together with other organo-
tin(IV) species were formed in all reactions studied. Nevertheless,
at least in the case of 5 a viable way of preparation and isolation is
described leading to 95% purity (with 5% of LC4NSn as impurity
which shall not influence the future proposed reactivity studies of
5). Further reactivity studies of 5 (e.g. preparation of its hydride,
hydroxide etc. derivatives) are currently in progress.
ꢁ
methyl moiety with CeH ¼ 0.96, 0.97, and 0.93 A for methyl,
methylene and hydrogen atoms in aromatic rings, respectively.
The hydrogen atoms of the OH or H2O groups were placed according
to maxima on the Fourier difference maps. Disordered non-coordi-
nated solvents (THF or diethyl ether) were found in crystals of 6 and
5a. Attempts were made to model this disorder or split into two
positions, but wereunsuccessful. PLATON/SQUEZZE [37] was used to
correct the data for the presence of disordered solvent. A potential
4. Experimental
3
ꢁ
solvent volume of 2074 and 246 A was found.1056 and 98 electrons
per unit cell worth of scattering were located in the voids. The
calculated stoichiometry of solvent was calculated to be twenty four
additional molecules of THF and two Et2O per unit cell.
4.1. General methods
4.1.1. Mass spectrometry
Positive-ion electrospray ionization (ESI) mass spectra (MS)
were measured on the LCQ ion trap analyser (Thermo Fisher Sci-
entific, Waltham, MA, USA) in the range m/z 50e1000. The samples
were dissolved in acetonitrile and analysed by direct infusion at the
4.2. Synthesis
All solvents and starting materials such as n-butyltin trichloride,
phenyltin trichloride, SnBr4 and dimethylbenzylamine were pur-
chased from commercial sources (SigmaeAldrich) and purified by
vacuum distillation. 2,6-Bis(N,N-dimethylaminomethyl)benzene
and appropriate lithium compounds were prepared as described
elsewhere [38]. LC4NSn [4] and LCN(n-Bu)2SnF [30] were synthesized
according to procedures described in the literature. Solvents were
distilled from K/Na alloy and stored over a potassium mirror under
and the argon atmosphere or dried and degassed using commercial
drying columns (Innovative Technology Inc., USA). Single crystals
suitable for XRD analyses were obtained from corresponding satu-
rated solutions or upon a long standing of distilled compound (1).
flow rate 10 ml/min. The ESI ion source spray voltage was set to 4 kV,
capillary temperature was 200 ꢂC, capillary voltage 30 V and tube
lens offset 15 V.
4.1.2. NMR spectroscopy
NMR spectra were recorded from solutions in CDCl3, C6D6 and
THF-d8 on a Bruker Avance 500 spectrometer (equipped with z-
gradient
5
mm probe) at frequencies 500.13 MHz for 1H,
125.76 MHz for 13C{1H}, and 186.50 MHz for 119Sn{1H} at 295 K. VT-
NMR experiments were carried out using this spectrometer, too.
The rest of NMR measurements was performed on a Bruker Avance
II 400 spectrometer operating at 400.13 MHz for 1H, 100.62 MHz for
13C{1H}, 40.56 MHz for 15N{1H}, 376.50 MHz for 19F{1H}, and
149.17 MHz for 119Sn{1H} at 295 K. Solutions were obtained by
dissolving of approximately 40 mg (100 mg for 15N measurements)
4.2.1. Preparation of LC3NSn(n-Bu) (1)
The suspension of 4.2 g of LCNLi (29.7 mmol) in 20 ml of benzene
was added dropwise to the solution of 2.80 g (9.92 mmol) of n-

ꢁꢀ ꢀ
A. Ruzicka et al. / Journal of Organometallic Chemistry 732 (2013) 47e57
54
Table 1
Crystallographic data for 1, 2, 4, 5a and 6.
Compound
1
2
4
5a$0.5Et2O
6$6THF
Empirical formula
Crystal system
Space group
C
31H45N3Sn
C33H41N3Sn
Triclinic
P-1
C36H58N6OSn
Monoclinic
P21/c
12.7960(10)
22.2431(14)
18.1280(10)
90
133.425(5)
90
4
3747.3(5)
0.31 ꢃ 0.25 ꢃ 0.19
ꢀ16,16;ꢀ27,28;ꢀ20,23
1.80e27.50
34,561
C29H43BrN3O1.5Sn
Monoclinic
P21/c
9.1390(8)
24.163(2)
13.7750(12)
90
108.140(6)
90
4
2890.7(4)
0.51 ꢃ 0.24 ꢃ 0.15
ꢀ11,11;ꢀ28,31;ꢀ17,17
1.69e27.50
23,919
C51H98Br3N3O6Sn
Monoclinic
C2
35.1540(10)
14.4641(6)
9.5970(3)
90
105.349(3)
90
4
4705.7(3)
0.31 ꢃ 0.22 ꢃ 0.07
ꢀ43,43;ꢀ17,17;ꢀ11,11
4.25e26.37
20,009
Triclinic
P-1
ꢁ
a (A)
8.9920(2)
11.9701(8)
14.4119(7)
91.120(5)
96.735(3)
99.448(4)
2
1518.43(13)
0.54 ꢃ 0.30 ꢃ 0.22
ꢀ11,11;ꢀ15,15;ꢀ18,18
2.28e27.50
27,702
9.2710(5)
9.6890(8)
17.5859(13)
88.172(6)
87.961(6)
73.775(4)
2
1515.41(19)
0.29 ꢃ 0.23 ꢃ 0.12
ꢀ12,12;ꢀ12,12;ꢀ22,22
2.29e27.40
27,630
ꢁ
b (A)
ꢁ
c (A)
a
b
g
Z
(ꢂ)
(ꢂ)
(ꢂ)
3
ꢁ
V (A )
Crystal size (mm)
h;k;l range
q
range/ꢂ
Reflections measured
a
Independent (Rint
Observed [I > 2 (I)]
Parameters refined
)
6875
5980
316
6803
5775
334
8566
6572
397
6491
4169
314
8143
6589
251
s
ꢁꢀ3
/e A
Max/min
s
0.394/ꢀ0.472
0.447/ꢀ0.470
0.734/ꢀ0.436
0.543/ꢀ0.879
1.343/ꢀ1.344
GOFb
1.165
1.132
1.181
1.035
1.054
Rc/wRc
0.0280/0.0591
0.0330/0.0594
0.0410/0.0732
0.0499/0.0838
0.0626/0.1567
P
P
a
Rint
¼
jFo2 ꢀ Fo2;meanj= Fo2:
P
S ¼ ½ ðwðFo2 ꢀ Fc2Þ2Þ=ðNdiffr: ꢀ Nparam:Þꢄ1=2
:
b
c
P
P
P
P
1
2
Weighting scheme: w ¼ ½
s
ðFo2Þ þ ðw1PÞ2 þ w2Pꢄꢀ1; where P ¼ ½maxðFo2Þ þ 2Fc2ꢄ; RðFÞ ¼ jjFoj ꢀ jFcjj= jFoj; wRðF2Þ ¼ ½ ðwðFo2 ꢀ Fc2Þ2Þ= wðFo2Þ2ꢄ
:
BuSnCl3 in 30 ml of benzene during 10 min at w10 ꢂC. The reaction
mixture was warmed to the room temperature and 30 ml of chlo-
roform was added gradually. The solution was filtered in air and the
white precipitate washed by 20 ml of hexanes. Volatiles were
removed in high vacuo and the residue fractionally distilled up to
210ꢂC/20 Pa; 4.30 g of pure colourless oily 1 is obtained in 75% yield.
Mp 57e62 ꢂC. 1H NMR (CDCl3, 400.13 MHz, 295 K, ppm): 7.52 (d, 3H,
H(6), 3J ¼ 8.1 Hz, 3J(119Sn, 1H) ¼ 56.1 Hz); 7.31 (d, 3H, H(3),
3J ¼ 8.1 Hz); 7.26 (dd, 3H, H(4), 3J ¼ 8.1 Hz, 8.1 Hz); 7.15 (dd, 3H,
H(5), 3J ¼ 8.1 Hz, 8.1 Hz); 3.35 (s, 6H, NCH2); 1.86 (s, 18H, N(CH3)2);
1.51 (m, 2H, H(n-Bu)); 1.36 (m, 4H, H(n-Bu)); 0.82 (t, 3H, H(n-Bu),
3J(1H,1H) ¼ 7.2 Hz). 13C NMR (CDCl3,100.62 MHz, 295 K, ppm): 146.0
(C(2), 2J(119Sn,13C) ¼ 27.5 Hz); 143.2 (C(1), 1J(119Sn,13C) ¼ 484.9 Hz);
128.3 (C(5), 3J(119Sn,13C)
¼
43.4 Hz); 128.2 (C(4),
4J(119Sn,13C) ¼ 10.6 Hz); 127.7 (C(m-Ph), 3J(119Sn,13C) ¼ 52.7 Hz);
127.5 (C(p-Ph), 4J(119Sn,13C)
¼
11.7 Hz); 126.3 (C(3),
3J(119Sn,13C) ¼ 52.7 Hz); 66.1 (NCH2, 3J(119Sn,13C) ¼ 22.5 Hz); 44.8
(N(CH3)2). 119Sn NMR (CDCl3, 149.17 MHz, 295 K, ppm): ꢀ161.9. 15
N
NMR (CDCl3, 40.56 MHz, 295 K, ppm): ꢀ352.0. ESI-MS:
molecular weight (MW) ¼ 599; m/z 555 [MꢀCH3N(H)CH3þH]þ,
48%; m/z 522 [MꢀPh]þ, 70%; m/z 477 [MꢀPhꢀCH3N(H)CH3]þ, 30%;
m/z 465 [Mꢀ3*CH3N(H)CH3þH]þ, 30%; m/z 254 [LCNSn]þ, 11%.
Elemental analysis: found: C 66.3; H 7.0; N 7.2. Calcd (%) for
C33H41SnN3 (598.40): C 66.24; H 6.91; N 7.02.
4.2.3. Preparation of LN3CNSn(n-Bu) (3)
138.2
(C(6),
2J(119Sn,13C)
¼
35.6
Hz); 128.1
(C(5),
Using the same procedure as for 1 starting from 1.5 g of LNCNLi
(7.57 mmol) and 0.71 g (2.52 mmol) of n-BuSnCl3. Then the hexanes
were added, solution was filtered under argon atmosphere and
1.30 g (69%) of oily 3 was obtained after evaporation of all volatiles
from filtrate in high vacuo. 1H NMR (C6D6, 500.13 MHz, 295 K,
ppm): 7.52 (broad, 6H, H(3)); 7.31 (broad, 3H, H(4)); 3.42 (broad,
12H, NCH2); 1.94 (s, 36H, N(CH3)2); 1.31 (broad, 2H, H(n-Bu)); 1.18
(broad, 4H, H(n-Bu)); 0.86 (t, 3H, 3J ¼ 7.6 Hz, H(n-Bu)). 119Sn NMR
(C6D6, 186.50 MHz, 295 K, ppm): ꢀ135.0 (broad).
3J(119Sn,13C) ¼ 39.7 Hz); 127.9 (C(4), 4J(119Sn,13C) ¼ 9.8 Hz); 126.1
(C(3), 3J(119Sn,13C) ¼ 48.0 Hz); 66.2 (NCH2, 3J(119Sn,13C) ¼ 20.3 Hz);
45.1 (N(CH3)2); 29.0 (C(n-Bu), 2J(119Sn,13C) ¼ 20.1 Hz); 27.5 (C(n-Bu),
3J(119Sn,13C) ¼ 94.8 Hz); 13.7 (C(n-Bu), 1J(119Sn,13C) ¼ 480.1 Hz);
13.5 (C(n-Bu)). 119Sn NMR (CDCl3, 149.17 MHz, 295 K, ppm): ꢀ109.9.
15N NMR (CDCl3, 40.56 MHz, 295 K, ppm): ꢀ352.2. ESI-MS:
molecular weight (MW) ¼ 578; m/z 463 [MꢀBuꢀ(CH3)3N]þ,
100%; m/z 386 [MꢀLCNꢀ(CH3)3N]þ, 42%; m/z 344 [L2CNSnꢀCH3N(H)
CH3þH]þ, 43%, m/z 254 [LCNSn]þ, 20%, m/z 224 [L2CNSnꢀCH3N(H)
CH3ꢀSn þ H]þ, 15%, m/z 179 [L2CNSnꢀ2*CH3N(H)CH3ꢀSn þ H]þ, 6%.
Elemental analysis (%): found: C 64.6; H 7.6; N 7.4. Calcd (%) for
C31H45SnN3 (578.41): C 64.37; H 7.84; N 7.26.
4.2.4. Preparation of LN3CNSnOH (4)
When 1.10 g (1.47 mmol) of oily 3 was exposed on air in benzene
solution for an hour and afterwards all volatiles were removed in
high vacuo, 0.88 g (85%) of viscous oily residue is gained which
crystallized after one week. Mp 167e170 ꢂC. 1H NMR (CDCl3,
4.2.2. Preparation of LC3NSnPh (2)
Using the same procedure as for 1 starting from 4.7 g of LCNLi
(33.3 mmol) and 3.35 g (11.1 mmol) of PhSnCl3, 5.48 g (83%) of pure
2 was crystallized after addition of hexanes to the supernatant
solution. Mp 110e112 ꢂC. 1H NMR (CDCl3, 400.13 MHz, 295 K, ppm):
7.77 (d, 2H, H(o-Ph), 3J ¼ 7.2 Hz, 3J(119Sn,1H) ¼ 60.3 Hz); 7.67 (d, 3H,
H(6), 3J ¼ 8.2 Hz, 3J(119Sn,1H) ¼ 55.4 Hz); 7.41e7.21 (m, 12H, H(3),
H(4), H(5), H(m-Ph), H(p-Ph)); 3.43 (s, 6H, NCH2); 1.67 (s, 18H,
N(CH3)2). 13C NMR (CDCl3, 100.62 MHz, 295 K, ppm): 146.0 (C(2),
2J(119Sn,13C) ¼ 29.9 Hz); 144.0 (C(i-Ph), 1J(119Sn,13C) ¼ 594.8 Hz);
500 MHz, 295 K) d: 7.30 (broad, 9H, H(3), H(4)); 3.49 (broad, 12H,
NCH2); 1.96 (s, 36H, N(CH3)3); 119Sn NMR (CDCl3,149.17 MHz, 295 K)
d
: ꢀ158.1 (broad).1H NMR (THF-d8, 500 MHz, 295 K)
d: 7.45 (broad);
7.33 (broad); 4.0 (broad); 3.51 (broad); 2.04 (broad); 119Sn NMR
(THF-d8, 149.17 MHz, 295 K)
NMR (THF-d8, 500 MHz, 220 K) d: 13.5 (broad); 12.3 (broad); 7.41
d
: ꢀ145.6 and ꢀ163.5 ppm (broad). 1H
(broad); 7.36 (broad); 7.27 (broad); 5.02 (broad); 4.77 (broad); 4.11
(broad); 3.21 (broad); 3.03 (broad); 2.85 (broad); 2.55 (broad); 119Sn
NMR (THF-d8, 149.17 MHz, 220 K)
d
: ꢀ147.7 and ꢀ165.6 ppm ratio
142.7 (C(1), 1J(119Sn,13C)
¼
557.4 Hz); 138.2 (C(6),
2:3. ESI-MS: molecular weight (MW) ¼ 710; m/z 693 [LN3CNSn]þ,
100%; m/z 501 [L3NCNSnꢀLNCNH]þ, 4%; m/z 311 [LNCNSn]þ, 10%.
2J(119Sn,13C) ¼ 35.6 Hz); 136.7 (C(o-Ph), 2J(119Sn,13C) ¼ 37.1 Hz);

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A. Ruzicka et al. / Journal of Organometallic Chemistry 732 (2013) 47e57
55
4.2.5. Preparation and isolation of LC3NSnBr (5)
7.73 (m, LCN); 7.53e7.40 (br, LCN); 7.14 (d, LCN); 3.30 (br, NCH2); 4.22
(br, N(CH3)2); 2.57(br, N(CH3)2); 2.35(br, N(CH3)2); 1.90(br,
N(CH3)2). No signal was observed in the 119Sn NMR spectrum even
after recording for one day.
LC4NSn (4.65 g, 7.1 mmol) was reacted with anhydrous SnBr4
(1.05 g, 2.4 mmol) in boiling toluene/THF mixture of solvents (75/
25 mL) for two days. Afterwards the reaction mixture was filtered
and the filtrate was evaporated to dryness in vacuo. The residue was
treated with diethyl ether (2 ꢃ 10 mL per 1 g of the residue) in order
to separate the insoluble L2CNSnBr2. After evaporation of the clear
yellowish etheric filtrate to dryness a mixture containing only 5 and
LC4NSn is obtained. This mixture was consequently treated with
chloroform (1 mL of chloroform per 1 g of the mixture) and filtered.
Evaporation of the filtrate in vacuo gave crude oily 5 which was then
crystallized from dichloromethane/hexane mixture (ca 1:20 v/v) in
ca. 95% purity. The overall yield usually varies in between 25 and 35%
with respect to the starting amount of LC4NSn. 1H NMR (THF-d8,
500.13 MHz, 295 K, ppm): 8.02 (br, 3H, H(6), 3J(119Sn, 1H) z 65 Hz);
7.34 (br, 3H, LCN); 7.28 (br, 6H, LCN); 3.61 (br, 6H, NCH2); 1.85 (br,18H,
N(CH3)2). 119Sn NMR (THF-d8, 186.50 MHz, 295 K, ppm): ꢀ201.8
4.2.9. Attempts to prepare compounds of the LC3NSnX type
By the reaction of 1 (1.7 g, 2.93 mmol) in 15 ml of DMF and 0.24 g
(1.47 mmol) of bromine which was added dropwise via a syringe,
0.252 g (29% to 1) of pure 2-(Me2NCH2)C6H4Br$HBr (8) was crys-
tallized and isolated by filtration after an addition of hexanes to the
supernatant solution. Mp 177e182 ꢂC. 1H NMR (CDCl3, 500.13 MHz,
295 K, ppm): 11.69 (br, 1H, NH); 8.18 (d, 1H, H(6), 3J(1H(5),
1H(6))¼ 7.7 Hz);7.66 (d,1H, H(3), 3J(H(4), H(3)¼7.7Hz);7.49 (dd,1H,
H(4), 3J ¼ 8.1 Hz, 8.1 Hz); 7.34 (dd, 1H, H(5), 3J ¼ 7.8 Hz, 7.8 Hz); 4.49
(d, 2H, NCH2, 3J(1H(NH), 1H(NCH2)) ¼ 5.9 Hz); 2.86 (d, 6H, N(CH3)2,
3J(1H(NH), 1H(N(CH3)2) ¼ 5.0 Hz). ESI-MS: molecular weight
(MW) ¼ 293; m/z 214 [M ꢀ Br]þ, 100%; m/z 169 [MꢀBrꢀCH3N(H)
CH3]þ, 5%. Elemental analysis (%): found: C, 36.9; H, 4.7; N, 4.4. Calcd.
for C9H13Br2N (295.02): C, 36.64; H, 4.44; N, 4.75.
Nearly all volatiles (ca. 80%) from pale yellow filtrate were
removed in high vacuo, unreacted 1 was then removed by centri-
fugation, and the high vacuo was applied again in order to pump off
the rest of the volatiles to give 0.64 g of yellowish oil of LC2NSn(n-Bu)
Br (7) in 42% yield to 1. 1H NMR (CDCl3, 500.13 MHz, 295 K, ppm):
7.50 (d, 1H, H(6), 3J ¼ 7.6 Hz, 3J(119Sn, 1H) ¼ 56.8 Hz); 7.48 (d, 1H,
H(60), 3J ¼ 7.2 Hz, 3J(119Sn, 1H) ¼ 56.0 Hz); 7.30 (m, 1H, H(LCN));
7.22e7.11 (m, 5H, H(LCN)); 3.32 (s, 2H, NCH2); 3.20 (s, 2H, NCH02);
1.87 (s, 6H, N(CH3)2); 1.84 (s, 6H, NðCH3Þ02); 1.43 (m, 2H, H(n-Bu));
1.30 (m, 2H, H(n-Bu)); 0.85 (m, 5H, H(n-Bu)). 119Sn NMR (CDCl3,
186.50 MHz, 295 K, ppm): ꢀ125.3. ESI-MS: molecular weight
(MW) ¼ 524; m/z 525 [M þ H]þ, 22%; m/z 445 [M ꢀ Br]þ, 100%; m/z
388 [LC2NSn]þꢁ, 21%. Elemental analysis (%): found: C, 50.6; H, 6.6; N,
5.2. Calcd. for C22H33BrN2Sn (524.12): C, 50.42; H, 6.35; N, 5.34.
The reaction of 2 (1.00 g, 1.67 mmol, solution in 20 ml of ben-
zene) with I2 (0.42 g, 1.67 mmol) in 10 ml of benzene yielded after
2 h of reflux a mixture of LC2NSnI2 [16a], LCNPh2SnI [16b] and Ph4Sn
[24b] (as identified by the multinuclear NMR spectroscopy) which
was not further separated.
(broad). 119Sn
NMR
(THF-d8, 186.50
MHz,
263
K,
ppm): ꢀ122.9, ꢀ182.9, and ꢀ216.7. 119Sn NMR (THF-d8, 186.50 MHz,
243 K, ppm): ꢀ124.8, ꢀ183.6, and ꢀ220.3. 119Sn NMR (THF-d8,
186.50 MHz, 213 K, ppm): ꢀ125.7, ꢀ185.1, and ꢀ221.5. 1H NMR
(CDCl3, 500.13 MHz, 295 K, ppm): 7.80 (very broad, 3H, H(6), 3J(119Sn,
1H) could not be read); 7.40 (br, 9H, LCN); 3.78 (br, 6H, NCH2); 2.13 (br,
18H, N(CH3)2). 119Sn NMR (CDCl3, 186.50 MHz, 295 K, ppm): ꢀ123.8
(broad). 119Sn NMR (CDCl3, 186.50 MHz, 243 K, ppm): ꢀ127.0. 119Sn
NMR (CDCl3, 186.50 MHz, 233 K, ppm): ꢀ127.5. Elemental analysis
was not carried out due to the limited purity of the product.
4.2.6. Crystallization of [LC3NSn(H2O)]þBrꢀ (5a)
5 (95% purity) was dissolved in wet THF and was left to crys-
tallize in the air. Single crystals of pure 5a grew on the walls of the
glass tube within several days. Mp 65e67 ꢂC. 1H NMR (THF-d8,
400.13 MHz, 295 K, ppm): 8.06 (br, 3H, H(6), 3J(119Sn, 1H) z 63 Hz);
7.37 (br, 3H, LCN); 7.32 (br, 6H, LCN); 3.65 (br, 6H, NCH2); 1.90 (br,
18H, N(CH3)2); signal of solvating water molecule was not observed.
119Sn NMR (THF-d8, 149.17 MHz, 295 K, ppm): ꢀ202.0 (broad). 1H
NMR (CDCl3, 400.13 MHz, 295 K, ppm): 7.76 (very broad, 3H, H(6),
3J(119Sn, 1H) could not be read); 7.49 (br, 3H, LCN); 7.41 (m, 6H, LCN);
5.67 (very broad, solvating H20); 3.83 (br, 6H, NCH2); 2.23 (br, 18H,
N(CH3)2). 119Sn NMR (CDCl3, 149.17 MHz, 295 K, ppm): ꢀ185.0
(broad). Elemental analysis (%): found: C, 52.0; H, 6.6; N, 6.3. Calcd.
for C27H38BrN3OSn (619.22): C, 52.37; H, 6.19; N, 6.79.
On the other hand, the reaction of 2 (0.50 g, 0.83 mmol) with
aqueous HI (57%, 120
system (water/benzene) afforded
m
L, d ¼ 1.70 g cmꢀ3, 0.91 mmol) in a biphase
a mixture of L
CNH$HI and
LC2NSnPhI$HI (9). 9 was isolated by crystallization from the organic
phase after separation of both phases. Very complex 1H NMR
spectrum was obtained when recorded in CDCl3 and therefore the
detailed assignment of signals was not carried out but the presence
of the protonated ligand is evident (e.g. the presence of the
CH2N(H)Me2 fragment). Due to the limited solubility of 9 no 119Sn
NMR spectra were recorded. Mp 221 ꢂC (dec.). ESI-MS: molecular
weight (MW) ¼ 720; m/z 515 [LC2NSnI]þ, 25%; m/z 465 [L2CNSnPh]þ,
100%; m/z 134 [LCN]þ, 18%; m/z 91 [C6H5CH2]þ, 12%. Elemental
analysis (%): found: C, 40.3; H, 4.5; N, 3.7. Calcd. for C22H33BrN2Sn
(524.12): C, 40.09; H, 4.21; N, 3.90.
4.2.7. Preparation of LC3NSnF (5b)
5 (95%, 240 mg, 0.38 mmol) was reacted with LCN(n-Bu)2SnF
(146 mg, 0.38 mmol) in THF for two days. Afterwards the reaction
mixture was evaporated to dryness and carefully washed with cold
pentane (2ꢃ3 mL) in order to remove soluble LCN(n-Bu)2SnBr.
Nearly pure 5a was then isolated as a yellowish oil after evaporation
of volatiles in vacuo. Yield 158 mg (77%). 1H NMR (THF-d8,
400.13 MHz, 295 K, ppm): 8.02 (d, 3H, H(6), 3J(1H(5),
1H(6)) ¼ 9.0 Hz, 3J(119Sn, 1H) ¼ 65.7 Hz); 7.35 (m, 3H, LCN); 7.30 (m,
6H, LCN); 3.62 (s, 6H, NCH2); 1.96 (s, 18H, N(CH3)2). 19F NMR (THF-d8,
376.50 MHz, 295 K, ppm): ꢀ196.9 (1J(119Sn, 19F) ¼ 2236 Hz). 119Sn
NMR (THF-d8, 149.17 MHz, 295 K, ppm): ꢀ204.9 (broad d, 1J(19F,
Similar reaction of 2 (0.207 g, 0.35 mmol) with aqueous HF (38%,
ca. 20 mg, w0.40 mmol) in water/benzene biphasic system
gave mixture of presumably LC2NSnPhF [16c] and free ligand LCNH as
the by-product which was confirmed by multinucelar NMR
spectroscopy.
119Sn)
¼
2251 Hz). 119Sn NMR (CDCl3, 149.17 MHz, 295 K,
ppm): ꢀ207.8 (broad d, 1J(19F, 119Sn) ¼ 2162 Hz). Elemental analysis
was not carried out due to the limited purity of the sample.
LC4NSn (0.116 g, 0.18 mmol) and HgCl2 (0.048 g, 0.18 mmol) were
dissolved in THF and stirred overnight in the air. Afterwards the
suspension thus formed was filtered and the filtrate was evapo-
rated to dryness. The multinuclear NMR spectroscopy proved only
the presence of LC2NSnCl2 [16a] and LC2NHg [1c] in the sample ob-
tained from the evaporated filtrate. According to 119Sn NMR spec-
troscopy no desired 5c was formed and thus the mixture of
compounds was not separated.
4.2.8. Isolation of [LC2NLCN(H)SnBr]þ[Br.HBr]ꢀ (6)
6 was isolated in ca. 20% yield when complete workup of 5 was
done in the air. Mp >270 ꢂC. Due to the limited solubility of 6 in
inert deuterated solvents and therefore of poor quality of recorded
1H NMR spectrum the complete assignment of all signals was not
carried out. 1H NMR (CDCl3, 500.13 MHz, 295 K, ppm): 8.38 (d, LCN);

ꢁꢀ ꢀ
A. Ruzicka et al. / Journal of Organometallic Chemistry 732 (2013) 47e57
56
Similarly, the reaction of LC4NSn (0.236 mg, 0.36 mmol) and HgCl2
G. Huttner, Inorg. Chim. Acta 324 (2001) 266e272;
(b) A. Chandrasekaran, N.V. Timosheva, R.O. Day, R.R. Holmes, Inorg. Chem. 41
(2002) 5235e5240;
(c) H. Lang, M. Leschke, M. Melter, B. Walfort, K. Kohler, S.E. Schulz, T. Gessner,
Z. Anorg. Allg. Chem. 629 (2003) 2371e2380;
(d) M. Leschke, M. Melter, B. Walfort, A. Driess, G. Huttner, H. Lang, Z. Anorg.
Allg. Chem. 630 (2004) 2022e2030;
(e) V.M. Demyanovich, I.N. Shishkina, K.A. Potekhin, E.V. Balashova,
Y.T. Struchkov, N.S. Zefirov, Dokl. Akad. Nauk SSSR 360 (1998) 645e648;
(f) M. Leschke, G. Rheinwald, H. Lang, Z. Anorg. Allg. Chem. 628 (2002) 2470e
2477;
(g) M.A. Alonso, J.A. Casares, P. Espinet, K. Soulantica, A.G. Orpen,
H. Phetmung, Inorg. Chem. 42 (2003) 3856e3864;
(h) Y. Shen, H. Pritzkow, B. Walfort, T. Rueffer, H. Lang, Acta Crystallogr., Sect. E
60 (2004) M91eM93;
(0.048 g, 0.18 mmol) in a 2:1 ratio was carried out. In this particular
case the formation of desired 5c was observed together with
LC2NSnCl2 and L2CNHg in the reaction mixture. The starting LC4NSn was
identified as well (only minor assay). Although the target compound
wasnot separatedfromthereaction mixturetheinterpretation of the
1H NMR spectrum allowed assignmentof all signals corresponding to
5c. 1H NMR (CDCl3, 400.13 MHz, 295 K, ppm): 7.96 (br, 3H, H(6),
3J(119Sn,1H) could not be read); 7.51e7.15 (m, 9H, H(LCN); 3.75 (s, 6H,
NCH2); 2.00 (s, 18H, N(CH3)2). 119Sn NMR (CDCl3, 149.17 MHz, 295 K,
ppm): ꢀ190.2 (broad). According to 1H and 119Sn NMR spectroscopy
the mutual ratio of 5c to LC2NSnCl2 is approximately 1:1.
(i) M. Leschke, H. Lang, M. Melter, G. Rheinwald, C. Weber, H.A. Mayer,
H. Pritzkow, L. Zsolnai, A. Driess, G. Huttner, Z. Anorg. Allg. Chem. 628 (2002)
349e356;
Acknowledgements
(j) C. Chuit, R.J.P. Corriu, P. Monforte, C. Reye, J.-P. Declercq, A. Dubourg,
Angew. Chem., Int. Ed. 32 (1993) 1430e1432;
(k) H. Lang, Y. Shen, T. Rueffer, B. Walfort, Inorg. Chim. Acta 361 (2008) 95e102;
(l) H. Lang, M. Leschke, G. Rheinwald, M. Melter, Inorg. Chem. Commun. 1 (1998)
254e256;
The authors would like to thank the Grant Agency of the Czech
Republic (grant no. P207/10/0215) for the financial support of this
work.
(m) M. Leschke, M. Melter, C. Weber, G. Rheinwald, H. Lang, A. Driess, G. Huttner,
Z. Anorg. Allg. Chem. 627 (2001) 1199e1203;
Appendix A. Supplementary data
(n) A. Rotar, A. Covaci, A. Pop, A. Silvestru, Rev. Roum. Chim. 55 (2010) 823e829.
[8] F.A. Cotton, G.N. Mott, Organometallics 1 (1982) 38e43.
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[12] (a) H. Kooijman, A.L. Spek, G. van Koten, Private Communication to CCDC,
2007;
CCDC 918470e918476 contain the supplementary crystallo-
graphic data for this paper. These data can be obtained free of
charge from The Cambridge Crystallographic Data Centre via www.
cccdc.cam.ac.uk/data-request/cif.
Supplementary material associated with this article can be
found, in the online version, at http://dx.doi.org/10.1016/j.
jorganchem.2013.02.018.
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