The differences in solid state structures of C,N-chelated nbutyltin(IV) fluorides

Article abstract of DOI:10.1016/j.jorganchem.2008.06.010

The solid state structures of products of fluorination of L^CNnBuSnCl₂ (where L^CN is 2-[(CH₃)₂NCH₂]C₆H₄ -) by different methods are reported. The reaction of 3 equiv. o

Full text of DOI:10.1016/j.jorganchem.2008.06.010

Journal of Organometallic Chemistry 693 (2008) 2937–2941
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The differences in solid state structures of C,N-chelated nbutyltin(IV) fluorides
a
a
a
b
a,
ˇ
*
ˇ
ˇ
ˇ
ˇ ˇ
Petr Švec , Zdenka Padelková , Zdenek Cernošek , Frank De Proft , Aleš Ru˚ zicka
a
ˇ
Department of General and Inorganic Chemistry, Faculty of Chemical Technology, University of Pardubice, nám. Cs. legií 565, CZ-532 10, Pardubice, Czech Republic
b Eenheid Algemene Chemie (ALGC), Department of Chemistry (DSCH), Faculty of Sciences, Vrije Universiteit Brussel (VUB), Pleinlaan 2, B-1050 Brussels, Belgium
a r t i c l e i n f o
a b s t r a c t
The solid state structures of products of fluorination of LCNnBuSnCl2 (where LCN is 2-[(CH3)2NCH2]C6H4–)
by different methods are reported. The reaction of 3 equiv. of [NH4]+[LCNnBuSnF3]ꢀ and Pr(OTf)3 led to
Article history:
Received 6 March 2008
Received in revised form 26 May 2008
Accepted 5 June 2008
dimeric arrangement [LCNnBuSnF(
l
-F)2SnLCNnBuF] ꢁ 2HOTf. Two different polymorphs of polymeric
[LCNnBuSnF2]n have been obtained by crystallization. Prepared compounds were studied by X-ray crystal-
lographic methods, DSC and theoretical calculations at the B3LYP/LANL2DZ level.
Ó 2008 Published by Elsevier B.V.
Available online 11 June 2008
Keywords:
Organotin(IV) fluorides
CN-ligand
Structure
1. Introduction
tures in solution and in the solid state. Compound 2 is monomeric
in solution of non-coordinating solvent such as CDCl3 with fivefold
The tri- and diorganotin(IV) fluorides were described as insolu-
ble polymeric species with changeable composition and properties
[1,2]. Two- or three-dimensional structures connected via F–Sn–F
bridges have been determined or suggested for majority of these
compounds. This aggregation can be prevented in the case of trior-
ganotin fluorides either by use of bulky substituents and/or donor
ligands especially chelating ones in both cases [3–9].
coordinated tin i.e., two carbon and one of chlorine atoms in equa-
torial positions and both nitrogen and the remaining chlorine atom
in axial ones. The six-coordinated tin has been found in the coordi-
nating solvents such as DMSO-d6. The tendency of tin atom to in-
crease the coordination number is clearly seen in the solid state
as well. The solid state structure of 2 (Fig. 1) can be described as
a polymer with Cl–Sn–Cl zig-zag chain having two different
structural motifs of a mononuclear unit. The main difference is
the shape of the n-butyl substituent and the Sn–Cl bond lengths.
The four different Cl atoms are present; Sn1–Cl(bridging-a)
2.4686(10) Å and Sn2–Cl(bridging) 3.4440(11) Å), Sn1–Cl(termi-
nal-a) 2.3877(11) Å, Sn2–Cl(bridging-b) 2.4620(10) Å and Sn10–
Cl3 3.6256(11) Å), iv) Sn2–Cl(terminal-b) 2.3926(10) Å.
Two different methods were used for replacing chlorine by fluo-
rine atom(s) in 2. The first method is based on the known fluorina-
tion ability of LCNnBu2SnF and the second one is reaction with dried
NH4F (excess) in dichloromethane under an argon atmosphere
yielding the same species or ionic stannates ([NH4]+[LCNnBuS-
nF3]ꢀ). In chloroform, a polymeric structure is probably retained
which is also supported by the 19F NMR spectra, where two very
broad signals were found at room temperature and no signal was
observed at 220 K. In weakly coordinating solvents such as nitro-
benzene or acetonitrile, the tetrameric structure was deduced from
ESI-MS measurements. The structure in DMSO is monomeric with
dynamically exchanging fluorine atoms (from axial to equatorial
position of trigonal bipyramid).
We have reported previously on monomeric triorganotin(IV)
fluorides of general formula LCNR2SnF, where LCN is {2-[(CH3)2-
NCH2]C6H4}ꢀ and R is alkyl (Me, nBu, tBu) or aryl (Ph) groups of dif-
ferent steric bulk and electronic properties [10] which can be used
for metathetical halide for fluoride exchange reactions for inor-
ganic salts or complexes, chlorosilanes, chlorophosphines and dif-
ferent kinds of organometallic compounds [11]. We also reported
the first monomeric diorganotin(IV) difluoride wearing the same li-
gands (LC2NSnF2 (1) with sixfold coordinated tin centre and C,C-tran-
soid geometry – Sn1–F1 1.981(1), Sn1–F2 1.991(1), Sn1–N1 2.496(2),
Sn1–N2 2.597(1)) [12,13] having no interaction of tin atom with an-
other atom from adjacent molecule. When only one ligand is used
(LCNRSnF2; R = Ph [12], nBu [11a], F [14]) the di- or monoorgano-
tin(IV) fluorides are presumably tri- or tetranuclear species with
rather low solubility in common organic solvents and we used them
recently as a part of selective and sensitive carriers for fluoride ion
recognition [15].
The investigation of LCNnBuSnCl2 (2) [16,17] and products of its
fluorination [11a] showed interesting differences between struc-
Although a large number of attempts have been made, no solid
state structure of these complexes was determined up to now. In
this paper, we would like to communicate different solid state
* Corresponding author. Tel.: +420 466037151; fax: +420 466037068.
ˇ ˇ
E-mail address: ales.ruzicka@upce.cz (A. Ru˚ zicka).
0022-328X/$ - see front matter Ó 2008 Published by Elsevier B.V.
doi:10.1016/j.jorganchem.2008.06.010

2938
P. Švec et al. / Journal of Organometallic Chemistry 693 (2008) 2937–2941
Table 1
Selected crystallographic data for 3a–c
Compound
3a
3b
3c
Empirical formula
Crystal system
Space group
a (Å)
b (Å)
c (Å)
C
28H48F10N2O6S2Sn2
C13H21F2NSn
Triclinic
P1
8.4120(5)
8.563(2)
10.0910(16)
108.690(15)
90.636(9)
92.476(11)
2
C13H21F2NSn
Triclinic
P1
4.276(2)
8.4020(12)
9.453(6)
87.65(3)
83.98(5)
87.31(3)
1
Triclinic
P1
ꢀ
ꢀ
ꢀ
10.0890(11)
10.7420(8)
11.4180(12)
108.455(7)
95.985(7)
117.955(6)
1
a
(°)
b (°)
c
(°)
Z
V (Å3)
988.57(17)
1.680
687.7(2)
1.748
337.2(3)
1.734
Dc (g cmꢀ3
)
Crystal size (mm)
Crystal shape
0.293 ꢂ 0.226 ꢂ 0.096
0.193 ꢂ 0.140 ꢂ 0.084
0.119 ꢂ 0.098 ꢂ 0.043
Block
Needle
Block
l
(mmꢀ1
)
1.455
1.866
1.898
F(000)
500
362
178
h, k, l range
h Range (°)
Temperature
ꢀ13, 13, ꢀ12, 13, ꢀ14, 14
2.36–27.50
150(1)
ꢀ10, 10, ꢀ11, 11, ꢀ13, 13
2.13–27.49
200(1)
ꢀ5, 5, ꢀ10, 10, ꢀ12, 12
3.20–27.49
100(1)
Reflections measured
18700
8450 (0.061)
7587
12630
5667 (0.065)
4243
5844
2840 (0.068)
2835
a
Independent (Rint
Observed [I>2
Parameters refined
)
r(I)]
441
313
149
Max/min
s
(e Åꢀ3
)
1.280/ꢀ1.095
0.909/ꢀ1.270
2.511/ꢀ1.254
Goodness-of-fitb
1.058
1.149
1.075
Rc/wRc
0.0431/0.1059
0.0380/0.0955
0.0513/0.1323
P
P
a
Rint
=
|F2o ꢀ F2o,mean|/ F2o.
P
b
c
½
S = [ (w(F2o ꢀ F2c)2)/(Ndiffrs ꢀ Nparams)]
.
P
P
P
P
½
Weighting scheme: w = [
r
2(F2o) + (w1P)2 + w2P]ꢀ1, where P = [max(Fo2) + 2Fc2], R(F) = ||Fo| ꢀ |Fc||/ |Fo|, wR(F2) = [ (w(Fo2 ꢀ Fc2)2)/( w(F2o)2)]
.
Fig. 1. Supramolecular architecture of 2.
structures determined by X-ray techniques supported by theory
and DSC techniques.
2. Results and discussion
The dimeric structure 3a ([LCNnBuSnF(
l
-F)2SnLCNnBuF] ꢁ 2HOTf
(Fig. 2)) has been obtained by crystallization of reaction mixture
of 3 equiv. of [NH4]+[LCNnBuSnF3]ꢀ and Pr(OTf)3. This reaction has
been carried out in order to prepare species with Sn–F–lanthanide
structural motif analogous to complexes of Demsar’s praseodym-
ium and neodymium fluorotitanates [18], but 3a and white insol-
uble powder, probably a praseodimium fluoride, were the only
isolable products. When 3a was dissolved in non-coordinating sol-
vent, the same spectra were obtained as for previously reported
products of fluorination of 2 [11a]. This can be explained by the
hypothesis that 3a exists only in the solid state. The basic building
block of the structure of 3a (Fig. 2) consists of two tin atoms
bridged by nearly symmetrical bridge of two fluorine atoms
(Sn2–F2 2.146(12), Sn2–F3 2.128(8), F2–Sn1 F3 73.3(3), F2–Sn2–
F3 72.1(3)). Each tin atom is six-coordinated with two carbon
Fig. 2. ORTEP plot of molecule 3a showing 50% probability displacement ellipsoid
and the atom numbering scheme. Hydrogen atoms and trifluoromethane sulphonic
0
acid moieties were omitted for clarity. The selected bonding lengths (ÅA) and angles
(deg): Sn1–C10 2.090(14), Sn1–F2 2.107(12), Sn1–F3 2.106(8), Sn1–C1 2.143(17),
Sn1–F1 2.352(12), Sn1–N1 2.434(14), Sn2–C14 2.089(15), Sn2–F2 2.146(12), Sn2–
F3 2.128(8), Sn2–C23 2.147(12), Sn2–F4 2.348(6), Sn2–N2 2.465(15), F2–Sn1–F3
73.3(3), C10–Sn1–C1 161.7(5), F2–Sn1–F1 161.9(4), F3–Sn1–F1 88.7(4), F3–Sn1–N1
160.4(4), F2–Sn2–F3 72.1(3), F2–Sn2–F4 89.2(3), F3–Sn2–F4 161.3(2), F2–Sn2–N2
162.3(5).
atoms of ligand and butyl moieties in mutually trans positions
(C10–Sn1–C1 161.7(5)), two bridging fluorine atoms, one coordi-
nated nitrogen atom and one terminal fluorine atom with extre-
mely long Sn–F distance(s) (Sn1–F1 2.352(12) and Sn2–F4

P. Švec et al. / Journal of Organometallic Chemistry 693 (2008) 2937–2941
2939
2.348(6)). Each nitrogen atom is located in trans position (Sn1–N1
2.434(14) and Sn2–N2 2.465(15)) to one of bridging fluorine atoms
and the second bridging fluorine atom is trans to the terminal one
(F2–Sn1–F1 161.9(4), F3–Sn1–N1 160.4(4), F3–Sn2–F4 161.3(2),
F2–Sn2–N2 162.3(5)). The hypothesis that 3a exists only in the so-
lid state is supported by the stabilization of 3a into the linear mo-
tifs connected by hydrogen bridging via trifluoromethane
sulphonic acid moieties (Fig. 3).
When the product of fluorination of 2 has been crystallized
from methanol solution crystals of 3b (Figs. 4 and 5) were ob-
tained. The almost linear polymeric structure where the six-coor-
dinated tin atoms are connected by one fluorine bridge is very
different of previously found structure of 2, where a zig-zag chain
is taking place, dimeric 3a or monomeric 1. This fact is demon-
strated mainly in differences in Sn-F bond lengths and Sn–F–Sn an-
gles (Fig. 5). Both distances of the terminal and bridging fluorine to
tin atoms are comparable to the values found in the literature and
for example for 1 [12]. The non-equal distances for bridging Sn-F
bonds were found. Very strong intramolecular connection Sn–N
comparable to monomeric triorganotin fluorides [10] or monoorg-
anotin halides [14] was found for all compounds.
The different polymorph 3c (Figs. 4 and 5) of the same com-
pound has been obtained from methanolic solution of fluorination
product of 2 and ammonium fluoride in the first crystallization
crop. The second crop gave the mixture of 3c (needles) and 3b
(blocks) in approx. 4:1 ratio. The structure of 3c is similar to 3b
from the point of view of found main interatomic distances and an-
gles (Fig. 5) but in the closer investigation of polymeric chain there
is the major difference in mutual orientation of butyl and ligand
moieties through this chain. While in 3c is the same orientation
of butyl moieties in 3b is the opposite one (ca. 180° rotated per-
pendicularly to polymer axis). This phenomenon can be inter-
preted either by the polymer chemistry or inorganic chemistry
nomenclature as isotactic (3c) and syndiotactic (3b) polymers or
infinite chain of optical (in octahedral coordination vicinity of tin
atoms) A,C (alternating) or A,A isomers.
When the structure of 3c was determined at higher tempera-
tures a phenomenon of slight change of polymer from ‘rod-like’
to ‘zig-zag’ one is observed (increase of residual electronic maxima
in the direction of proposed zig-zag chain, for a similar change
from polymeric to monomeric structure with temperature change
see Ref. [19]). On the other hand, isomer 3b retained unchanged in
the range of 100–250 K. This is probably caused by a repulsion of
p-electrons of Ph rings in 3c.
The difference between these isomers (3b and 3c) is also re-
flected in different patterns of DSC curves (Fig. 6). Starting at
196 °C an exothermic process with enthalpy change ꢀ18 J/g can
be seen for both isomers. Using optical microscopy we have found
gradual crystal growth in the temperature range 196–239 °C,
immediately before crystall melt accompanied at the same time
by decomposition. Starting temperatures and total enthalpy
changes of melting and decomposition were found: 239 °C and
ꢀ278 J/g for isomer 3b, and 244 °C and ꢀ780 J/g for isomer 3c,
see Fig. 6. As one can see on Fig. 6, the isomer 3c contains observa-
ble amout of isomer 3b manifesting itself by small exothermic
peak at 257 °C. More complicated peak shape of melting and
decomposition of isomer 3c is not fully clear up to now.
The pathway going from monomeric compound 1, through di-
meric 3a and a monomer-like 2 to polymeric 3b and 3c in both
rod-like and zig-zag version have been examined also at the theory
level. The geometries of all compounds were optimized at the B3LYP
[20]/LANL2DZ [21,22] level of theory starting from the different crys-
tal structures obtained. It has previously been shown that this level
of theory is capable of qualitatively describing intramolecular
interactions in organotin compounds [23].
Tables S1–S5 (see Supplementary material) provide a compari-
son of a series of different relevant geometrical parameters for the
different compound considered in this work. In the case of LC2NSnF2
(1) (Table S1) it can be seen that the agreement of the computed
distances and bond angles with the values from the crystal struc-
tures is very good in the majority of cases; the largest difference
occurs in the case of the F–Sn–F angle, where the computed angle
is somewhat larger than the experimental one. The similar situa-
tion appeared in the case of staring compound 2, where only the
small differences between calculated and measured distances
and angles are caused by weak van der Waals interactions in the
solid state (Table S2). When going to the dimer 3a (Table S3), F–
Sn–F angle decreases, the decrease being larger in the case of the
computed structures. In the dimer, the largest differences between
the computed and experimental values are related to both the F–Sn
bond distances and the F–Sn–F bond angles. The Sn–F distances for
the atoms involved in the bridge are much more asymmetric for
the computed structures than in the case of the crystal structures,
where these values are very close to one another. On of the two cal-
culated distances however is always very close to the experimental
distance. As can be seen, the change in the Sn–F distances for the
fluorine atoms not involved in the bridge when going from the
monomeric LC2NSnF2 to the dimer is much less pronounced for the
calculated values than for the experimental ones.
Fig. 3. View of H-bonding in 3a with O-F distances being 2.749(3), 2.774(1), and
2.774(3) ÅA.
0
Next, we consider the optimized geometry for the syndio (3b)
and isotactic form 3c (Tables 4S and 5S). As can be seen, most com-
puted bond distances and angles are in reasonable agreement with
the experimental values. The largest deviation occurs for the dis-
tance between Sn1 and F2. For 3c, the Sn1–F2–Sn1a angle amounts
to the value of 170.98° in the crystal structure and decreases
153.50°, indicating a more zig-zag character of the gas phase struc-
ture as compared to the solid phase structure. This is accompanied
by an increased degree of atacticity in the gas phase structure.
Fig. 4. ORTEP view of one of building blocks of 3b (n = 3) or 3c (n = 2a) showing 50%
probability displacement ellipsoid and the atom numbering scheme. Hydrogen
atoms were omitted for clarity.

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P. Švec et al. / Journal of Organometallic Chemistry 693 (2008) 2937–2941
0
Fig. 5. Comparative view of 3b and 3c. Selected bond lengths (ÅA) and angles (deg) for 3b: Sn1–F1 1.972(9), Sn1–C1 2.133(15), Sn1–F2 2.13(3), Sn1–C10 2.162(15), Sn1–F4
2.17(3), Sn1–N1 2.574(14), Sn2–C23 2.026(18), Sn2–F3 2.041(10), Sn2–C14 2.081(17), Sn2–F4 2.13(3), Sn2–F2 2.13(3), Sn2–N2 2.427(12), F1–Sn1–F2 87.7(10), C1–Sn1–C10
160.2(5), F1–Sn1–F4 89.2(9), F2–Sn1–F4 176.8(18), F1–Sn1–N1 172.0(5), C23–Sn2–C14 165.9(7), F3–Sn2–F4 93.0(9), F3–Sn2–F2 88.5(10), C14–Sn2–F2 91.5(11), F4–Sn2–F2
178.3(18), F3–Sn2–N2 169.2(4), Sn2–F2–Sn1 177.9(19), Sn2–F4–Sn1 177.5(18). For 3c: Sn1–C1 2.111(12), Sn1–F1 1.966(8), Sn1–F2 2.168(8), Sn1–F2a 2.121(8), Sn1–C10
2.131(12), Sn1–N1 2.470(12), F1–Sn1–F2 84.8(3), F1–Sn1–F2a 86.7(3), F2–Sn1–F2a 171.0(3), C1–Sn1–C10 162.0(4), F1–Sn1–N1 171.4(4), Sn1–F2–Sn1a 171.0(3).
3.2. NMR spectroscopy
3c
3c
3b
The NMR spectra were recorded as solutions in methanol-d4, or
-18 J/g
-780 J/g
0
-10
-20
CDCl3 on a Bruker Avance 500 spectrometer (equipped with Z-gra-
dient 5 mm probe) at 300, 250 or 220 K 1H (500.13 MHz), 119Sn{1H}
(186.50 MHz) and 19F{1H} (470.53 MHz). The solutions were ob-
tained by dissolving of 5–40 mg of each compound in 0.5 ml of
deuterated solvents.
3b
-278 J/g
3.3. X-ray crystallography
Data for colorless crystals (Table 1) were collected on a Nonius
KappaCCD diffractometer using Mo K radiation (k = 0.71073 Å),
a
and graphite monochromator. The structures were solved by direct
methods (SIR92 [24]). All reflections were used in the structure
refinement based on F2 by full-matrix least-squares technique
175
200
225
250
275
300
(
SHELXL97 [25]). Heavy atoms were refined anisotropically except
T [oC]
of bridging fluorine atoms. The highest residual maximum in 3c
is described above as the second position of bridging fluorine
(zig-zag chain, and is very low at 100 K). Hydrogen atoms were
mostly localized on a difference Fourier map, however to ensure
uniformity of treatment of crystal, all hydrogen were recalculated
into idealized positions (riding model) and assigned temperature
factors Hiso(H) = 1.2 Ueq(pivot atom) or of 1.5Ueq for the methyl
moiety. Absorption corrections were carried on, using Gaussian
integration from crystal shape [26].
Fig. 6. Observed DSC parameters for 3b and 3c.
3. Experimental
LCNnBuSnCl2 (2) was prepared and fluorinated as published
elsewhere [16,17,11a]. All solvents and starting compounds were
obtained from commercial sources (Aldrich). THF was dried by dis-
tillation from sodium–potassium alloy, dichloromethane from cal-
cium hydride and degassed.
3.4. DSC
3.1. [LCNnBuSnF(
l
-F)2SnLCNnBuF] ꢁ 2HOTf (3a)
The DSC measurements were performed on differential scan-
ning calorimeter Pyris 1 (Perkin–Elmer). Calorimeter was carefully
calibrated and nitrogen gas of precisely regulated constant flow
20 ml/min was used as a purging gas. Crystalline samples (weight
around 4 mg) were encapsulated into aluminium pans and DSC
scans were done using heating rate 10 K/min.
The Pr(OTf)3 (0.033 g, 0.056 mmol) was dissolved in 15 ml of
THF and 3 equiv. of [NH4]+[LCNnBuSnF3]ꢀ (0.065 g, 0.169 mmol)
were added. The reaction mixture was stirred overnight. After-
wards, the reaction mixture was reduced to approx. half of its ori-
ginal volume, the soluble part was filtered off and the volatiles
were vacuo removed. The product was dissolved in dichlorometh-
ane. Colourless single crystals were obtained from this solution at
ꢀ30 °C. Yield 0.029 g (52%). M.p. 202–203 °C. Elemental Anal. Calc.
for C28H44F10N2O6S2Sn2 (996.17): C, 33.76; H, 4.45; N, 2.81; S, 6.44.
Found: C, 33.65; H, 4.58; N, 2.90; S, 6.35%.
3.5. Computations
All geometries were optimised at the B3LYP [20]/LANL2DZ [21,22]
level starting from the experimental crystal structures of the com-
pounds using the GAUSSIAN 03 program [27].

P. Švec et al. / Journal of Organometallic Chemistry 693 (2008) 2937–2941
2941
ˇ
ˇ
˚ ˇ ˇ
ˇ
[11c] P. Novák, I. Císarová, L. Kolárová, A. Ruzicka, J. Holecek, J. Organomet.
Chem. 692 (2007) 4287–4296.
Acknowledgements
ˇ
˚ ˇ ˇ
ˇ
[12] P. Novák, J. Brus, I. Císarová, A. Ruzicka, J. Holecek, J. Fluorine Chem. 126 (2005)
The financial support of the Science Foundation of the Czech
Republic (Grant No. 203/07/0468) and the Ministry of Education
of the Czech Republic (Project VZ0021627501) is acknowledged.
F.D.P. wishes to acknowledge the Fund for Scientific Research Flan-
ders (Belgium) and the Free University of Brussels (VUB) for con-
tinuous support to his research group.
1531–1538.
ˇ
ˇ
˚ ˇ ˇ
ˇ
[13] P. Novák, Z. Padelkova, L. Kolárová, J. Brus, A. Ruzicka, J. Holecek, Appl.
Organomet. Chem. 19 (2005) 1101–1108.
[14] P. Novák, Z. Padelková, I. Císarová, L. Kolárová, A. Ruzicka, J. Holecek, Appl.
Organomet. Chem. 20 (2006) 226–232.
[15] S. Chandra, A. Ru˚ zicka, P. Švec, H. Lang, Anal. Chim. Acta 577 (2006) 91–97.
[16] A. Ru˚ zicka, V. Pejchal, J. Holecek, A. Lycka, K. Jacob, Collect. Czech. Chem.
ˇ
ˇ
ˇ
˚ ˇ ˇ
ˇ
ˇ ˇ
ˇ ˇ
ˇ
ˇ
Commun. 63 (1998) 977–989.
ˇ
ˇ
˚ ˇ ˇ
ˇ
[17] P. Švec, Z. Padelková, I. Císarová, A. Ruzicka, J. Holecek, Main Group Metal
Chem. (2007) in press.
Appendix A. Supplementary material
ˇ
[18] [18a] F. Perdih, A. Demšar, A. Pevec, S. Petricek, I. Leban, G. Giester, J. Sieler,
H.W. Roesky, Polyhedron 20 (2001) 1967–1971;
CCDC 673998, 673999 and 674000 contain the supplementary
crystallographic data for 3a, 3b and 3c. These data can be obtained
free of charge from The Cambridge Crystallographic Data Centre
via www.ccdc.cam.ac.uk/data_request/cif. Comparative tables and
figures for situation of 1–3c in solid state and in gas phase are gi-
ven. All computed (as xyz files) and measured (as cif files) struc-
tures are also given. Supplementary data associated with this
article can be found, in the online version, at doi:10.1016/
j.jorganchem.2008.06.010.
ˇ
[18b] A. Pevec, M. Mrak, A. Demšar, S. Petricek, H.W. Roesky, Polyhedron 22
(2003) 575–579.
[19] A. Asadi, P.B. Hitchcock, C. Eaborn, Inorg. Chem. 42 (2003) 4141–4146.
[20] [20a] A.D. Becke, J. Chem. Phys. 98 (1993) 5648–5652;
[20b] C. Lee, W. Yang, R.G. Parr, Phys. Rev. B 37 (1988) 785–789;
[20c] P.J. Stevens, F.J. Delvin, C.F. Chablaoski, M.J. Frisch, J. Phys. Chem. 98
(1994) 11623–11627.
[21] W.R. Wadt, P.J. Hay, J. Chem. Phys. 82 (1985) 270–283.
[22] [22a] M.A. Buntine, V.J. Hall, F.J. Kosovel, E.R.T. Tiekink, J. Phys. Chem. A 102
(1998) 2472–2482;
[22b] M. Ryner, A. Finne, A.-C. Albertsson, H.R. Kricheldorf, Macromolecules
34 (2001) 7281–7287;
[22c] Y. Obora, M. Nakanishi, M. Tokunaga, Y. Tsuji, J. Org. Chem. 67 (2002)
5835–5837;
References
[22d] Y.-H. Hu, M.-D. Su, J. Phys. Chem. A 107 (2003) 4130–4135;
[22e] K. Peveling, M. Henn, C. Löw, M. Mehring, M. Schürmann, B. Costisella, K.
Jurkschat, Organometallics 23 (2004) 1501–1508;
[22f] J. Fischer, M. Schürmann, M. Mehring, U. Zachwieja, K. Jurkschat,
Organometallics 25 (2006) 2886–2893.
[1] [1a] For reviews see: E.F. Murphy, R. Murugavel, H.W. Roesky, Chem. Rev. 97
(1997) 3425–3460;
[1b] B. Jagirdar, E.F. Murphy, H.W. Roesky, Prog. Inorg. Chem. 48 (1999) 351–
455;
[1c] H. Dorn, E.F. Murphy, H.W. Roesky, J. Fluorine Chem. 86 (1997) 121–125.
[2] J.L. Wardell, G.M. Spenser, in: R.B. King (Ed.), Encyclopedia of Inorganic
Chemistry, vol. 8, Wiley, New York, 1994, p. 4172.
ˇ ˇ
ˇ
ˇ
[23] L. Dostál, R. Jambor, A. Ru˚ zicka, I. Císarová, J. Holecek, M. Biesemans, R. Willem,
F. De Proft, P. Geerlings, Organometallics 26 (2007) 6312–6319.
[24] A. Altomare, G. Cascarone, C. Giacovazzo, A. Guagliardi, M.C. Burla, G. Polidori,
M. Camalli, J. Appl. Crystallogr. 27 (1994) 1045–1050.
[3] S.S. Al-Juaid, S.M. Dhaher, C. Eaborn, P.B. Hitchcock, J. Organomet. Chem. 325
(1987) 117–127.
[25] G.M. Sheldrick, SHELXL-97,
A Program for Crystal Structure Refinement,
University of Göttingen, Germanyn, 1997.
[26] P. Coppens, in: F.R. Ahmed, S.R. Hall, C.P. Huber (Eds.), Crystallographic
Computing, Copenhagen, Munksgaard, 1970, pp. 255–270.
[4] H. Reuter, H. Puff, J. Organomet. Chem. 379 (1989) 223–234.
[5] J. Beckmann, D. Horn, K. Jurkschat, F. Rosche, M. Schürmann, U. Zachwieja, D.
Dakternieks, A. Duthie, E.K.L. Lim, Eur. J. Inorg. Chem. (2003) 164–174.
[6] U. Kolb, M. Draeger, M. Dargatz, K. Jurkschat, Organometallics 14 (1995) 2827–
2834.
[7] M. Mehring, I. Vrasidas, D. Horn, M. Schürmann, K. Jurkschat, Organometallics
20 (2001) 4647–4653.
[8] N. Pieper, C. Klaus-Mrestani, M. Schürmann, K. Jurkschat, M. Biesemans, I.
Verbruggen, J.C. Martins, R. Willem, Organometallics 16 (1997) 1043–1052.
[9] N. Pieper, R. Ludwig, M. Schürmann, K. Jurkschat, M. Biesemans, I. Verbruggen,
R. Willem, Phosphorus Sulfur Silicon Relat. Elem. 151 (1999) 305–310.
[27] M.J. Frisch, G.W. Trucks, H.B. Schlegel, G.E. Scuseria, M.A. Robb, J.R. Cheeseman,
Jr., J.A. Montgomery, T. Vreven, K.N. Kudin, J.C. Burant, J.M. Millam, S.S. Iyengar,
J. Tomasi, V. Barone, B. Mennucci, M. Cossi, G. Scalmani, N. Rega, G.A.
Petersson, H. Nakatsuji, M. Hada, M. Ehara, K. Toyota, R. Fukuda, J. Hasegawa,
M. Ishida, T. Nakajima, Y. Honda, O. Kitao, H. Nakai, M. Klene, X. Li, J.E. Knox,
H.P. Hratchian, J.B. Cross, V. Bakken, C. Adamo, J. Jaramillo, R. Gomperts, R.E.
Stratmann, O. Yazyev, A.J. Austin, R. Cammi, C. Pomelli, J.W. Ochterski, P.Y.
Ayala, K. Morokuma, G.A. Voth, P. Salvador, J.J. Dannenberg, V.G. Zakrzewski, S.
Dapprich, A. D. Daniels, M.C. Strain, O. Farkas, D.K. Malick, A.D. Rabuck, K.
Raghavachari, J.B. Foresman, J.V. Ortiz, Q. Cui, A.G. Baboul, S. Clifford, J.
Cioslowski, B.B. Stefanov, G. Liu, A. Liashenko, P. Piskorz, I. Komaromi, R.L.
Martin, D.J. Fox, T. Keith, M.A. Al-Laham, C.Y. Peng, A. Nanayakkara, M.
Challacombe, P.M.W. Gill, B. Johnson, W. Chen, M.W. Wong, C. Gonzalez, J.A.
Pople, GAUSSIAN 03, Revision B.03, Gaussian, Inc., Wallingford CT, 2004.
[10] J. Bareš, P. Novák, M. Nádvorník, T. Lébl, R. Jambor, I. Císarová, A. Ruzicka, J.
˚ ˇ ˇ
ˇ
ˇ
Holecek, Organometallics 23 (2004) 2967–2972.
ˇ
ˇ
ˇ
[11] [11a] P. Švec, P. Novák, M. Nádvorník, Z. Padelková, I. Císarová, L. Kolárová, A.
ˇ ˇ
ˇ
Ru˚ zicka, J. Holecek, J. Fluorine Chem. 128 (2007) 1390–1395;
ˇ ˇ
ˇ
ˇ
[11b] L. Dostál, R. Jambor, A. Ru˚ zicka, R. Jirásko, I. Císarová, J. Holecek, J.
Fluorine Chem. 129 (2008) 167–172;