Structure of C, N-chelated nButyltin(IV) fluorides and their use as fluorinating agents of some chlorosilanes, chlorophosphine and metal halides

Article abstract of DOI:10.1016/j.jfluchem.2007.07.001

The tin atom in the solid-state structure of {2-[(CH₃)₂NCH₂]C₆H₄}nBu₂SnF is five coordinated with carbon atoms in equatorial and fluorine and nitrogen atoms in axial positions. The fluorina

Full text of DOI:10.1016/j.jfluchem.2007.07.001

Journal of Fluorine Chemistry 128 (2007) 1390–1395
www.elsevier.com/locate/fluor
Structure of C, N-chelated nButyltin(IV) fluorides and their
use as fluorinating agents of some chlorosilanes, chlorophosphine
and metal halides
a
Petr Svec , Petr Novak , Milan Nadvornık , Zdenka Padelkova ,
a
a
a
ˇ
´
´
´
ˇ
ˇ
´
Ivana Cısarova , Lenka Kolarova , Ales Ruzicka , Jaroslav Holecek
´ ˇ ´ b
´ˇ ´ c
ˇ
ˇ ˇ
ˇ
a,
a
*
˚
a Department of General and Inorganic Chemistry, Faculty of Chemical Technology, University of Pardubice,
ˇ
´
´
nam. Cs. legiı 565, CZ-532 10, Pardubice, Czech Republic
b Department of Inorganic Chemistry, Faculty of Natural Science, Charles University in Prague,
Hlavova 2030, 128 40 Praha 2, Czech Republic
c Department of Analytical Chemistry, Faculty of Chemical Technology, University of Pardubice,
ˇ
´ ´
nam. Cs. legiı 565, CZ-532 10, Pardubice, Czech Republic
Received 1 February 2007; received in revised form 2 July 2007; accepted 2 July 2007
Available online 10 July 2007
Abstract
The tin atom in the solid-state structure of {2-[(CH3)2NCH2]C6H4}nBu2SnF is five coordinated with carbon atoms in equatorial and fluorine
and nitrogen atoms in axial positions. The fluorination of {2-[(CH3)2NCH2]C6H4}nBuSnCl2 is described by NMR methods. The successful
attempts to fluorinate various chlorosilanes, chlorophosphine and metal halides are also reported.
# 2007 Elsevier B.V. All rights reserved.
Keywords: Organotin(IV) fluorides; C,N-ligand; Structure
1. Introduction
fluorides of general formula LCNR2SnF, where LCN is {2-
[(CH3)2NCH2]C6H4}ꢀ and R is alkyl (Me, nBu, tBu) or aryl (Ph)
groups of different steric bulk and electronic properties [7]. The
compounds have five-coordinated tin and are able to fluorinate
titanocene dichloride essentialy quantitatively. In our latest
reports on this field, we reported the di- [8] and monoorgano-
tin(IV) [9] fluorides having the same ligand. These compounds
are presumably tri- or tetranuclear species with rather low
solubility in common organic solvents and we used them as a part
ofselectiveandsensitivecarriersforfluorideionrecognition[10].
In this paper, we communicate on solid-state structure {2-
[(CH3)2NCH2]C6H4}nBu2SnF, earlier used as fluorinating agent
[7], solution structure of {2-[(CH3)2NCH2]C6H4}nBuSnCl2 [11]
andproductsofitsfluorination. Theattemptstofluorinatevarious
chlorosilanes, chlorophosphine and metal halides are also
reported.
One of the goals in the chemistry of tri- and diorganotin(IV)
compoundsistoprepareandstructurallycharacterizemonomeric
organotin fluorides, which are of great interest due to their ability
toundergothemetatheticalhalideforfluorideexchangereactions
with different kinds of organometallic halides [1]. The structures
of many tri- and a limited number of diorganotin fluorides have
been determined and found to be either oligo- or polymeric with
the ‘‘rod-like’’ or ‘‘zig-zag’’ F–Sn–F chains [2]. These
compounds have relatively high melting points, and are rather
insoluble in common organic solvents, which is a limitation in
studies of their structure and reactivity. Only a small number of
compounds containing bulky ligands, e.g., Sn[C(SiMe2Ph)3]-
Me2F [3], Sn[C(SiMe3)3]Ph2F [3], Sn[C6H2 Me3-2,4,6)3]Me2F
[4] and Sn(CH2SiMe3)3F [5], with a four-coordinated tin central
atom, are monomeric with a Sn–F terminal single bond distance
˚
about 1.96 A [6]. Recently, we have reported triorganotin(IV)
2. Results and discussion
Both {2-[(CH3)2NCH2]C6H4}nBu2SnCl (1) and {2-[(CH3)2
NCH2]C6H4}nBu2SnF (2) were described in the previous papers
* Corresponding author. Fax: +420 466037068.
ˇ
E-mail address: ales.ruzicka@upce.cz (A. Ruzicka).
˚ˇ
0022-1139/$ – see front matter # 2007 Elsevier B.V. All rights reserved.
doi:10.1016/j.jfluchem.2007.07.001

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P. Svec et al. / Journal of Fluorine Chemistry 128 (2007) 1390–1395
1391
fluorination ability of {2-[(CH3)2NCH2]C6H4}nBu2SnF (2)
[7,8,9,10] and the second one is reaction with dried NH4F
(excess) in dichloromethane under an argon atmosphere.
The first method yields the white crystals which are insoluble
in non-polar solvents, but slightly soluble in chloroform and
soluble in coordinating solvents such as DMSO, acetonitrile or
nitrobenzene. Thebestsolubilitywasdeterminedforchloroform/
DMSO 10/1 mixture. The composition and structure in solution
depends dramaticaly on the solvent used and temperature
(Scheme 1). In chloroform, is proposed a polymeric structure
suggestion 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
nitrobenzene or acetonitrile, the tetrameric structure was
deduced from ESI-MS measurements. The structure in DMSO
ismonomericwithdynamicallyexchangingfluorineatoms(from
axial to equatorial position of trigonal bipyramid).
Fig. 1. The molecular structure (ORTEP 40% probability level) of {2-
[(CH3)2NCH2]C6H4}nBu2SnF (2), hydrogen atoms are omitted for clarity.
˚
Selected interatomic distances [A] and angles [8]: Sn–F 2.0804(16), Sn–C10
2.144(3), Sn–C14 2.143(3), Sn–C1 2.139(3), Sn–N 2.526(3), C10–Sn–C14
123.28(13), C10–Sn–C1 113.86(12), C14–Sn–C1 121.81(12), F–Sn–N
168.80(8), F–Sn–C1 94.52(10), C1–Sn–N 74.38(11), C10–Sn–N 92.57(12),
C14–Sn–N 92.25(11), C3–C2–C7–N 30.6(2).
When compound 3 was treated with two equivalents of
NH4F the product of similar properties was found as for the first
method. Addition of one equivalent of NH4F to 4 in methanol
led to the formation of dimeric ionic species 5 which upon
addition of further equivalents of NH4F gave probably
monomeric species 5a. Structures were deduced from MS
spectra patterns and low temperature 19F NMR spectra where
three terminal fluorine atoms are bonded to tin (1J(119Sn,19F)
ꢁ3100 Hz). Also broad quartet in 119Sn NMR spectra located in
region typical for a six-coordinated tin atom (ꢀ438.4 ppm)
supporting the same structure and behavior prediction which
was recently found for a Ph analog of 4 [8].
as a yellowish oil [7,11] which cannot be crystallized. The
crystalline and sublimable material was obtained by changing
slightly the preparation procedure, which facilitate easier
handling with it (see Section 3).
2.1. Structure of 2
Structure of 2 (Fig. 1) is similar to analogous chlorides and
fluorides (Me or Ph instead of nBu) [7,12,13], i.e. trigonal
bipyramidal geometry of the tin atom with electronegative atoms
(N, Cl (F)) in axial and carbon atoms in equatorial positions. The
˚
Sn–F distance (2.0804(16) A) is the longest known for the
terminal Sn–F bond which is caused by trans effect of nitrogen
2.2. Fluorination activity of 2
˚
donor atom. The adjacent fluorine atom is located 4.898 A from
˚
the tin centre (4.610 and 6.257 A for Me or Ph analogs) [7].
Based on the previous successful fluorination [7,8] of
titanocene dichloride and several organotin(IV) chlorides by
2, we tried to fluorinate some chlorosilanes, chlorophosphine and
metal halides. In the case of chlorosilanes (Table 1) this
Two different methods were used for replacing chlorine by
fluorine atom(s) in 3. The first method is based on the known
Scheme 1.

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P. Svec et al. / Journal of Fluorine Chemistry 128 (2007) 1390–1395
1392
Table 1
Fluorination experiments
Run
Substrate
Conditions
Product
Conversion [%]a
1
2
(4-CH3O-Ph)Ph2SiCl
(4-CH3O-Ph)Ph2SiCl
Benzene, R.T., 1 eq. of 2, 1 d
Benzene, R.T., 5 eq. of KF, 1 mol% of 2,
1% mol of 18-crown-6, 7 d
THF, R.T., 1 eq. of 2, 5 h
CDCl3, R.T., 1 eq. of 2, 2 h
THF, reflux, 5 eq. of KF, 1% mol of 2,
1% mol of 18-crown-6, 15 h
CDCl3, R.T., 1 eq. of 2, 2 h
THF, reflux, 5 eq. of KF, 1% mol of 2,
1% mol of 18-crown-6, 15 h
Benzene, R.T., 2 eq. of 2, 1 d
Toluene, R.T., 5 eq. of KF, 1% mol of 2,
1% mol 18-crown-6, 8 d
(4-CH3OPh)Ph2SiF
(4-CH3OPh)Ph2SiF
100
90
3
4
5
c-HexPh2SiCl
BzPh2SiCl
c-HexPh2SiF
BzPh2SiF
100
100
95
BzPh2SiCl
BzPh2SiF
6
7
n-OctPh2SiCl
n-OctPh2SiCl
n-OctPh2SiF
n-OctPh2SiF
100
95
8
9
t-Bu2SiCl2
t-Bu2SiCl2
t-Bu2SiF2
100
–
t-Bu2SiF2 + t-Bu2SiFCl + t-Bu2SiCl2
10
11
12
13
14
15
16
17
18
19
20
21
22
Me2SiHCl
Benzene, R.T., 1 eq. of 2, 1 d
Toluene, R.T., 1 eq. of 2, 1 d
C6D6, R.T., 1 eq. of 2, 1 min
C6D6, R.T., 2 eq. of 2, 1 h
Me2SiHF
100
100
100
100
100
100
100
100
100
100
45
PhSiH2Cl
(h1-C5H5)-1-SiMe3-1-SiMe2Cl
PhSiH2F
(h1-C5H5)-1-SiMe3-1-SiMe2F
PhPCl2
FeBr2
AlCl3
NiCl2
CoCl2
CaCl2
CoCl3
PbCl2
ZrCl4
PdCl2
PhPF2
FeF2
AlF3
NiF2
CoF2
CaF2
CoF3
PbF2
ZrF4
PdF2
THF, R.T., 2 eq. of 2, 2 d
Benzene, R.T., 3 eq. of 2, 2 d
THF, reflux, 2 eq. of 2, 1 h
THF, R.T., 2 eq. of 2, 1 d
THF, R.T., 2 eq. of 2, 2 d
THF, R.T., 3 eq. of 2, 2 d
THF, reflux, 2 eq. of 2, 1 d
Toluene, R.T., 4 eq. of 2, 2 d
THF, R.T., 2 eq. of 2, 1 d
90
n.o.
a
Based on 1H, 29Si, 31P and 119Sn NMR spectra.
fluorination method seems to be very effective, hence a catalytic
version was also attempted. Chlorosilanes can be transformed to
appropriate fluorosilanes by several methods and reagents
[14,15]: BF3ꢂOEt2, SbF3, ZnF2, NH4F, CuF2, Na2SiF6, NaPF6,
NaSbF6, NaBF4, Me3SnF, AgF, PF5, Ph3CBF4, SbF3, NOBF4,
NO2BF4 and CuF2/CCl4, but it is not very easy to obtain
selectively fluorosilanes containing Si–H bond(s). Van Dyke
et al. made partially fluorinated polysilanes by PF5 or Ph3CBF4
methods. There are disadvantages of these reagents as for
example price, instability, lower selectivity, toxicity and the need
to use more than an equimolar amount of reagent. Reaction times
may be long and high temperature is also needed to obtain
satisfactory yields of fluorinated products. Lickiss and Lucas
[16] made fluorosilanes using ultrasound activation or started the
reactions by small amount of water. As reagents they used
Na2SiF6 or (NH4)2SiF6 in 1,2-dimethoxyethane (DME, less than
0.005% H2O) but when the starting chlorosilanes contained
sterically demanding groups (as for example t-Bu2SiCl2) the
reaction time at reflux conditions was about 2 weeks. Fluoro-
phospines can be prepared by several methods including (i)
reaction of RLi with ClPF2 [17] (ii) reaction of RPCl2 with SbF3
or HF [18]. The yield of the appropriate fluorophospine is about
20% in case of R = alkyl and increases up to 35% if R = aryl.
Chlorosilanes and PhPCl2 (runs 1, 3, 4, 6, 8, 10, 11, 12 and 13
Table 1) were fluorinated by an equimolar amount of 2,
essentially quantitatively and selectively in a few minutes (run
12) or hours. The catalytic versions of the reactions (18-crown-6
was used for KF transfer) were successful and it seems that the
only limitation is the reaction time which is much longer for
sterically hindered silanes (run 9). The fluorination of metal
halides is also successful even for such strong fluorination agents
as CoF3. Problems occurred only in the case of PbF2, where the
lowsolubilityofstartingmaterialisprobablythereasonofslower
reaction and PdCl2 cannot be fluorinated by this method.
3. Experimental
Both {2-[(CH3)2NCH2]C6H4}nBu2SnCl (1) and {2-
[(CH3)2NCH2]C6H4}nBu2SnF (2) have been prepared by
procedures reported in refs. [7,11], NaF was used as
fluorinating agent instead of KF. Single crystals of both
compounds were obtained by vacuo sublimation (30 8C/1 Pa)
of crude material and reveal the same patterns of NMR spectra
and elemental analysis as published previously. {2-
[(CH3)2NCH2]C6H4}nBuSnCl2 (3) was prepared as published
elsewhere [11]. Chlorosilanes, phosphines and metal halides
were prepared according to literature [19] or obtained from
commercial sources. The purity and composition of metal
fluorides (except of GeF4 and WF6, where the identity was
deduced only from boiling points) were checked by powder
diffraction methods on a Bruker D8 ADVANCE or Nonius
Kappa CCD device in powder diffraction mode and compared
to the library (DIFFRACplus Evaluation Package Diffracplus
SEARCH) and crystallographic databases displaying good
agreement with stored data.
3.1. NMR spectroscopy
The NMR spectra were recorded as solutions in methanol
D4, C6D6, CDCl3 on a Bruker Avance 500 spectrometer

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P. Svec et al. / Journal of Fluorine Chemistry 128 (2007) 1390–1395
1393
(equipped with Z-gradient 5 mm probe) at 300, 250 or 220 K 1H
electron density = 1.863, ꢀ1.895 eAꢀ3. CCDC deposition
˚
(500.13 MHz), 119Sn{1H} (186.50 MHz) and 19F{1H} (470.53
number: 607136.
1
MHz). The assignments of signals in H spectra were made
from standard 2D measurements. The solutions were obtained
by dissolving of 5–40 mg of each compound in 0.5 ml of
1
deuterated solvents. The H chemical shifts were calibrated
3.4. {2-[(CH3)2NCH2]C6H4}nBuSnF2 (4)
Thecompound 3 (2.20 g, 5.8 mmol)was dissolvedin 50 mlof
toluene and 2 (4.47 g, 11.6 mmol) was added. White crystals of 4
appeared immediately upon addition. The soluble part was
filtered off and the solid was washed twice with the same solvent
and dried in vacuo. The volatiles from the filtrate were vacuo
removed and the {2-[(CH3)2NCH2]C6H4}nBu2SnCl was identi-
fied by NMR and m.p. as the sole product [11]. For 4: yield 71%.
m.p. 251–255 8C. 1H NMR (CDCl3, 300 K, ppm): 7.98 (br, 1H-
6); 7.38 (br, 2H-4,5), 7.18 (d, 1H-3); 3.72 (s, 2H-NCH2); 2.45 (s,
6H-NCH3); 1.65 (br anisochronous, 2H-H10); 1.41 (br, 2H-H20);
1.24 (br, 2H-H30); 0.94 (t, 3H-H40). 19F{1H} NMR (CDCl3,
relative to the signal of residual CHCl3 (d = 7.27) and benzene
(7.16), methanol (d = 3.31), respectively, and the 19F chemical
shifts are referred to external CCl3F (d = 0.0). The 119Sn
chemical shifts are referred to external neat tetramethylstan-
nane (d = 0.0). Positive chemical shifts values denote shifts to
the higher frequencies relative to the standards. 119Sn NMR
spectra were measured using the inverse gated-decoupling
mode.
3.2. Mass spectrometry
1
295 K, ppm): ꢀ177.6 (bs), ꢀ181.9 (bs). H NMR (DMSO-d6,
Electrospray ionization (ESI) mass spectra (MS) were
measured on the ion trap analyser Esquire3000 or qTOF
analyser micrOTOF-Q (both Bruker Daltonics, Bremen,
Germany) in the range m/z 50–2000. The sample was dissolved
in acetonitrile or methanol and analysed by direct infusion at
the flow rate 5 ml/min both in the negative- and positive-ion
modes. The ion source temperature was 300 8C (180 8C,
qTOF), the flow rate and the pressure of nitrogen were 4 l/min
and 10 psi (0.4 bar, qTOF), respectively. The isolation width for
MS/MS experiments was Dm/z = 8, and the collision amplitude
was 0.9 V (qTOF, colision energy 20 eV).
295 K, ppm): 7.80 (br s, 1H-6);7.30 (br, 2H-4,5), 7.15 (br, 1H-3);
2.28 (s, 6H-NCH3); 1.67 (br, 2H-H10); 1.37 (br, 2H-H20); 1.27
(br, 2H-H30);0.89(t, 3H-H40). 19F{1H}NMR(DMSO-d6, 295 K,
ppm): ꢀ159.8 (br, w1/2 = 300 Hz). 1H NMR (CDCl3/DMSO-d6
(v/v)10/1, 300 K, ppm): 7.80 (br s, 1H-6);7.24 (bs, 2H-4,5), 7.07
(br, 1H-3); 3.59 (s, 2H-NCH2); 2.33 (s, 6H-NCH3); 1.66 (m, 2H-
H10); 1.37 (br m, 4H-H20, H30); 0.87 (t, 3H-H40). 19F{1H} NMR
(CDCl3/DMSO-d6 (v/v) 10/1, 295 K, ppm): ꢀ157.2 (br - w1/
2 = 224 Hz, 1J(19F, 119Sn) = 2884 Hz). 119Sn{1H} NMR
(CDCl3/DMSO-d6 (v/v) 10/1, 295 K, ppm): ꢀ364.9 (t
1
1J(119Sn, 19F) = 2886 Hz). H NMR (CDCl3/DMSO-d6 (v/v)
10/1, 250 K, ppm): 7.88 (br s, 1H-6); 7.38 (bs, 2H-4,5), 7.21 (br,
1H-3); 3.70 (s, 2H-NCH2); 2.46 (s, 6H-NCH3); 1.75 (br s, 2H-
H10); 1.45 (br m, 4H-H20, H30); 0.99 (t, 3H-H40). 19F{1H} NMR
(CDCl3/DMSO-d6 (v/v)10/1, 250 K, ppm): ꢀ153.6 (br), ꢀ156.6
(br). 1H NMR (CDCl3/DMSO-d6 (v/v) 10/1, 220 K, ppm): 7.88
(br s, 1H-6); 7.40 (bs, 2H-4,5), 7.24 (br, 1H-3); 3.71 (d, 2H-
NCH2, 2J(1HA, 1HB) = 120 Hz)); 2.23 (AX pattern, 6H-NCH3,
3.3. X-ray crystallography
The single crystals of 2 were obtained by vacuo sublimation.
Data for colorless crystals were collected at 150(1) K on a
Nonius KappaCCD diffractometer using Mo Ka radiation
˚
(l = 0.71073 A), and graphite monochromator. The structures
1
were solved by direct methods (SIR92 [20]). All reflections
were used in the structure refinement based on F2 by full-matrix
least-squares technique (SHELXL97 [21]). 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 1.5 Ueq for the methyl moiety. Absorption corrections
were carried on, using either multi-scans procedure (PLATON
[22] or SORTAV [23]) or Gaussian integration from crystal
shape (Coppens [24]).
2J(1HA, HX) = 115 Hz); 1.74 (br s, 2H-H10); 1.45 (br m, 4H-
H20, H30); 1.00 (br, 3H-H40). 19F{1H} NMR (CDCl3/DMSO-d6
(v/v) 10/1, 220 K, ppm): ꢀ153.6 (br), ꢀ156.6 (br). ESI-MS:
MW = 349. Positive-ion ESI/MS: m/z 679, [2MꢀF]+, 3%; m/z
330, [MꢀF]+, 18%; m/z 136, [H(LCN)+H]+, 100%. Negative-ion
ESI/MS: m/z 945, [3MꢀBu-(CH3)2NH]ꢀ, 100%. Elemental
analysis (%): C, 44.8; H, 6.0; N, 4.1; calcd. for C13H21F2NSn: C,
44.9; H, 6.1; N, 4.0.
3.5. ([{2-[(CH3)2NCH2]C6H4}nBuSnF3]ꢀ)2 2([NH4]+) (5)
A full list of crystallographic data and parameters including
fractional coordinates is deposited at the Cambridge Crystal-
lographic Data Center, 12 Union Road, Cambridge, CB2 1EZ,
UK [Fax: +44 1223 336 033; e-mail: deposit@ccdc.cam.ac.uk].
Crystallographic data for 2: C17H30NFSn, M = 386.11,
The compound 4 (291 mg, 0.84 mmol) was dissolved in
25 ml of dichloromethane and 1 eq. of NH4F (31 mg,
0.84 mmol) was added. The reaction mixture was stirred
for 1 h. Afterwards dichloromethane was vacuo removed and
white crystals of 5 were obtained. Yield 93%. m.p. 276–
279 8C. 1H NMR (CD3OD, 295 K, ppm): 7.84 (d, 1H-6), 7.33
(m, 2H-4,5), 7.17 (d, 1H-3), 3.69 (s, 2H-NCH2), 2.44
(s, 6H-NCH3), 1.81 (m, 2H-H10), 1.48 (m, 4H-H20, H30), 0.98
(t, 3H-H40).1H NMR (CD3OD, 250 K, ppm): 7.86 (d, 1H-6),
7.35 (m, 2H-4,5), 7.20 (d, 1H-3), 3.73 (s, 2H-NCH2), 2.46
(s, 6H-NCH3), 1.79 (m, 2H-H10), 1.36 (m, 4H-H20, H30), 1.00
orthorhombic, Pbca, a = 16.2540(2), b = 11.8460(3), c =
3
˚
˚
19.0280(4) A, b = 90.008, Z = 8, V = 3663.74(13) A , Dc =
g cmꢀ3, m = 1.396 mmꢀ1, Tmin = 0.737, Tmax = 0.812; 48031
reflections measured (umax = 27.58), 4207 independent (Rint
0.0415), 3442 with I > 2s(I), 185 parameters, S = 1.055, R1(obs.
=
data) = 0.0356, wR2(all data) = 0.0930; max., min. residual

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P. Svec et al. / Journal of Fluorine Chemistry 128 (2007) 1390–1395
1394
(t, 3H-H40).19F{1H} NMR (CD3OD, 250 K, ppm): ꢀ164.6
4.2. c-HexPh2SiF
1
(br). H NMR (CD3OD, 220 K, ppm): 7.81 (d, 1H-6), 7.25
(s, 2H-4,5), 7.14 (br, 1H-3), 3.62 (br s, 2H-NCH2), 2.42
(s, 6H-NCH3), 1.74 (m, 2H-H10), 1.43 (m, 4H-H20, H30), 0.97
(t, 3H-40). 19F{1H} NMR (CD3OD, 220 K, ppm): ꢀ131.8 (br),
ꢀ161.8 (br), ꢀ165.1 (br). ESI-MS: MW = 772 Positive-ion
ESI/MS: m/z 679, [Mꢀ2*NH4F-F]+, 18%; m/z 368, [1/
2MꢀF + H]+, 38%, m/z 350, [1/2MꢀNH4F+H]+, 17%; m/z
330, [1/2MꢀNH4F-F]+, 100%. Negative-ion ESI/MS: m/z
717, [MꢀNH4F-NH4]ꢀ, 1%; m/z 368, [1/2MꢀNH4]ꢀ, 100%,
m/z 348, [1/2MꢀNH4-HF]ꢀ, 12%; m/z 328, [1/2MꢀNH4-
2*HF]+, 14%; m/z 308, [1/2MꢀNH4-3*HF]ꢀ, 1%. Elemental
analysis (%): C, 40.7; H, 6.5; N, 7.5; calcd. for
C26H32F6N4Sn2: C, 40.45; H, 6.75; N, 7.3.
1H NMR (CDCl3, 300 K, ppm): 7.63 (d, phenyl H);
7.40 (m, phenyl H), 1.83 (m, cyclohexyl H), 1.74 (m,
cyclohexyle H), 1.36 (m, cyclohexyle H). 19F{1H} NMR
(CDCl3, 300 K, ppm): ꢀ177.9 (s, 1J(29Si, 19F) = 315 Hz).
1
29Si{1H} NMR (CDCl3, 300 K, ppm): ꢀ3.2 (d, J(19F, 29Si)
= 315 Hz).
4.3. BzPh2SiF
1H NMR (CDCl3, 300 K, ppm): 7.78 (d, phenyl and benzyl
H); 7.63 (m, phenyl and benzyl H), 2.72 (d, phenyl-CH2- H).
19F{1H} NMR (CDCl3, 300 K, ppm): ꢀ169.8 (s, 1J(29Si,
19F) = 285 Hz).
3.6. [{2-[(CH3)2NCH2]C6H4}nBuSnF3]ꢀ[NH4]+ (5a)
4.4. n-OctPh2SiF
Compound 3 (250 mg, 0.66 mmol) was dissolved in 10 ml of
dichloromethane and NH4F (20 eq., excess) was added. The
reaction mixture was stirred for 8 h. Afterwards the soluble part
was filtered off and the volatiles were vacuo removed. The
1H NMR (CDCl3, 300 K, ppm): 7.55 (d, phenyl H); 7.37 (m,
phenyl H), 1.33 (m, octyl H), 1.17 (m, octyl H), 0.85 (t, octyl
1
H). 19F{1H} NMR (CDCl3, 300 K, ppm): ꢀ171.3 (s, J(29Si,
1
product was dissolved in CD3OD. H NMR (CD3OD, 300 K,
19F) = 287 Hz).
ppm): 7.80 (s, 1H-6), 3J(119Sn, 1H) = 94.6 Hz, 7.36 (s, 1H-4, 5),
7.11 (s, 1H-3), 3.69 (s, 2H, NCH2), 2.45 (s, 6H, NCH3), 1.78
(m, 2H-10), 1,45 (m, 4H ꢀ20,30), 0.96 (t, 3H ꢀ40). 19F{1H}
NMR (CD3OD, 300 K, ppm): ꢀ133.3 (bs, NH4F), ꢀ135.4 (s),
ꢀ153.8 (s), ꢀ157.5 (bs). 119Sn{1H} NMR (CD3OD, 300 K,
4.5. t-Bu2SiF2
b.p. 129–130 8C. 1H NMR (CDCl3, 300 K, ppm): 1.06
(s, t-butyle H). 19F{1H} NMR (CDCl3, 300 K, ppm): ꢀ156.5
(s, 1J(29Si, 19F) = 327 Hz). 29Si{1H} NMR (CDCl3, 300 K,
ppm): ꢀ8.2 (t, J(19F, 29Si) = 327 Hz).
1
ppm): ꢀ438.4 (bq), J(119Sn,19F) ꢁ3100 Hz. 19F{1H} NMR
(CD3OD, 250 K, ppm): ꢀ131 (bs), ꢀ137.43 (s); 1J(19F,
119Sn) = 2945 Hz, ꢀ137.96 (bs, NH4F), ꢀ159.4 (s); 1J(19F,
119Sn) = 2902 Hz. 19F{1H} NMR (CD3OD, 220 K, ppm): ꢀ131
1
4.6. PhSiH2F
1
(s); J(19F, 119Sn) = 2531 Hz, ꢀ137.96 (bs, NH4F), ꢀ159 (s);
1J(19F, 119Sn) = 2880 Hz.
b.p. 112–113 8C. H NMR (CDCl3, 300 K, ppm): 7.66 (d,
1
phenyl H), 7.33 (m, phenyl H), 5.17 (d, J(19F, H) = 51 Hz).
19F{1H} NMR (CDCl3, 300 K, ppm): ꢀ156.5 (s, 1J(29Si,
19F) = 286 Hz). 29Si{1H} NMR (CDCl3, 300 K, ppm): ꢀ7.16
1
1
4. Typical procedure of chlorosilanes, chlorophosphine
and metal halides fluorination
1
(d, J(19F, 29Si) = 286 Hz).
The amount of 40–200 mg of appropriate substrate was
added to 2 at conditions summarized in Table 1, and the
mixture was stirred for 1 min (run 12) up to 8 days (catalytic
run 9), the sample was filtered, in the case of heterogenous
reactions or paramagnetic species, and the solvent removed in
vacuo (in the case of run 9 the product was trapped at liquid
nitrogen temperature), then deuterated benzene or chloroform
was added and the composition and composition of material
was checked by GC–MS and multinuclear NMR spectroscopy
[7,11,14,15,16]. The products were separated by washing of 1
by pentane in the case of insoluble metal fluorides or by
(vacuo) distillation in the case of fluorosilanes and fluoropho-
sphine.
4.7. Me2SiHF
b.p. ꢀ9 8C. NMR spectra were not recorded due to low
boiling point.
4.8. (h1-C5H5)-1-SiMe3-1-SiMe2F
b.p. 50 8C/400 Pa. 1H NMR (CDCl3, 295 K, ppm): 6.76 (br
s, h1-C5H5), 6.38 (br s, h1-C5H5), 0.00 (d, SiMe2F J(1H,
1
19F) = 6.85 Hz), ꢀ0.02 (s, SiMe3). 19F{1H} NMR (CDCl3,
295 K, ppm): ꢀ151.43 (s, J(29Si, 19F) = 279 Hz).
1
4.9. PhPF2
4.1. (4-CH3OPh)Ph2SiF
b.p. 122–123 8C. 1H NMR (CDCl3, 300 K, ppm): 7.40 (m,
phenyl H), 7.20 (m, phenyl H). 19F{1H} NMR (CDCl3,
300 K, ppm): ꢀ90.75 (d, 1J(15P, 19F) = 1163 Hz). 15P{1H}
NMR (CDCl3, 300 K, ppm): 206.54 (t, 1J(19F, 15P) =
1163 Hz).
1H NMR (CDCl3, 300 K, ppm): 7.67 (m, phenyl H); 7.45 (m,
phenyl H), 3.61 (s, methoxy H). 19F{1H} NMR (CDCl3, 300 K,
ppm): ꢀ167.9 (s, 1J(29Si, 19F) = 282 Hz). 29Si{1H} NMR
(CDCl3, 300 K, ppm): ꢀ11.1 (d, J(19F, 29Si) = 282 Hz).
1

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P. Svec et al. / Journal of Fluorine Chemistry 128 (2007) 1390–1395
1395
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[7] J. Bares, P. Novak, M. Nadvornık, T. Lebl, R. Jambor, I. Cısarova, A.
Acknowledgements
ˇ ˇ
ˇ
Ru˚zicka, J. Holecek, Organometallics 23 (2004) 2967–2972.
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[8] P. Novak, J. Brus, I. Cısarova, A. Ruzicka, J. Holecek, J. Fluorine Chem.
˚
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The authors wish to thank Ms. Hana Vankatova, Mr. Jakub
ˇ ˇ
Vokoun and Mr. Jan Vecera for synthetic help. The financial
126 (2005) 1531–1538.
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˚
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[9] P. Novak, Z. Padelkova, I. Cısarova, L. Kolarova, A. Ruzicka, J. Holecek,
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.
Appl. Organomet. Chem. 20 (2006) 226–232.
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[10] S. Chandra, A. Ruzicka, P. Svec, H. Lang, Anal. Chim. Acta 577 (2006)
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[11] A. Ruzicka, V. Pejchal, J. Holecek, A. Lycka, K. Jacob, Collect. Czech.
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