Intramolecular nucleophilic substitution in a C6F5 moiety assisted by antimony

Article abstract of DOI:10.1002/ejic.200400074

Antimony tris-amides - (Et₂N)_3-n-Sb[N(C ₆F₅)(2-C₅H₄N)]_n [n = 1 (3), 2 (4) or 3 (5)] - have been prepared by treatment of Sb(NEt ₂)₃ (1) with stoichiometric

Full text of DOI:10.1002/ejic.200400074

FULL PAPER
Intramolecular Nucleophilic Substitution in a C6F5 Moiety Assisted by
Antimony
Pavel L. Shutov,[a] Sergey S. Karlov,*[b] Klaus Harms,[a] Daniil A. Tyurin,[b]
Jörg Sundermeyer,[a] Jörg Lorberth,[a] and Galina S. Zaitseva[b]
Keywords: Antimony / Amides / Density functional calculations / Fluorinated ligands / Nucleophilic substitution
Antimony tris-amides
—
(Et2N)3−nSb[N(C6F5)(2-C5H4N)]n
[N(C6F5)(2-C5H4N)] (7). The structure of 7 was confirmed by
X-ray diffraction studies. DFT calculations, which reproduce
the principal features of compound 7’s geometry, have been
used to explain the possible reaction pathway of this ortho-
directed metathetical fluoride-amide exchange.
( Wiley-VCH Verlag GmbH & Co. KGaA, 69451 Weinheim,
Germany, 2004)
[n = 1 (3), 2 (4) or 3 (5)] — have been prepared by treatment
of Sb(NEt2)3 (1) with stoichiometric amounts of (2-
C5H4N)(C6F5)NH (2). In contrast to amide 5, compounds 3
and 4 are unexpectedly unstable and react further to give the
bis-amido antimony fluorides [(2-Et2N-C6F4)(2-C5H4N)N]-
Sb(F)[N(C2H5)2] (6) and [(2-Et2N-C6F4)(2-C5H4N)N]Sb(F)-
Introduction
reaction of C6F5ϪCHϭNϪ(C6H4-o-NH2) or similar Schiff
bases with different TMCs [W(CO)3(PrCN)3, Ni(COD)2
(COD ϭ 1,5-cyclooctadiene) etc.], which give stable prod-
ucts of metal insertion into a CϪF bond, should be
noted.[4,6,7] Two different mechanisms have been suggested
by Roundhill and co-workers for aromatic nucleophilic
During the past 50 years there has been a continuing
interest in the chemistry of polyfluoro aromatic com-
pounds. The main reason for this is that the unique proper-
ties of these derivatives suggest their possible use in various
technological fields.[1,2] One of the most urgent aims of or-
ganofluorine chemistry is the preparation of polyfluorin-
ated compounds with desired structures. As is well-known,
organofluorine ligands have found widespread application
substitution
of
the
ortho-F
atom
in
trans-
[PtMe(THF)(PPh2C6F5)2] by hydroxide or alkoxide ion,
one of which is an intramolecular process.[8]
Nucleophilic substitution reactions of an aryl carbon-flu-
in recent years for the stabilization of low-valent transition orine bond assisted by main group element compounds (al-
metal or main group species or for achieving unusual mo- kali, alkaline earth metals and silicon derivatives) have been
lecular geometries.[1,2] There is also a strong interest in acti- investigated to a considerable extent.[3,4,9Ϫ11] However, to
vation of the CϪF bond in polyfluoro organic compounds the best of our knowledge, most of the mechanistically
due to the possible utilization of these activation processes studied examples have been ascribed to intermolecular pro-
in organic synthesis.[3] A variety of methods for activating cesses, although suppositions about intramolecular origins
CϪF bonds with transition metal centers have been pub- have been made for exclusively ortho-directed fluorine-atom
lished in the last two decades. Several catalytic systems substitution for C6F5X species (X containing carbon or sul-
based on transition metals have been used for the replace- fur multiple bonds to oxygen or nitrogen atoms) in reac-
ment of an F atom in polyfluoro aryl moieties, mostly by tions with Li or Mg reagents, such as ArLi, AlkMgHal,
oxidative addition reactions.[3Ϫ5] Although only a few ex- ArMgHal or ArN(R)MgHal.[11,12]
amples of early transition metal complexes (TMCs) useful
for CϪF bond activation have been found, most of the re-
ported processes involving TMCs occur with late transition
metals. As a common example of intramolecular oxidative
addition of a CϪF bond to a transition-metal center the
As part of our program to investigate the structure and
the chemical behavior of hypervalent main-group-element
compounds
with
intramolecular
transannular
interactions[13Ϫ15] we herein report the reaction of
Sb(NEt2)3 (1) with C6F5NH(2-C5H4N) (2, LH), which leads
to the antimony tris-amides 3Ϫ5 with one, two or three
C6F5-(2-pyridyl)-amine groups, respectively. Compounds 3
and 4 are unexpectedly unstable and they react further to
give bis-amido antimony fluorides 6 and 7, respectively,
after 21 days in almost quantitative yield. To the best of
our knowledge no such intramolecular rearrangements have
been reported previously. Schrock et al. have found that a
[a]
Fachbereich Chemie, Philipps-Universität Marburg,
Hans-Meerwein-Strasse, 35032 Marburg/Lahn, Germany
Fax: (internat.) ϩ49-(0)6421-28-28917
E-mail: jsu@chemie.uni-marburg.de
[b]
Chemistry Department Moscow State University,
B-234 Leninskie Gory, 119899 Moscow, Russia
Fax: (internat.) ϩ7-095-932-8846
E-mail: sergej@org.chem.msu.su
2498
 2004 Wiley-VCH Verlag GmbH & Co. KGaA, Weinheim
DOI: 10.1002/ejic.200400074
Eur. J. Inorg. Chem. 2004, 2498Ϫ2503

Intramolecular Nucleophilic Substitution in a C6F5 Moiety
FULL PAPER
similar nucleophilic substitution product formed (23% to the Sb atom, adjacent to the C6F4 ring in fluorides 6 and
yield) in the reaction of Mo(NMe2)4 with 7 stops the rotation of the C6F4NEt2 group and the Py
(C6F5NHCH2CH2)2NMe. However, they were unable to group of this ligand about the CϪN bonds in C6D6 solu-
determine whether this was due to an intra- or intermolecu- tion. This immobility results in the presence of two different
lar process.[16] The structure of 7 was confirmed by X-ray signals for the N(CH2)2 carbon atoms of the NEt2 group
diffraction studies. DFT calculations, which reproduce the adjacent to the C6F4 ring (marked with an asterisk below)
principal features of the geometry of compound 7, have in the 13C NMR spectra of 6 and 7, a broadening of the
1
been used to distinguish possible reaction pathways.
N(CH2)2 signal in the H NMR spectra of 6 and 7 (broad
singlet instead of a quadruplet) as well as the presence of
two different signals for the protons and carbons of CH2ЈЈ.
Results and Discussion
Treatment of Sb(NEt2)3 (1) with two or three equivalents
of ligand LH (2) in toluene afforded amides 4 or 5, respec-
tively (Scheme 1). Compound 4 is unstable in toluene solu-
tion as well as in C6D6 solution and reacts further to give
fluoride 7 after 21 days at room temperature. The reaction
of 1 with one equivalent of LH led to reaction mixture A,
consisting of 3 (as a major component) and 4 as well as
starting material 1, after 12 hours. Unfortunately, it was
impossible to prepare compound 3 in a pure form. How-
ever, NMR spectroscopy data unambiguously confirm its
structure. As for 4, compound 3 (reaction mixture A) is un-
stable in solution and reacts further to give fluoride 6 after
21 days at room temperature. After recrystallization in or-
der to remove traces of compound 7 partially formed from
4, fluoride 6 was obtained as a pure solid. At the same time
only compound 5 has been found in the reaction of 1 with
three equivalents of LH (2) and no traces of fluorides 6 or
7 have been detected during this process. Hydrolysis of 6
after standard workup led, with moderate yield, to free am-
ine 8, which is difficult to access by other methods.
Single crystals of 7 were obtained as a toluene solvate
from toluene solution (Ϫ30 °C). The molecular structure is
presented in Figure 1; selected bond length and angles are
summarized in Table 1. The primary coordination environ-
ment of the Sb atom is formed by the nitrogen atoms N(1)
and N(14) and the F(1) atom, and may be treated as a trig-
˚
onal pyramid. The SbϪNcov distances [2.103(2), 2.089(2) A]
are similar to those found for the closely related diamide
ClSb[N(SiMe3){2-(6-Mepy)}]2 (6-MepyH ϭ 6-methylpyri-
[17]
˚
dine) [2.074(3)Ϫ2.127(8) A]
and somewhat shorter
than in the tris-amide Sb[N(SiMe3){2-(6-Mepy)}]3
[18]
˚
[2.159(3)Ϫ2.167(3) A].
The Sb(1)ϪF(1) distance
˚
[1.931(1) A] is slightly shorter than those in the monofluor-
ide FSb(1,2-O2C6H4)·1,10-phenanthroline [1.965(7) A]
[19]
˚
and the difluoride F2Sb[OC(OCH3)(2-pyridyl)2] [1.967(4)
[20]
˚
A], but slightly longer than those in [SbF3·{3-NH2C(O)-
[21]
˚
pyridine}2] [1.911(8), 1.986(6) A].
Internal coordination
of both NPyridine atoms and the N atom of the Et2N group
to antimony leads to a six-coordinate antimony in a
Scheme 1
The 1H, 13C, and 19F NMR spectra of 3Ϫ8 are consistent
with the proposed structural formula. In particular, the
presence of the NEt2 group, which is probably coordinated toluene molecule are omitted for clarity
Figure 1. Molecular structure of 7; hydrogen atoms and solvate
Eur. J. Inorg. Chem. 2004, 2498Ϫ2503
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S. S. Karlov et al.
FULL PAPER
˚
Table 1. Most important bond lengths (A) for 7 (X-ray data) and for 4, ts and 7 (calculated data)
Compound
N(1)ϪSb(1)
N(9)ϪSb(1)
N(14)ϪSb(1)
N(22)ϪSb(1)
N(27)ϪSb(1)
F(1)ϪSb(1)
N(27)ϪC(16)
F(1)ϪC(16)
7 (X-ray data)
2.103(2)
N(20)ϪSb(1)
2.163
2.160
2.197
2.780
N(22)ϪSb(1)
2.679
2.768
2.763
2.089(2)
N(2)ϪSb(1)
2.172
2.126
2.201
2.664
N(4)ϪSb(1)
2.647
2.563
2.685
2.848
N(38)ϪSb(1)
3.070
2.326
2.057
1.931(1)
F(16)ϪSb(1)
1.984
2.802
3.364
1.429(2)
N(38)ϪC(11)
1.428
1.714
3.290
3.006
F(16)ϪC(11)
3.135
1.560
1.349
4 (calcd. data)
ts (calcd. data)
7 (calcd. data)
strongly distorted octahedral environment, with the N(22)
and F(1) atoms in axial positions and the four nitrogen
atoms N(1), N(9), N(14), and N(27) in equatorial sites. It
should be noted that the axial transannular Sb(1)ϪN(22)
bond is considerably shorter than the equatorial transannu-
lar N(27)ϪSb(1) and N(9)ϪSb(1) bonds. The SbϪNPyridyl
bond lengths [Sb(1)ϪN(22), N(9)ϪSb(1)] are similar to the
values reported for an Sb compound contained pyridine
moieties (2.371Ϫ2.837 A).[22,23] The SbϪNEt2 transannular
˚
bond length is similar to analogous SbϪNMe2 contacts re-
[24Ϫ26]
˚
ported previously [2.766(4)Ϫ3.04(2) A]
and shorter
than those in the hexacoordinate complex [Sb(2-
[26]
˚
Me2NCH2C6H4)3] [3.03(2)Ϫ3.04(2) A].
Finally, there is
no short intramolecular contact between Sb and any of the
F atoms (the sum of the van der Waals radii of Sb and F
is 3.66 A).
Figure 2. DFT calculated structure of 4; hydrogen and fluorine
atoms (except F16) are omitted for clarity
[27]
˚
In order to get a better understanding of the driving for-
ces of this unusual ortho-directed methatetic fluoride-amide
rearrangement of 4 to 7 (Figure 2Ϫ4) we carried out DFT
calculations on compounds 4 and 7 up to the PBE level of
theory. The most important calculated geometric param-
eters of these compounds are listed in Table 1. Taking into
consideration that no X-ray derived structure of 4 is avail-
able, the calculated geometric data for this molecule are of
particular interest. The primary coordination environment
of the Sb atom in 4 may be treated as a trigonal pyramid.
The SbϪNPy distances are significantly smaller than the
sum of the van der Waals radii of antimony and nitrogen
[27]
˚
(3.74 A). Consequently, the Sb atom can be regarded as
[3ϩ2]-coordinated in 4; the presence of an additional short
contact between the Sb atom and one fluorine atom of the
˚
C6F5 group (3.36 A) should be noted. Such steric proximity
may be one of reasons for the easy rearrangement.
The DFT calculations predict that the geometry of 7 is
significantly more stable (30.25 kcal molϪ1) than that of 4.
The relative energies and reaction barriers calculated at
various computational levels are listed in Table 2. Taking
into consideration the calculated structure of compound 4
(steric proximity of Sb atom and one fluorine atom of the
Figure 3. DFT calculated structure of ts; hydrogen and fluorine
atoms (except F16) are omitted for clarity
C6F5 group) and the absence of meta- or para-substitution ometry should be noted. The computed barrier of gas-
products a concerted reaction pathway may be proposed for phase interconversion of 4 into 7 is low (27.70 kcal molϪ1).
the nucleophilic process. We have calculated the transition- According to the literature the calculated activation barrier
state geometry (ts) of this process (Figure 3). A considerable of insertion reactions of Pd(PH3)2 into the CϪF bond of
shortening of the Et2NϪC distances accompanied by an different fluoroarenes (FϪC6H3XY, X,Y ϭ H, CN, NO2)
elongation of the CϪF bond was found in ts in comparison lies within the range 21.8Ϫ41.2 kcal molϪ1 (RB3LYP/
with that in 4. An analogous alteration is observed for the DZVP level of theory).[28] The use of the COSMO solvation
SbϪF and SbϪNEt2 distances. The considerable shift of model does not drastically change these results. The compu-
the F atom from the plane of the phenyl ring in the ts ge- tational investigation of a single-step mechanism for the
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Eur. J. Inorg. Chem. 2004, 2498Ϫ2503

Intramolecular Nucleophilic Substitution in a C6F5 Moiety
FULL PAPER
and C6F5NH(2-C5H4N)[31] were
[30]
Starting materials Sb(NEt2)3
prepared according to the literature. C6D6 was obtained from De-
1
utero GmbH and dried over sodium. H, 13C, and 19F NMR spec-
tra were recorded on a Bruker AC200 FT NMR and Bruker AC300
FT NMR spectrometers (in C6D6 at 23 °C). Chemical shifts in the
1H and 13C NMR spectra are given in ppm relative to internal
SiMe4; 19F NMR experiments are referenced to CFCl3 as an exter-
nal standard. Mass spectra (EI-MS) were recorded on a Varian
CH-7a device using electron-impact ionization at 70 eV; mass spec-
tra (FD-MS) were recorded on an HP-5989B device; all assign-
ments were made with reference to the most abundant isotopes.
Elemental analyses were carried out by the Fachbereich Chemie of
the Philipps University Marburg (Heraeus Rapid Analyzer). In this
work, the nonempirical generalized gradient approximation (GGA)
for the exchange-correlation functional of Perdew et al. (PBE) was
employed and single point RI-MP2//PBE calculations were
used.[32Ϫ36] All calculations were performed using the program
‘‘PRIRODA’’ developed by Laikov, which implements an economi-
cal computational procedure.[37] The all-electron large orbital basis
sets of contracted Gaussian-type functions of the size (5s1p):[3s1p]
for H, (11s6p2d):[4s3p2d] for C, (11s6p2d):[4s3p2d] for N,
(11s6p2d):[4s3p2d] for F and (22s19p12d):[7s6p4d] for Sb were
used for DFT-PBE. The all-electron basis set of contracted Gaus-
sian-type functions of the size Sb {17,18,19,20,21,22/
13,14,15,16,17/9,10,11}, N {8,9,10/5,6/2}, C {8,9,10/5,6/2}, H {5,6/
2}, F {8,9,10/5,6/2} were used for RI-MP2. The frozen-core
approximation was used in the RI-MP2 calculations. Full geometry
optimization was performed by DFT-PBE for a number of struc-
tures followed by vibrational-frequency calculation using analytical
first and second derivatives. Each structure was characterized by
the vibrational analysis. The transition state has only one imagin-
ary normal mode and equilibrium geometry states have only real
normal modes. An IRC (intrinsic reaction coordinate) calculation
was run starting from the transition-state geometry in both direc-
tions and verified the initial and final structures linked to the tran-
sition state. Transition-state normal modes were animated using
MOLDEN.[38] Coordinates and normal modes for 1, 2, and ts in
MOLDEN format are available from the author upon request. The
present theoretical method has previously given very useful results
in antimony chemistry.[8]
Figure 4. DFT calculated structure of 7; hydrogen and fluorine
atoms (except F16) are omitted for clarity
aromatic nucleophilic substitution of halobenzenes and
halonitrobenzenes with halide anions for the reaction
C6H5X ϩ XϪ Ǟ C6H5X ϩ XϪ (X ϭ Cl, Br, I) gave similar
values for the activation barrier (24.0Ϫ24.5 kcal molϪ1) at
the MP2/6-31ϩG(d) ϩ ZPE(HF/6-31ϩG(d) level.[29]
Table 2. Relative energies (kcal·molϪ1) of compounds 4 and 7 as
well as the transition state (ts) of the rearrangement 4 Ǟ 7 (acti-
vation barrier in square brackets) calculated at various compu-
tational levels
PBE
PBE-ZPE
RI-MP2//PBE
4
ts
7
30.25
57.95 [27.70]
0
29.26
57.18 [27.92]
0
29.78
62.37 [32.59]
0
Conclusion
Diethylaminobis[N-pentafluorophenyl-N-(2-pyridyl)amino]stibane,
[Et2NSb{N(C6F5)(2-C5H4N)}2] (4): A solution of amine 2 (1.09 g,
4.2 mmol) in toluene (20 mL) was added dropwise at Ϫ78 °C to a
stirred solution of the stibane 1 (0.70 g, 2.1 mmol) in toluene
(15 mL). The reaction mixture was stirred for 12 h at room tem-
perature and all volatiles were removed under reduced pressure to
give 4 as a yellow oil (yield 1.43 g, 97%). 1H NMR (C6D6,
300.130 MHz): δ ϭ 0.74 (t, 6 H, CH3), 2.98 (q, 4 H, NCH2), 5.69
(m, 2 H), 6.18 (m, 2 H), 6.85 (m, 2 H), 7.73 (m, 2 H) (hydrogen
atoms of pyridyl group) ppm. 13C NMR (C6D6, 75.47 MHz): δ ϭ
15.22 (CH3), 43.82 (NCH2), 107.00, 114.11, 138.93, 145.79, 160.76
(carbon atoms of pyridyl groups) ppm; the signals of the carbon
atoms of C6F5 were not detected. 19F NMR (C6D6, 200.13 MHz):
δ ϭ Ϫ164.45 (br. t, 4 F), Ϫ159.58 (br. t, 2 F), Ϫ143.95 (br. d, 4 F)
ppm. FD-MS: m/z (%) ϭ 711 (100) [Mϩ].
This paper reports the syntheses of antimony tris-amides
(Et2N)3ϪnSb[N(C6F5)(2-C5H4N)]n [n ϭ 1 (3), 2 (4) or 3 (5)]
upon reaction of antimony tris-diethylamide (1) with
stoichiometric amounts of HN(C6F5)(2-C5H4N) (2).
Compounds 3 and 4 are unstable in solution and rearrange
to
the
corresponding
fluorides
[(2-Et2N-C6F4)-
(2-C5H4N)N]Sb(F)[N(C2H5)2] (6) and [(2-Et2N-C6F4)-
(2-C5H4N)N]Sb(F)[N(C6F5)(2-C5H4N)] (7). A concerted
mechanism of nucleophilic substitution has been proposed
for this rearrangement according to density functional cal-
culations. Hydrolysis of 6 provides a new entry to the tri-
dentate amine [(2-Et2N-C6F4)(2-C5H4N)NH.
Bis(diethylamino)[N-pentafluorophenyl-N-(2-pyridyl)amino]stibane,
[(Et2N)2Sb{N(C6F5)(2-C5H4N)}] (3): Following the same exper-
imental procedure as for 4 using 1 (0.67 g, 2.0 mmol), 2 (0.52 g,
2.0 mmol), and toluene (20 mL). Isolated as a yellow oil (reaction
mixture A, 1.01 g; according to 1H NMR spectroscopy the ratio
1:3:4 was approximately 1:2:1). Data for 3: 1H NMR (C6D6,
200.130 MHz): δ ϭ 0.92 (t, 12 H, CH3), 3.00 (q, 8 H, CH2), 5.80
Experimental Section
General Remarks: All manipulations were performed under a dry,
oxygen-free argon atmosphere using standard Schlenk techniques.
Solvents were dried by standard methods and distilled prior to use.
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S. S. Karlov et al.
FULL PAPER
(m, 1 H), 6.30 (m, 1 H), 7.00 (m, 1 H), 7.91 (m, 1 H) (hydrogen
N-(2-Diethylamino-3,4,5,6-tetrafluorophenyl)-N-(2-pyridyl)amine,
atoms of pyridyl group) ppm. 13C NMR (C6D6, 50.32 MHz): δ ϭ HN(C6F5)(2-C5H4N) (8): Water (2 mL) was added to a solution of
16.23 (CH3), 42.91 (CH2), 106.79, 114.10, 138.54, 147.05, 161.00
(carbon atoms of pyridyl groups) ppm; the signals of the carbon
stibane 6 (0.55 g, 1.1 mmol) in toluene (10 mL). The organic layer
was separated, dried over Na2SO4 and all volatiles were removed
atoms of C6F5 were not detected. 19F NMR (C6D6, 188.28 MHz): under reduced pressure. Recrystallization of the residue from n-
1
δ ϭ Ϫ164.04 (br. t, 2 F), Ϫ159.12 (t, 1 F), Ϫ145.46 (br. d, 2 F)
heptane gave colorless crystals of 8 (yield 0.10 g, 61%). H NMR
(C6D6, 200.13 MHz): δ ϭ 0.65 (t, 6 H, CH3), 2.66 and 2.67 (2 q, 4
H, NCH2), 5.25 (br. s, 1 H, NH), 6.25 and 6.27 (2 m, 1 H), 6.39
(m, 1 H), 7.03 (m, 1 H), 8.14 (m, 1 H) (hydrogen atoms of pyridyl
group) ppm. 19F NMR (C6D6, 188.28 MHz): δ ϭ Ϫ166.09 (br. t,
1 F), Ϫ160.77 (br. t, 1 F), Ϫ148.91 (br. d, 1 F), Ϫ141.88 (br. d, 1
F) ppm. C15H15F4N3 (313.29): calcd. C 57.51, H 4.83, N 13.41;
found C 57.23, H 4.69, N 12.94.
ppm. FD-MS: m/z (%) ϭ 524 (3) [Mϩ].
Tris[N-pentafluorophenyl-N-(2-pyridyl)amino]stibane, [Sb{N-
(C6F5)(2-C5H4N)}3] (5): Following the same experimental pro-
cedure as for 4 using 1 (0.56 g, 1.7 mmol), 2 (1.29 g, 5.0 mmol),
and toluene (20 mL); yellow crystals (1.27 g, 83%) were obtained.
1H NMR (C6D6, 200.13 MHz): δ ϭ 5.56 (m, 3 H), 6.04 (m, 3 H),
6.77 (m, 3 H), 7.68 (m, 3 H) (hydrogen atoms of pyridyl group)
ppm. 13C NMR (C6D6, 50.32 MHz): δ ϭ 107.05, 113.92, 139.53,
145.46, 160.42 (carbon atoms of pyridyl groups) ppm; the signals
of the carbon atoms of C6F5 were not detected. 19F NMR (C6D6,
188.28 MHz): δ ϭ Ϫ164.53 (br. s, 6 F), Ϫ160.83 (br. t, 3 F), 144.51
(br. s, 6 F) ppm. EI-MS: m/z (%) ϭ 898 (52) [Mϩ], 639 (39) [Mϩ
Ϫ N(C5H4N)(C6F5)]. C33H12F15N6Sb (899.25): calcd. C 44.08, H
1.35, N 9.35; found C 43.87, H 1.31, N 9.15.
X-ray Crystallographic Study. Crystal Data for 2: C33H26F10N5Sb,
Mr ϭ 804.34, triclinic, a ϭ 8.5318(5), b ϭ 11.6819(7), c ϭ 16.680(1)
3
˚
˚
A, α ϭ 83.687(5), β ϭ 77.456(5), γ ϭ 83.518(5)°, V ϭ 1606.2(2) A ,
space group P1, Z ϭ 2, Dc ϭ 1.663 g·cmϪ3, F(000) ϭ 800, µ(Mo-
¯
Kα) ϭ 0.950 mmϪ1. Colourless crystal of approximate dimensions
0.45 ϫ 0.27 ϫ 0.18 mm3 was used for data collection. Total of
23604 reflections (6418 unique, Rint ϭ 0.0366) were measured on
a Stoe IPDS-2 diffractometer (graphite-monochromatized Mo-Kα
Diethylamino[N-(2-diethylamino-3,4,5,6-tetrafluorophenyl)-N-(2-
pyridyl)amino]fluorostibane, [(Et2N)Sb(F){N(C6F5)(2-C5H4N)}] (6):
A solution of amide 3 (from reaction mixture A, 0.55 g, 1.1 mmol)
in toluene (5 mL) was stirred for 21 days at room temperature and
all volatiles were then removed under reduced pressure. Recrystalli-
zation of the residue from toluene/n-pentane (Ϫ30 °C) gave color-
˚
radiation, λ ϭ 0.71073 A) at 193(2) K. Data were collected in the
range 1.76 Ͻ θ Ͻ 26.19° (Ϫ10 Յ h Յ 10, Ϫ14 Յ k Յ 14, Ϫ20 Յ 1
Յ 20). Absorption correction based on measurements of equivalent
reflections resulted in transmission factors 0.6607/0.9884. The
structure was solved by direct methods (SHELXS-86)[39] and re-
fined by full-matrix least-squares on F2 (SHELXL-97)[40] with an-
isotropic thermal parameters for all non-hydrogen atoms. All H
atoms (except methyl hydrogens of solvate toluene) were refined
isotropically. All other H atoms were refined by using a riding
model. The final residuals were: R1 ϭ 0.0232 for 5935 reflections
with I Ͼ 2σ(I) and wR2 ϭ 0.0619 for all data with 535 parameters.
less crystals of
6
(yield 0.36 g, 66%). 1H NMR (C6D6,
200.13 MHz): δ ϭ 0.83 (br. s, 6 H, CH3 of o-Et2NC6F4 group),
1.03 (t, 6 H, CH3 of Et2NSb group), 2.95 (br. s, 4 H, CH2 of o-
Et2NC6F4 group), 3.23 (q, 4 H, CH2 of SbNCH2), 5.79 and 5.80
(2 m, 1 H, CHЈЈ), 6.17 (m, 1 H,), 6.96 (m, 1 H), 7.62 (m, 1 H)
(hydrogen atoms of pyridyl group) ppm. 13C NMR (C6D6,
50.32 MHz): δ ϭ 12.13 (CH3 of o-Et2NC6F4 group), 16.38 (CH3
of Et2NSb group), 43.56 (SbNCH2), 46.19 and 46.25 (CH2 of o-
Et2NC6F4 group), 106.55 and 106.58 (CHЈЈ), 112.96, 139.45,
145.42, 167.72 (carbon atoms of pyridyl groups) ppm; the signals
of the carbon atoms of C6F5 were not detected. 19F NMR (C6D6,
188.28 MHz): δ ϭ Ϫ162.04 (br. t, 1 F), Ϫ161.42 (br. t, 1 F),
Ϫ160.04 (br. s, 1 F, FϪSb), Ϫ148.02 (br. d, 1 F), Ϫ146.01 (br. d,
1 F) ppm. FD-MS: m/z (%) ϭ 524 (13) [Mϩ], 505 (23) [Mϩ Ϫ F],
452 [Mϩ Ϫ NEt2]. C19H24F5N4Sb (525.17): calcd. C 43.45, H 4.61,
N 10.67; found C 42.63, H 4.74, N 10.29.
Ϫ3
˚
Goof ϭ 1.030, max. ∆ρ ϭ 0.370 e·A
.
CCDC-225205 (for 2) contains the supplementary crystallographic
data for this paper. These data can be obtained free of charge at
www.ccdc.cam.ac.uk/conts/retrieving.html [or from the Cambridge
Crystallographic Data Centre, 12 Union Road, Cambridge
CB2 1EZ, UK; Fax: (internat.) ϩ44-1223-336-033; E-mail:
deposit@ccdc.cam.ac.uk].
Acknowledgments
We thank Dr. A. V. Churakov for helpful discussions and Dr. D.
N. Laikov for placing at our disposal the program ‘‘PRIRODA’’.
We thank also the Research Computing Center of the Moscow
State University for computational time.
[N-(2-Diethylamino-3,4,5,6-tetrafluorophenyl)-N-(2-pyridyl)amino]-
[N-(pentafluorophenyl)-N-(2-pyridyl)amino]fluorostibane, [{(2-Et2N-
C6F4)(2-C5H4N)N}Sb(F){N(C6F5)(2-C5H4N)}] (7): A solution of
amide 4 (1.23 g, 1.7 mmol) in toluene (5 mL) was stirred for 21
days at room temperature. Storage at Ϫ30 °C overnight resulted in
colorless crystals of 7 (yield 0.87 g, 71%). 1H NMR (C6D6,
300.130 MHz): δ ϭ 0.74 (br. t, 6 H, CH3), 2.82 (br. s, 4 H, NCH2),
5.60 and 5.62 (2 m, 1 H, CHЈЈ), 5.77 (m, 1 H), 6.02 (m, 1 H), 6.31
(m, 1 H), 6.77 (m, 1 H), 6.99 (m, 1 H), 7.66 (m, 1 H), 7.99 (m,
1 H) (hydrogen atoms of pyridyl group) ppm. 13C NMR (C6D6,
75.47 MHz): δ ϭ 11.61 (CH3), 46.20 and 46.30 (NCH2), 106.26
and 106.35 (CHЈЈ), 106.81, 113.66, 114.16, 139.11, 139.97, 144.56,
146.43, 160.73, 161.23 (carbon atoms of pyridyl groups) ppm; the
signals of the carbon atoms of C6F5 were not detected. 19F NMR
(C6D6, 188.28 MHz): δ ϭ Ϫ164.45 (br. s, 2 F), Ϫ160.64 (br. t, 1
F), Ϫ160.07 (br. t, 1 F), Ϫ159.18 (br. t, 1 F), Ϫ154.72 (br. s, 1 F,
FϪSb), Ϫ147.20 (br. d, 1 F), Ϫ146.85 (br. d, 1 F), Ϫ143.96 (br. t,
2 F) ppm. FD-MS: m/z (%) ϭ 711 (45) [Mϩ]. C26H18F10N5Sb
(712.20): calcd. C 43.85, H 2.55, N 9.83; found C 43.47, H 2.64,
N, 9.08.
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