ortho-oirected metathetical fluoride/amide exchange in (pentafluorophenyl)- amides

Article abstract of DOI:10.1002/ejic.200700772

The indium tris(amide)s [(Et₂N)_3-nIn{N(C ₆F₅)(2-C₅H₄N)}_n] [n = 1 (15), 2 (16) or 3 (9)] have been prepared by treatment of [In(NEt ₂)₃]₂ (3) with a stoichiometric amount of (2-C₅H₄N)-(C₆F₅)NH (1). The analogous reaction of Bi(NMe₂)₃ (2) with 3 equiv. of amine 1 and the treatment of BiCl₃ (5) with a stoichiometric amount of (2-C₅H₄N)(C₆F₅)NLi (4) both lead to [Bi{N(C₆F₅)(2-C₅H₄N)}₃] (10). In contrast, only the difluoride 11 or the monofluoride 12, which are the products of intramolecular ortho-directed exchange of NMe₂ and F substituents, are obtained from the reaction of 2 with 1 or 2 equiv. of 1, respectively. The reaction between Me₃Sb(Hal)₂ [Hal = Br (7) Cl, (8)] and 1 or 2 equiv. of lithium salt 4 gives the corresponding stable monoamides [Me₃(Hal)Sb{N(C₆F₅)(2-C ₅H₄N)}] [Hal = Br (17), Cl (18)] or bis(amide) [Me ₃Sb(N(C₆F₅)(2-C₅H ₄N)}₂] (19), respectively. The structure of 9 has been confirmed by an X-ray structure analysis, and density functional calculations data have been used to explain the possible reaction pathway of the ortho-directed metathetical fluoride/amide exchange. Wiley-VCH Verlag GmbH & Co. KGaA, 2007.

Full text of DOI:10.1002/ejic.200700772

FULL PAPER
DOI: 10.1002/ejic.200700772
ortho-Directed Metathetical Fluoride/Amide Exchange in (Pentafluorophenyl)-
amides[‡]
Pavel L. Shutov,[a] Sergey S. Karlov,*[b] Klaus Harms,[a] Maxim V. Zabalov,[b]
Jörg Sundermeyer,*[a] Jörg Lorberth,[a] and Galina S. Zaitseva[b]
Keywords: Fluorinated ligands / Amides / Nucleophilic substitution / Density functional calculations
The indium tris(amide)s [(Et2N)3–nIn{N(C6F5)(2-C5H4N)}n] [n
= 1 (15), 2 (16) or 3 (9)] have been prepared by treatment of
[In(NEt2)3]2 (3) with a stoichiometric amount of (2-C5H4N)-
(C6F5)NH (1). The analogous reaction of Bi(NMe2)3 (2) with
3 equiv. of amine 1 and the treatment of BiCl3 (5) with a stoi-
chiometric amount of (2-C5H4N)(C6F5)NLi (4) both lead to
[Bi{N(C6F5)(2-C5H4N)}3] (10). In contrast, only the difluoride
11 or the monofluoride 12, which are the products of intramo-
lecular ortho-directed exchange of NMe2 and F substituents,
are obtained from the reaction of 2 with 1 or 2 equiv. of 1,
respectively. The reaction between Me3Sb(Hal)2 [Hal = Br (7)
Cl, (8)] and 1 or 2 equiv. of lithium salt 4 gives the corre-
sponding stable monoamides [Me3(Hal)Sb{N(C6F5)(2-
C5H4N)}] [Hal
=
Br (17), Cl (18)] or bis(amide)
[Me3Sb{N(C6F5)(2-C5H4N)}2] (19), respectively. The structure
of 9 has been confirmed by an X-ray structure analysis, and
density functional calculations data have been used to ex-
plain the possible reaction pathway of the ortho-directed
metathetical fluoride/amide exchange.
(© Wiley-VCH Verlag GmbH & Co. KGaA, 69451 Weinheim,
Germany, 2007)
in reactions with Li or Mg reagents such as ArLi,
RMg(Hal), ArMg(Hal) or ArN(R)Mg(Hal).[13,14]
Introduction
There has been a strong interest in activation of the C–
F bond in polyfluoro organic compounds during the past
several decades due to the possible utilization of these acti-
vation processes in organic synthesis.[2,3] A variety of meth-
ods for activating C–F bonds with transition metal centers
have been published recently, and several examples based
on early, middle, or late transition metal compounds have
been used for the replacement of an F atom in polyfluo-
roaryl moieties, mostly by oxidative addition reactions.[4–11]
Nucleophilic substitution reactions of an aryl carbon–fluor-
ine bond assisted by main group element compounds (alkali
and alkaline earth metals or silicon derivatives) have also
been widely investigated.[4,5,12,13] However, to the best of
our knowledge, most of the mechanistically studied exam-
ples have been ascribed to intermolecular processes. As-
sumptions about intramolecular pathways have been made
exclusively for ortho-directed fluorine atom substitution for
C6F5X species (X is a ortho-directing donor functionality)
Recently, we reported the reaction of Sb(NEt2)3 with
C6F5(2-C5H4N)NH (1), which leads to the antimony tris-
(amide)s [(Et2N)2Sb{N(C6F5)(2-C5H4N)}], [(Et2N)Sb{N-
(C6F5)(2-C5H4N)}2], and [Sb{N(C6F5)(2-C5H4N)}3] with
one, two, or three pentafluoro(2-pyridyl)anilido groups.[1]
Trivalent antimony compounds containing one or two NEt2
groups are unexpectedly unstable, and they rearrange to
give the bis(amido)antimony fluorides [SbF{N(C6F5)(2-
C5H4N)}2] and [(Et2N)SbF{N(C6F5)(2-C5H4N)}], in al-
most quantitative yield at room temperature within 21 d.[1]
To the best of our knowledge no such intramolecular re-
arrangements have been reported previously except in a pa-
per by Schrock et al., where a similar nucleophilic substitu-
tion product is reported in low yield in the reaction of
Mo(NMe2)4 with (C6F5NHCH2CH2)2NMe.[15] In order to
gain further insight into the fluoride/amide metathesis as-
sisted by antimony, and to expand the scope of this reac-
tion, we report herein our investigation of the analogous
transamination reactions of Bi(NMe2)3 (2) and [In-
(NEt2)3]2 (3) with C6F5NH(2-C5H4N) (1). The reactions of
the lithium salt of amine 1, namely C6F5NLi(2-C5H4N) (4),
with BiCl3 (5), InCl3 (6), Me3SbBr2 (7), and Me3SbCl2 (8)
are also reported. The structure of the novel monomeric
indium tris(amide) [In{N(C6F5)(2-C5H4N)}3] (9) is con-
firmed by X-ray crystallography, and density functional cal-
culations are used to distinguish possible rearrangement
pathways.
[‡] The Case of Bismuth and Indium, II. Part I: Ref.[1]
[a] Fachbereich Chemie, Philipps-Universität Marburg,
Hans-Meerwein-Strasse, 35032 Marburg/Lahn, Germany
Fax: +49-6421-28-28917
E-mail: jsu@chemie.uni-marburg.de
[b] Chemistry Department Moscow State University,
B-234 Leninskie Gory, 119899 Moscow, Russia
Fax: +7-95-932-8846
E-mail: sergej@org.chem.msu.ru
Supporting information for this article is available on the
WWW under http://www.eurjic.org or from the author.
5684
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Fluoride/Amide Exchange in (Pentafluorophenyl)amides
of 2 with 3 equiv. of 1. Thus, intramolecular nucleophilic
substitution at a C6F5 moiety assisted by bismuth proceeds
much faster than that for antimony derivatives. Hydrolysis
of 11 and 12 led to the tris(amine)s 13 and 14, which are
difficult to synthesize by other methods.
In contrast to the reaction patterns of Sb and Bi com-
pounds, the transamination of In amide 3 with 1, 2, and
3 equiv. of 1 selectively led to the corresponding tris-
(amide)s 15, 16, and 9, respectively. No similar rearrange-
ment processes were found in these studies [Equation (3)].
Results and Discussion
Synthesis
Ligand 1 was first prepared by treating 2-bromopyridine
with (pentafluorophenyl)amine,[16] although recently Ash-
enhurst et al. have used the approach of Koppang for the
synthesis of 1,[17] which involves the treatment of C6F6 with
an equimolar mixture of (2-pyridylamido)lithium and
LiNH2.[18] We also used this reaction to prepare amine 1,
although we modified the method according to Equa-
tion (1). The twofold excess of lithiated 2-pyridylamine per
mol of C6F6 is essential as product 1 is acidic enough to
quench the nucleophile.
(3)
The tendency to rearrange is higher for compounds with
a large covalent radius, low coordination number, and
highly polar M–N bonds. We assume that this is probably
more due to kinetic than to thermodynamic reasons. If the
covalent character in M–N bonding is increased, for exam-
ple by increasing the formal oxidation state of the central
atom, the compounds become more inert with respect to
rearrangement reactions: we observed that reaction of 1 or
2 equiv. of lithium amide 4 with (Hal)2SbMe3 (7 and 8) led
to the expected unrearranged monoamides 17 and 18 or
diamide 19 [Equation (4)]. While SbIII amides tend to re-
arrange, SbV amides are inert with respect to this fluoride/
amide exchange under ambient conditions.
(1)
Treatment of Bi(NMe2)3 (2) with 3 equiv. of amine 1 in
toluene and the reaction of lithium amide 4 with BiCl3 (5)
both afforded tris(amide) 2 in good yield [Equation (2)].
(2)
(4)
Treatment of Bi(NMe2)3 (2) with 1 or 2 equiv. of amine
1 led to difluoride 11 and monofluoride 12, respectively,
as products of a rearrangement reaction (Scheme 1). The
instability of the plausible intermediates [(NMe2)3–n
-
NMR Spectroscopic Study
Bi{N(C6F5)(2-C5H4N)}n] is in sharp contrast to the corre-
sponding antimony compounds, which only rearrange after
1
The H, 13C, and 19F NMR spectra of all compounds
extended reaction times.[1] Moreover, traces of both 11 and are consistent with a κ2-N,NЈ-bonding mode of the 2-pyr-
12 were detected by NMR spectroscopy during the reaction idylamido ligands. The solution spectra of bismuth fluo-
Scheme 1.
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S. S. Karlov, J. Sundermeyer et al.
FULL PAPER
rides 11 and 12 are very similar to their previously charac- gands or have ionic structures such as In(NCS)63–. Interest-
terized Sb analogs.[1] As already observed, the presence of ingly, the most closely related structure, that of [In(N3)3-
one or two NMe2 groups adjacent to the ipso-C atom of Py3],[20] possesses a mer configuration. As expected, the co-
the aromatic rings inhibits the rotation of these moieties valent In–Namido bonds in 9 [2.174(3)–2.202(2) Å] are
about the N–Cipso bond. N-coordination in a chelate ring shorter than the donor–acceptor In–NPy bonds [2.259(2)–
leads to the appearance of two signals for the NMe2 group 2.324(3) Å].
1
in the H NMR spectra of 11 and 12. In accordance with
these data, we assume that indium compounds 9, 15, and
16 are monomeric chelate complexes in C6D6 solutions.
It should be noted that two different configurations (fac
and mer) are possible for indium and bismuth tris(amide)s
9 and 10. Ashenhurst et al. found recently that the closely
related Al derivative [Al{N(C6F5)(2-C5H4N)}3] undergoes a
dynamic fac/mer isomerization in CDCl3 solutions at
1
25 °C.[18] The broadening of the signals in the H and 13C
NMR spectra of 9 and 10 indicates that a similar isomeriza-
tion process probably takes place here as well. The ability
of both 9 and 10 to isomerize in solution was confirmed by
the very close values of total energy for both isomers (see
Figure 2. Thermal ellipsoid drawing of the indium coordination
polyhedron in complex 9.
Density Functional Calculations section below).
Table 1. Selected bond lengths [Å] and angles [°] for complex 9 with
estimated standard deviations in parentheses.
Molecular Structure of 9
N1–In1
N7–In1
N14–In1
2.324(3)
2.174(3)
2.265(3)
147.9(1)
97.3(1)
112.7(1)
103.98(9)
59.92(9)
102.20(8)
97.7(1)
N20–In1
N27–In1
N33–In1
N20–In1–N14
N27–In1–N14
N7–In1–N1
N33–In1–N1
N20–In1–N1
N27–In1–N1
N14–In1–N1
2.202(3)
2.259(2)
2.190(3)
59.75(8)
153.64(9)
58.8(1)
The molecular structure of 9 is shown in Figures 1 and
2, and Table 1 summarizes selected geometrical parameters.
Compound 9 possesses a monomeric structure in the solid
state. The coordination sphere of the indium atom is a dis-
torted InN6 octahedron with three amido groups and three
pyridyl nitrogen atoms in a fac arrangement similar to the
structurally related complex [Al{N(C6F5)(2-C5H4N)}3].[18]
The distortion from octahedral geometry appears to be in-
duced by the steric constraints of the C6F5N(2-C5H4N) li-
gand. Analysis of the Cambridge Structural Database (Ver-
sion 5.28, November 2006)[19] reveals more than ten struc-
N7–In1–N33
N7–In1–N20
N33–In1–N20
N7–In1–N27
N33–In1–N27
N20–In1–N27
N7–In1–N14
N33–In1–N14
95.4(1)
149.61(9)
101.83(9)
102.16(9)
106.94(9)
No short contacts between In and the fluorine atoms of
tures with a similar InN6 structural fragment, most of the C6F5 groups are found in the solid state. The shortest
which contain either pyrazolylborate or phthalocyanine li- In···F contact in 9 of 3.585 Å (where F is an ortho-fluorine
Figure 1. Thermal ellipsoid drawing of complex 9. Hydrogen atoms and disordered toluene have been omitted for clarity. Displacement
ellipsoids are drawn at the 50% probability level.
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Eur. J. Inorg. Chem. 2007, 5684–5692

Fluoride/Amide Exchange in (Pentafluorophenyl)amides
atom) is larger than the sum of the van der Waals radii of eters of species in series (a) are listed in Table 2; the calcu-
indium and fluorine (3.40 Å).[21]
lated molecular structures of the compounds studied, the
most important geometry parameters of these species, and
the values of their total energies are listed in the Supporting
Information. According to the results of the density func-
tional calculations, the values of total energy for derivatives
(a) with NPyǞM bonds are larger than those for the corre-
sponding compounds (b) without these contacts for all spe-
cies studied. The differences between the energy values for
the starting materials lie within the range 7.03 (20) to
35.04 kcalmol–1 (16). The analogous values for the re-
arrangement products are 5.89 (20) to 41.27 kcalmol–1 (16).
It is of interest to note that the total energy of 9a(fac) is
practically identical to that of 9a(mer): ∆E = E[9a(fac)] –
E[9a(mer)] = 1.16 kcalmol–1; the same ∆E value was found
for the Bi compound 10a. This energy equivalence testifies
to the possibility of fac/mer conformational exchange in
solution for 9 and 10, as proposed on the basis of the NMR
spectroscopic data. The total energy values of 9a and 10a,
which possess NPyǞM bonds, are also larger than those for
9b and 10b, respectively. These differences are 51.41 [9(fac)]
and 52.49 kcalmol–1 [9(mer)], and 39.56 [10(fac)] and
35.31 kcalmol–1 [10(mer)]. We can therefore expect that all
metal derivatives of the C6F5N(2-C5H4N) ligand in ques-
tion possess intramolecular coordination in solution [series
(a)].
Density Functional Study on Metal Complexes and
Nucleophilic Substitution Reactions
To gain a better understanding of the driving force be-
hind the ortho-directed metathetic fluoride/amide re-
arrangements we carried out density functional calculations
at the PBE level of theory on a number of stable com-
pounds and metastable intermediates on the reaction coor-
dinate. The calculated structures and the reactions studied
are presented in Scheme 2.
It should be noted that the calculated parameters of com-
pound 9a(fac) (In–Namido 2.256 Å; In–NPy 2.332–2.333 Å)
are close to those found for the solid-state structure of 9
(see above). Consequently, we believe that the theoretical
method used gives reasonable results for indium derivatives;
the appropriateness of this method for Sb and Bi com-
pounds was confirmed by us previously.[1,22]
Taking into consideration that no X-ray structure of pre-
pared or proposed compounds is reported except for that
of 9a, the calculated geometrical data for the molecules
studied [series (a), with NPyǞM] are of particular interest.
The primary coordination environment of the Bi atom in
11a, 12a, and 20a–22a may be treated as a trigonal pyramid
as the Bi–NPy distances are smaller than the sum of the
van der Waals radii of bismuth and nitrogen (3.94 Å).[21]
Consequently, the Bi atom can be regarded as [3+1]-coordi-
nate in 20a and [3+2]-coordinate in 22a. Analogous [3+2]-
coordination is found in 11a due to additional interaction
of the Bi atom with one NMe2 group. In contrast to 11a,
however, the Bi atom in 21a should be regarded as [3+1]-
coordinate because no interaction between the Bi atom and
NMe2 group is found in this compound. The Bi atom in
12a possesses three additional contacts with nitrogen atoms
(two NPy and one NMe2), which means that the distortion
Scheme 2.
The compounds are likely to possess intramolecular con- of the primary trigonal-pyramidal coordination environ-
tacts between the metal atom and the pyridine nitrogen ment of the bismuth atom is maximal. The starting com-
atoms, therefore two different types of molecules were pounds 20a, 21a, and 22a also possess a short Bi–F contact
studied: derivatives containing additional intramolecular (3.592, 3.378, and 3.431 Å, respectively).
NPyǞM contacts (a) and derivatives without these contacts
The coordination polyhedron of the In atom in 15a and
(b). In the cases where several additional NPyǞM contacts 16a is a distorted tetrahedron (two In–NEt2 and one In–
are possible, structures with the maximum number of con- Namide and In–NPy bonds) and a distorted trigonal bipyr-
tacts were calculated. The most important geometry param- amid (In–NEt2 and two In–Namide and In–NPy bonds),
Eur. J. Inorg. Chem. 2007, 5684–5692
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S. S. Karlov, J. Sundermeyer et al.
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Table 2. Selected bond lengths [Å] for compounds 9a–12a, 15a–18a, 20a–26a, and TSIa–TSVIIa (calculated data). X-ray data for 9 are
given in square brackets.
Compound
M–Namide
M–N(py)
M–NR2
M–F[a]
M–Hal
9a(fac)
2.256, 2.256, 2.256,
[2.174(3)], [2.190(3)], [2.202(3)]
2.261, 2.267, 2.276
2.295, 2.397, 2.409
2.319, 2.349, 2.363
2.308
2.213
2.276
2.215
2.243
2.297, 2.299
2.262, 2.234
2.284, 2.406
2.280
2.198
2.224
2.244, 2.250
2.175, 2.269
2.201, 2.315
2.275
2.199
2.302
2.332, 2.332, 2.332,
[2.259(2)], [2.265(3)], [2.324(3)]
2.318, 2.333, 2.299
2.556, 2.558, 2.609
2.590, 2.641, 2.735
2.772
2.659
2.680
2.578
2.502
2.701, 2.781
2.650, 2.766
2.483, 3.026
2.317
2.355
2.276
2.336, 2.342
2.253, 2.424
2.303, 2.388
2.363
3.122
2.322
–
3.873 [3.585]
–
9a(mer)
10a(fac)
10a(mer)
20a
TSIa
21a
TSIIa
11a
22a
–
–
–
3.571
3.610
3.660
3.592
–
–
–
–
–
–
–
–
–
–
–
–
–
–
–
–
2.165, 2.190
2.150, 2.396[b]
3.122,[c]
2.077,[e] 3.378
2.07,4[e] 2.767[c]
2.150,[e] 2.168[e]
3.431
2.146, 4.838[d]
2.330,[b] 5.058[d]
2.551,[f] 5.019[d]
2.182
TSIIIa
12a
2.356[b]
2.938[c]
2.165[e]
3.524
2.581[f]
15
2.084, 2.092
IVa
2.080, 2.239[b]
2.437[c]
2.014[e]
3.420
23a
2.109, 4.008[d]
16
Va
2.084
2.245[b]
2.494[c]
2.035[e]
3.721
24a
2.608[f]
–
17a
–
–
–
–
–
–
2.707
2.905[b]
4.239[d]
2.528
2.761[b]
4.127[d]
VIa
2.260[c]
2.007
25a
18a
2.274
2.192
2.297
2.357
3.203
2.325
3.729
VIIa
26a
2.280[c]
2.007
[a] Shortest distance for the molecule. [b] Splitting bond. [c] Nascent bond. [d] No interaction. [e] Covalent bond. [f] Dative bond.
respectively. Compounds 15a and 16a also possess a short metries of reactions I–VI for structures with (TSIa–
In–F contact (3.524 and 3.420 Å, respectively). These values TSVIIa) and without (TSIb–TSVIIb) NPyǞM interactions.
are comparable with those found for bismuth derivatives The most important geometrical parameters of species in
(see above), although the smaller covalent and series (a) are listed in Table 2 and the molecular structures
van der Waals radii of indium in comparison with those of of the TSs studied, their atomic coordinates, and the total
bismuth should be noted.
energy values are given as Supporting Information. Table 3
The coordination polyhedron of the Sb atom in 17a and summarizes the relative energy values for the species
18a is a distorted octahedron (three Sb–CH3 and one Sb– studied, including the transition states I–VII (the activation
N
amide, Sb–Hal, and Sb–NPy bonds). These compounds do barriers).
not possess any short Sb–F contacts (shortest distance:
3.721 and 3.729 Å, respectively).
The computed barriers (Table 3) for the observed reac-
tions 20a Ǟ 21a, 21a Ǟ 11a, and 22a Ǟ 12a in the gas
As stated above, six reactions were studied during this phase are low (17.64–24.41 kcalmol–1), while those for reac-
work (Scheme 2). Analysis of the total energy values for tions
III–VI
are
considerably
higher
(46.23–
the starting materials and products (Table 3) shows that the 50.57 kcalmol–1). The values found for the activation bar-
products are thermodynamically more favored in all the re- rier in reactions I and II are very close to those previously
actions studied. However, the experimental results show found for the reaction [(Et2N)Sb{N(C6F5)(2-C5H4N)}2] Ǟ
that reactions I and II proceed completely and compounds [SbF{N(C6F5)(2-C5H4N)}2] (27.70 kcalmol–1).[1] Similarly
20–22 are not detected in the reaction mixtures, while reac- close values (21.8–41.2 kcalmol–1, RB3LYP/DZVP level of
tions III–VI do not take place. This means that kinetic fac- theory) have been found for the activation barrier for the
tors are the key to understanding the origin of these pro- insertion of Pd(PH3)2 into the C–F bond of different fluo-
cesses. We therefore calculated the transition-state (TS) geo- roarenes (FC6H3XY; X, Y = H, CN, NO2).[23]
Table 3. ∆H [Etotal(products) – Etotal(reactants); kcalmol–1] for reactions I–VI as well as activation barriers for these rearrangements (Eact
;
kcalmol–1).
Reaction
I
II
III
IV
V
VI
20a Ǟ 21a
–28.72
17.64 (TSIa)
20b Ǟ 21b
–29.85
21a Ǟ 11a
–26.67
24.41 (TSIIa)
21b Ǟ 11b
–24.80
22a Ǟ 12a
–22.86
20.30 (TSIIIa)
22b Ǟ 12b
–23.36
15a Ǟ 23a
–26.07
46.77 (TSIVa)
15b Ǟ 23b
–33.28
16a Ǟ 24a
–31.87
50.57 (TSVa)
16b Ǟ 24b
–25.64
17a Ǟ 25a
–9.82
47.88 (TSVIa)
17b Ǟ 25b
–2.15
18a Ǟ 26a
–9.36
46.23 (TSVIIa)
18b Ǟ 26b
–1.05
∆H
Eact
∆H
Eact
24.64 (TSIb)
29.02 (TSIIb)
25.59 (TSIIIb)
16.17 (TSIVb)
31.00 (TSVb)
36.17 (TSVIb)
34.01 (TSVIIb)
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Fluoride/Amide Exchange in (Pentafluorophenyl)amides
The computed barriers for the system without NPyǞM mentioned for indium derivatives. The comparatively strong
bonds [series (b)] are different from those previously dis- NPyǞSb interaction along with the presence of five coval-
cussed for species which contain NPyǞM contacts [series ent bonds around the antimony atom in 17a and 18a pre-
(a)]. While the values for reactions 20b Ǟ 21b, 21b Ǟ 11b, vent these Sb centers from participating in the supposed
22b Ǟ 12b, 17b Ǟ 25b, and 18b Ǟ 26b are close to those rearrangement. It should be noted, however, that the differ-
found previously (see Table 3), the barriers for reactions of ence between the reactants and products in these reactions
indium species 15b Ǟ 23b and 16b Ǟ 24b are dramatically is not as large as in other reactions studied (Table 3).
lower than those for reactions 15a Ǟ 23a and 16a Ǟ 24a.
Some general trends should be noted with regard to the
calculated transition state geometries [series (a)]. First of
all, the species are characterized by a considerable shorten-
Conclusions
In an extension of our studies on antimony(III) amides
we have investigated the transamination of pentafluoro(2-
pyridyl)aniline with dialkylamides of bismuth(III), anti-
mony(V), and indium(III). The reaction between Bi-
(NMe2)3 (2) and HN(2-C5H4N)(C6F5) (1) affords the ex-
pected tris(amide) 10, whereas replacement of only one or
two NMe2 groups leads to the isolation of the unexpected
bismuth fluorides 11 and 12 as a result of an F↔NMe2
metathesis. In contrast, the treatment of [In(NEt2)3]2 (2)
with the same amine 1 leads to the corresponding stable
monomeric tris(amide)s 9, 15, or 16. No F↔NEt2 re-
arrangement occurs for 15 and 16. Furthermore, anti-
mony(V) amides such as 17 and 18 tend to be more stable
with respect to this rearrangement than the antimony(III)
amides reported previously. These examples show that the
tendency to undergo this rearrangement increases with an
increase of the covalent radius and decreases with an in-
crease of coordination number of the central atom. This
rearrangement also requires a highly polar M–N bond,
therefore increasing the covalent character of the com-
pound (e.g. by a higher oxidation state) decreases the likeli-
hood of this metathesis to occur. Density functional calcu-
lations on the activation barriers of the studied reactions
have been found to be in agreement with the experimental
results. The steric demand of the substituents at the central
atom as well as its electron deficiency are the crucial factors
that define the stability of these tris(amide)s to F↔NR2 or
conceivable F↔Hal rearrangements.
ing of the M–F contacts in comparison with those found in
reactants 15a–18a and 20a–22a, while the splitting bond
(M–N or Sb–Hal) becomes elongated. Some elongation of
the M–NPy distances in the TSs in comparison with those
in the corresponding reactants should be mentioned, espe-
cially the significant alterations in TSVIa and TSVIIa.
A noticeable elongation of both C–C bonds (aromatic
C6F5 ring) at the carbon atom involved in the rearrange-
ment processes is also found for all TSs studied. The values
of the nascent C–N bond lengths in TS1a–TSVa vary be-
tween 1.760 and 1.991 Å, while the corresponding covalent
bonds in the products of reactions I–IV are 1.399–1.461 Å.
Analogously, the values of the splitting C–F bond lengths
in TS1a–TSVa vary between 1.482 and 1.565 Å, while the
corresponding covalent bonds in the reactants of reactions
I–IV are 1.348–1.356 Å. The F–C–N angles in TS1a–TSVa
vary between 85.6 and 92.6°. The geometry of the transition
states therefore allows us to define the proposed mechanism
of the nucleophilic addition under study as a concerted oxi-
dative addition.[11,24,25]
We believe that the main driving force behind the studied
rearrangements is the formation of thermodynamically
more favorable species. In the case of bismuth derivatives
20a, 21a, and 22a, as well as the previously studied anti-
mony compounds [(Et2N)2Sb{N(C6F5)(2-C5H4N)}] and
[(Et2N)Sb{N(C6F5)(2-C5H4N)}2],[1] these interconversions
proceed very easily as the weak NPyǞM contacts in these
substances do not prevent M–F bond formation. In our
opinion the rearrangement is likely to proceed through for-
mation of a hypervalent fragment CC F –F–Bi(Sb) with re-
6
5
Experimental Section
tention of the Bi(Sb)–NR2 bond in TS1a–TSIIIa. Thus, the
presence of additional electron density on the metal atom
is necessary to decrease the activation barrier of the studied
rearrangement.
In contrast, the indium derivatives 15 and 16 are stable
and do not participate in any rearrangement processes due
General Remarks: All manipulations were performed under dry,
oxygen-free argon using standard Schlenk techniques. All manipu-
lations of Bi-containing compounds were carried out in brown
glass equipment. Solvents were dried by standard methods and dis-
tilled prior to use. Bi(NMe2)3 (2),[26] [In(NEt2)3]2 (3),[27] Me3SbBr2
to the very strong NPyǞIn interaction. The presence of this (7),[28] and Me3SbCl2 (8)[29] were prepared according to the litera-
ture. C6D6 was obtained from Deutero GmbH and dried with so-
bond in indium derivatives increases the steric hindrance to
the attack of the F atom at the In atom, although the in-
dium center is more electron-deficient than in compounds
without additional interactions. Both these factors prevent
the rearrangement of 15 and 16 from occurring. This con-
clusion is confirmed by the decrease of the computational
barrier found for 15b Ǟ 23b and 16b Ǟ 24b (compounds
without NPyǞIn contacts).
1
dium. H, 13C, and 19F NMR spectra were recorded with Bruker
ARX 200, AC 300, AMX 400, or DRX 500 spectrometers at 23 °C.
1
Chemical shifts in the H and 13C NMR spectra are given in ppm
relative to internal Me4Si, and those in 19F NMR experiments rela-
tive to CFCl3 as an external standard. EI mass spectra were re-
corded with a Finnigan MAT CH7A device using electron impact
ionization at 70 eV, and FD mass spectra were recorded with a
Finnigan MAT 95S device; all assignments were made with refer-
ence to the most abundant isotopes. Elemental analyses were car-
As regards reactions V and VI, we believe that the high
barriers are caused by factors analogous to those previously ried out by the Fachbereich Chemie of the Philipps University
Eur. J. Inorg. Chem. 2007, 5684–5692
© 2007 Wiley-VCH Verlag GmbH & Co. KGaA, Weinheim
www.eurjic.org
5689

S. S. Karlov, J. Sundermeyer et al.
FULL PAPER
Marburg (Heraeus-Rapid-Analyzer). The nonempirical generalized
gradient approximation (GGA) for the exchange-correlation func-
tional of Perdew et al. (PBE) was employed in this work.[30,31] All
calculations were performed using the program PRIRODA devel-
oped by Laikov,[32] which implements an economical computa-
tional procedure. The one-electron wavefunctions were expanded
in the extended TZ2P atomic basis sets of the contracted Gaussians
Synthesis of [(2-C5H4N)(C6F5)N]3Bi (10). Method a: A solution of
amine 1 (0.76 g, 2.90 mmol) in toluene (10 mL) was added dropwise
at 0 °C to a stirred solution of 2 (0.33 g, 0.97 mmol) in toluene
(10 mL). The reaction mixture was stirred at room temperature for
12 h, and all volatiles were removed under reduced pressure. The
residue was recrystallized from n-pentane (–30 °C) to give 10 as a
yellow solid. Yield: 0.78 g (82%). Method b: A solution of 4·thf
{311/1} for H, {611111/411/11} for C, N, and F, {6111111111/ (1.67 g, 4.96 mmol) in thf (15 mL) was added dropwise to a stirred
611111/11} for Cl, {6111111111111/5111111111/51111} for Br, suspension of BiCl3 (0.52 g, 1.65 mmol) in thf (20 mL) at 0 °C. The
{711111111111111/611111111111/51111111} for In and Sb, and
reaction mixture was stirred for a further 12 h, and then all volatiles
{24,24,24,24,24,24,24,24/22,22,22,22,22,22,22/15,15,15,15,15/9} for were removed under reduced pressure. n-Pentane (30 mL) was
Bi. Full geometry optimization was performed by DFT-PBE meth-
ods for a number of structures followed by vibrational frequency
calculation using analytical first and second derivatives. Each struc-
ture was characterized by a vibrational analysis. Each transition
state has only one imaginary normal mode and equilibrium geome-
try states have only real normal modes. An IRC (intrinsic reaction
coordinate) calculation was run starting from the transition state
geometry in both directions and verified initial and final structures
linked to the transition state. The present theoretical method has
been used, and has given very useful results, in antimony and bis-
muth chemistry.[22]
added to the residue, and insoluble substances were removed by
filtration. The solution was reduced in volume to 20% of the origi-
nal volume and stored at –30 °C to obtain 10 as a yellow solid.
Yield: 1.20 g (74%). C33H12BiF15N6 (986.45): calcd. C 40.18, H
1.23, N 8.52; found C 39.79, H 1.43, N 8.03. EI-MS: m/z (%) =
1
727 (28) [M – N(C5H4N)(C6F5)]+. H NMR (C6D6, 200.13 MHz):
δ = 5.58 (br. s, 3 H), 6.14 (br. s, 3 H), 6.93–7.02 (m, 3 H), 7.89 (br.
s, 3 H) ppm. 13C NMR (C6D6, 50.32 MHz): δ = 107.96, 112.33,
140.96, 144.17 ppm; 4 signals for the carbon atoms of the C6F5
group and 1 signal for a carbon atom of the pyridyl group were
not observed in the spectrum. 19F NMR (C6D6, 188.28 MHz): δ =
–164.80 (br. s, 6 F), –162.64 (br. s, 3 F), –146.86 (d, 6 F) ppm.
Synthesis of (2-C5H5N)(C6F5)NH (1): n-Butyllithium (1.6  in hex-
ane, 325 mL, 0.52 mol) was added dropwise to a stirred solution of
2-aminopyridine (48.94 g, 0.52 mol) in thf (50 mL) at –78 °C. The
reaction mixture was warmed to 25 °C and stirred at room tem-
perature for 4 h, and then all volatiles were removed under reduced
pressure; thf (300 mL) was added to the residue, and then a solu-
tion of C6F6 (48.36 g, 0.26 mol) in thf (60 mL) was added dropwise
at –45 °C over about 1 h. The reaction mixture was warmed to
room temperature and refluxed for a further 24 h. Dilute hydro-
chloric acid was then carefully added to the reaction mixture to pH
= 4. The organic phase was washed twice with dilute hydrochloric
acid (100 mL), and the combined aqueous phases were extracted
with diethyl ether (2ϫ100 mL). All organic phases were combined
and dried with Na2SO4, and all volatiles were removed under re-
duced pressure. The residue was extracted with hot n-heptane, and
Synthesis of 11: A solution of 1 (0.86 g, 3.3 mmol) in toluene
(20 mL) was added dropwise to a stirred solution of 2 (1.15 g,
3.3 mmol) in toluene (15 mL) at –78 °C. The reaction mixture was
stirred at room temperaturefor 24 h, and all volatiles were then re-
moved under reduced pressure. The residue was recrystallized from
n-pentane (–30 °C) to give 11 as a yellow solid. Yield: 1.21 g (66%).
C15H16BiF5N4 (506.13): calcd. C 32.39, H 2.90, N 10.07; found C
31.27, H 2.98, N 9.20. FD-MS: m/z (%) = 519 (32) [M+ – 2 F +
1
H], 518 (20) [M+ – 2 F]. H NMR (C6D6, 200.13 MHz): δ = 2.37,
2.38 (2 s, 12 H, NMe2) 5.70 (m, 1 H), 6.00 (m, 1 H), 6.98 (m, 1 H),
7.63 (m, 1 H) ppm. 19F NMR (C6D6, 188.28 MHz): δ = –164.39
(br. s, 2 F, F2Bi), –163.25 (t, 1 F), –149.50 (d, 2 F) ppm.
Synthesis of 12: A solution of 1 (0.62 g, 2.4 mmol) in toluene
(10 mL) was added dropwise to a stirred solution of 2 (0.43 g,
1.3 mmol) in toluene (10 mL) at –78 °C. The reaction mixture was
stirred at room temperature for 24 h, and then all volatiles were
removed under reduced pressure. The residue was recrystallized
from n-pentane (–30 °C) to give 12 as a yellow solid. Yield: 0.56 g
(58%). C24H14BiF10N5 (771.37): calcd. C 37.37, H 1.83, N 9.08;
found C 36.09, H 2.08, N 8.22. EI-MS: m/z (%) = 771 (1) [M+].
FD-MS: m/z (%) = 772 (0.5) [M+ + H], 771 (0.5) [M+], 752 (2)
crystallized crude
1 was purified by sublimation (50 °C/
5ϫ10–3 bar). Colorless crystals. Yield: 60.72 g (90%). EI-MS: m/z
(%) = 260 (42) [M+], 241 (100) [M+ – F]. 1H NMR (C6D6,
200.13 MHz): δ = 5.99 (m, 1 H), 6.36 (m, 1 H), 6.84 (br. s, 1 H,
NH), 6.98 (m, 1 H), 8.07 (m, 1 H) ppm. 13C NMR (C6D6,
50.32 MHz): δ = 108.45, 116.25, 137.78, 148.29, 155.29 (all carbon
atoms of pyridyl groups) ppm; 4 signals for the carbon atoms of the
C6F5 group were not observed in the spectrum. 19F NMR (C6D6,
188.28 MHz): δ = –164.07 (t, 2 F), –161.80 (t, 1 F), –147.27 (d, 2
F) ppm.
1
[M+ – F]. H NMR (C6D6, 200.13 MHz): δ = 2.24, 2.25 (2 s, 6 H,
Me), 5.83 (m, 1 H), 6.04 (m, 1 H), 6.10 (m, 1 H), 6.39 (m, 1 H),
7.02 (m, 1 H), 7.06 (m, 1 H), 7.57 (m, 1 H), 7.75 (m, 1 H) ppm.
19F NMR (C6D6, 188.28 MHz): δ = –165.42 (t, 2 F), –165.26 (t, 1
F), –163.90 (t, 1 F), –162.96 (t, 1 F), –151.19 (d, 1 F), –146.70 (t,
2 F), –146.87 (br. s, 1 F, FBi), –142.78 (d, 1 F) ppm.
Synthesis of 2-C5H5N(C6F5)NLi·thf (4·thf): n-Butyllithium (1.6  in
hexane, 22.50 mL, 36.00 mmol) was added dropwise to a stirred
solution of 1 (9.33 g, 35.88 mmol) in thf (50 mL) at –78 °C. The
reaction mixture was warmed to 25 °C and stirred at room tem-
perature for 5 h, and then all volatiles were removed under reduced
pressure to give a white solid. The crude product was washed with
cold n–-pentane (3ϫ10 mL) and dried under reduced pressure.
Yield: 11.03 g (91%). White solid. C15H12F5LiN2O (338.20): calcd.
Synthesis of 13: Water (2 mL) was added dropwise to a stirred solu-
tion of 11 (0.72 g, 1.3 mmol) in toluene (10 mL), and the reaction
mixture was stirred for 12 h. The organic phase was separated,
dried with Na2SO4, and all volatiles were removed under reduced
pressure. The residue was recrystallized from n-heptane (2 mL) to
give 13 as a colorless solid. Yield: 0.26 g (65%). C15H17F3N4
(310.32): calcd. C 58.06, H 5.52, N 18.05; found C 57.63, H 4.09,
N 17.64. EI-MS: m/z (%) = 310 (100) [M+]. 1H NMR (C6D6,
1
C 53.27, H 3.58, N 8.28; found C 52.94, H 3.50, N 8.03. H NMR
(C6D6, 200.13 MHz): δ = 1.02–1.08 (m, 4 H, O-CH2-CH2), 3.20–
3.26 (m, 4 H, O-CH2), 6.16–6.27 (m, 2 H), 6.97–7.06 (m, 1 H), 7.84
(br. s, 1 H) ppm. 19F NMR (C6D6, 188.28 MHz): δ = –173.52 (br. 200.13 MHz): δ = 2.43, 2.44 (2s, 12 H, NMe2), 6.12 (m, 1 H), 6.45
s, 1 F), –166.15 (t, F), –155.10 (br. s, 2 F) ppm. 19F NMR (thf,
(m, 1 H), 7.06 (m, 1 H), 8.22 (m, 1 H) ppm. 13C NMR (C6D6,
188.28 MHz): δ = –179.22 (t, 1 F), –170.14 (t, 2 F), –153.64 (d, 2 50.32 MHz): δ = 42.49, 42.59 (NMe2), 109.17, 115.56, 136.52,
F) ppm.
5690
148.57, 155.44 ppm; 4 signals for the carbon atoms of C6F5 and 1
www.eurjic.org
© 2007 Wiley-VCH Verlag GmbH & Co. KGaA, Weinheim
Eur. J. Inorg. Chem. 2007, 5684–5692

Fluoride/Amide Exchange in (Pentafluorophenyl)amides
signal for a carbon atom of the pyridyl group were not observed
in the spectrum. 19F NMR (C6D6, 188.28 MHz): δ = –166.28 (t, 1
F), –150.42 (d, 2 F) ppm.
Synthesis of 17: A solution of 4·thf (1.64 g, 4.84 mmol) in thf
(20 mL) was added dropwise at room temperature to a stirred solu-
tion of 7 (1.58 g, 4.84 mmol) in thf (15 mL). The reaction mixture
was stirred at room temperature for 48 h, and all volatiles were
removed under reduced pressure. Toluene (30 mL) was added to
the residue, and insoluble substances were removed by filtration.
The solution was reduced in volume to 5 mL and stored at –30 °C
to obtain 17 as a white solid. Yield: 1.71 g (70%). C14H13BrF5N2Sb
(505.92): calcd. C 33.24, H 2.59, N 5.54; found C 33.05, H 2.51, N
Synthesis of 14: Water (2 mL) was added dropwise to a stirred solu-
tion of 12 (0.43 g, 0.6 mmol) in toluene (10 mL), and the reaction
mixture was stirred for 12 h. The organic phase was separated,
dried with Na2SO4, and all volatiles were removed under reduced
pressure. The residue was purified by chromatography (SiO2; n-hep-
tane/toluene (5:1), 30 mL) to give 14 as a colorless solid. Yield:
0.07 g (41%). C13H11F4N3 (285.24): calcd. C 54.74, H 3.89, N
14.73; found C 54.46, H 3.61, N 14.93. EI-MS: m/z (%) = 285 (100)
[M+]. 1H NMR (C6D6, 200.13 MHz): δ = 2.25, 2.26 (2s, 6 H,
NMe2), 6.17 (m, 1 H), 6.38 (m, 1 H), 7.01 (m, 1 H), 8.16 (m, 1 H)
ppm. 13C NMR (C6D6, 50.32 MHz): δ = 43.00, 43.09 (NMe2),
108.74, 116.23, 137.53, 148.60, 155.90 ppm. 19F NMR (C6D6,
188.28 MHz): δ = –165.26 (t, 1 F), –162.93 (t, 1 F), –151.18 (d, 1
F), –142.78 (d, 1 F) ppm.
5.33. EI-MS: m/z (%)
= –
506 (2) [M]+, 247 (100) [M
1
N(C5H4N)(C6F5)]+. H NMR (C6D6, 200.13 MHz): δ = 1.79 (s, 9
H, SbMe3), 5.55–5.59 (m, 1 H), 6.20–6.27 (m, 1 H), 6.85–6.94 (m,
1 H), 7.58–7.61 (m, 1 H) ppm. 13C NMR (C6D6, 50.32 MHz): δ =
20.83 (SbMe3), 106.31, 113.53, 138.57, 146.21, 159.07 ppm; 4 sig-
nals for the carbon atoms of the C6F5 group were not observed in
the spectrum. 19F NMR (C6D6, 188.28 MHz): δ = –162.18 (t, 2 F),
–157.64 (t, 1 F), –147.22 (d, 2 F) ppm.
Synthesis of 18: The procedure was analogous to that used to syn-
Synthesis of 15: A solution of amine 1 (0.30 g, 1.15 mmol) in tolu-
ene (10 mL) was added dropwise at –78 °C to a stirred solution of
3 (0.38 g, 0.58 mmol) in toluene (10 mL). The reaction mixture was
stirred at room temperature for 12 h, and all volatiles were removed
under reduced pressure. The residue was recrystallized from n-pen-
tane (–30 °C) to give 15 as a yellow solid. Yield: 0.52 g (87%).
C19H24F5InN4 (518.23): calcd. C 44.04, H 4.67, N 10.81; found
C 43.57, H 4.41, N 10.04. EI-MS: m/z (%) = 374 (15) [M –
thesize 17. Thus, treatment of
a solution of 4·thf (1.10 g,
3.24 mmol) in thf (20 mL) with a solution of 8 (0.77 g, 3.24 mmol)
in thf (15 mL) gave 18 as a white solid. Yield: 1.15 g (77%).
C14H13ClF5N2Sb (461.47): calcd. C 36.44, H 2.84, N 6.07; found
C 36.21, H 2.71, N 5.72. FD-MS: m/z (%) = 462 (1) [M]+, 384 (100)
[M – C5H4N]+. 1H NMR (C6D6, 200.13 MHz): δ = 1.67 (s, SbMe3),
5.56–5.61 (m, 1 H), 6.21–6.28 (m, 1 H), 6.86–6.95 (m, 1 H), 7.63–
7.64 (m, 1 H) ppm. 13C NMR (C6D6, 50.32 MHz): δ = 19.95
(SbMe3), 106.80, 113.63, 138.58, 146.43, 158.78 ppm; 4 signals for
the carbon atoms of the C6F5 group were not observed in the spec-
trum. 19F NMR (C6D6, 188.28 MHz): δ = –162.31 (t, 2 F), –158.10
(t, 1 F), –147.31 (d, 2 F) ppm.
1
2 NEt2]+. H NMR (C6D6, 200.13 MHz): δ = 0.97 (t, 12 H, CH3),
2.48 (q, 8 H, NCH2), 5.89–6.01 (m, 2 H), 6.78–6.86 (m, 1 H), 7.52–
7.54 (m, 1 H) ppm. 13C NMR (C6D6, 50.32 MHz): δ = 15.61 (CH3),
44.18 (NCH2), 107.96, 112.33, 140.96, 144.17 ppm; four signals for
the carbon atoms of the C6F5 group and one signal for a carbon
atom of the pyridyl group were not observed in the spectrum. 19F
NMR (C6D6, 188.28 MHz): δ = –165.63 (t, 1 F), –164.77 (t, 2 F),
–149.89 (d, 2 F) ppm.
Synthesis of 19: The procedure was analogous to that used to syn-
thesize 17. Thus, treatment of
a solution of 4·thf (2.64 g,
7.80 mmol) in thf (20 mL) with a solution of 8 (0.93 g, 3.90 mmol)
in thf (15 mL) gave 19 as a white solid (extraction with n-pentane).
Yield: 1.95 g (73%). C25H17F10N4Sb (685.17): calcd. C 43.82, H
2.50, N 8.18; found C 43.58, H 2.35, N 7.66. EI-MS: m/z (%) =
Synthesis of 16: The procedure was analogous to that used to syn-
thesize 15. Thus, treatment of a solution of 1 (1.46 g, 5.60 mmol) in
toluene (10 mL) with a solution of 3 (1.46 g, 5.60 mmol) in toluene
(10 mL) gave 16 as a light yellow solid. Yield: 1.46 g (74%).
C26H18F10InN5 (705.26): calcd. C 44.28, H 2.57, N 9.93; found C
43.52, H 2.61, N 9.49. EI-MS: m/z (%) = 633 (76) [M – NEt2]+. 1H
NMR (C6D6, 300.13 MHz): δ = 0.68 (t, 6 H, CH3), 3.29 (br. s, 4
H, NCH2), 5.80–5.83 (m, 2 H), 6.09–6.13 (m, 2 H), 6.90–6.95 (m,
2 H), 7.47–7.49 (m, 2 H) ppm. 13C NMR (C6D6, 75.47 MHz): δ =
12.10 (CH3), 41.15 (NCH2), 107.74, 110.81, 140.45, 144.27,
162.82 ppm; 4 signals for the carbon atoms of the C6F5 group were
not observed in the spectrum. 19F NMR (C6D6, 188.28 MHz): δ =
–164.74 (t, 2 F), –163.37 (t, 4 F), –147.14 (d) ppm.
669 (1) [M – Me]+, 425 (100) [M – N(C5H4N)(C6F5)]+. H NMR
1
(C6D6, 200.13 MHz): δ = 1.29 (br. s, SbMe3), 5.96–6.00 (m, 2 H),
6.31–6.37 (m, 2 H), 6.94–7.02 (m, 2 H), 8.04–8.06 (m, 2 H) ppm.
13C NMR (C6D6, 50.32 MHz): δ = 19.76 (SbMe3), 106.80, 112.48,
138.49, 146.29, 159.51 ppm; 4 signals for the carbon atoms of the
C6F5 group were not observed in the spectrum. 19F NMR (C6D6,
188.28 MHz): δ = –164.27 (t, 4 F), –161.72 (t, 2 F), –146.97 (d, 4
F) ppm.
X-ray Crystallographic Study. Crystal Data for 9·0.5C7H8: Triclinic
¯
unit cell, space group P1, with a = 10.7275(8), b = 12.9882(8), c =
14.4190(10) Å, α = 72.264(8), β = 79.030(9), γ = 69.388(8)°, V =
1783.2(2) Å3, Z = 2. 17664 reflections were collected at 193 K with
a STOE IPDS diffractometer using graphite-monochromated Mo-
Kα radiation and were corrected for absorption. 6471 reflections
were unique (Rint = 0.0517) and 4274 with I Ͼ 2σ(I) “observed”.
The structure was solved by direct methods[33] and refined using
the full-matrix least-squares procedure.[34] All non-hydrogen atoms
Synthesis of 9: A solution of amine 1 (1.87 g, 7.20 mmol) in toluene
(10 mL) was added dropwise at room temperature to a stirred solu-
tion of 3 (0.80 g, 1.20 mmol) in toluene (10 mL). The reaction mix-
ture was stirred for 12 h, and all volatiles were removed under re-
duced pressure. The residue was recrystallized from n-pentane
(–30 °C) to give 9 as colorless crystals. Yield: 2.00 g (93%).
C33H12F15InN6 (892.28): calcd. C 44.42, H 1.36, N 9.42; found C were treated anisotropically, and hydrogen atoms were treated with
44.20, H 1.27, N 8.86. EI-MS: m/z (%) = 892 (79) [M]+, 633 (63) fixed isotropic thermal parameters as “riding” on calculated posi-
1
[M – N(C5H4N)(C6F5)]+, 374 (10) [M – 2 N(C5H4N)(C6F5)]+. H tions. One molecule of disordered toluene is present in the unit
NMR (C6D6, 300.13 MHz): δ = 5.92–5.95 (m, 3 H), 5.99–6.03 (m, 3
cell and was refined with restraints for geometrical and thermal
H), 6.80–6.86 (m, 3 H), 7.56–7.58 (m, 3 H) ppm. 13C NMR (C6D6, parameters. Final residuals for 540 refined parameters and 70 re-
75.47 MHz): δ = 108.05, 112.69, 140.89, 144.41 ppm; 4 signals for
the carbon atoms of the C6F5 group and 1 signal for a carbon atom
of the pyridyl group were not observed in the spectrum. 19F NMR
(C6D6, 188.28 MHz): δ = –165.28 (br. s, 3 F), –164.66 (t, 6 F),
–149.54 (br. s, 6 F) ppm.
straints: wR2 = 0.053 (for all unique data), R1 = 0.0314 (for the
“observed” data). CCDC-631484 (9) contains the supplementary
crystallographic data for this paper. These data can be obtained
free of charge from The Cambridge Crystallographic Data Centre
via www.ccdc.cam.ac.uk/data_request/cif.
Eur. J. Inorg. Chem. 2007, 5684–5692
© 2007 Wiley-VCH Verlag GmbH & Co. KGaA, Weinheim
www.eurjic.org
5691

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Received: July 22, 2007
Published Online: November 8, 2007
5692
www.eurjic.org
© 2007 Wiley-VCH Verlag GmbH & Co. KGaA, Weinheim
Eur. J. Inorg. Chem. 2007, 5684–5692