On the chemistry of fluoroorgano derivatives of Group 13 elements Part 3. Syntheses of pentafluorophenylindium dibromide, In(C6F5)Br2·2D (D=THF, C5H5N), and related compounds - Single crystal structure analyses of In(C6F5) Br2·2THF and In(acac)Br2·2THF

Article abstract of DOI:10.1016/S0022-328X(03)00322-X

In(C₆F₅)Br₂·2D (D=THF, pyridine) are selectively and almost quantitatively formed through oxidative addition of C₆F₅Br to InBr in THF solution or dichloromethane-pyridine mixtures. The constitution of In(C₆ F₅)Br₂·2THF is confirmed by a single crystal structure analysis (monoclinic, P2₁/c, Z = 4, a = 1694.3(2), b = 1421.5(2), c = 813.42(9) pm, β= 100.3(1)°, R_all=0.1072). Reactions of In(C₆F₅) Br₂·2THF and Mg(C₆F₅)Br in diethylether after addition of 4-dimethylaminopyridine (DMAP) yield In(C₆F₅)₃·DMAP. In[SC(S) N(C₂H₅)₂] ₃ is formed by treatment of In(C₆F₅)Br₂·2THF with NaSC(S)N(C₂H₅)₂ while acidic hydrolysis with aqueous HBr quantitatively gives InBr₃·nH₂O and C₆F₅H. Reactions of In(C₆F₅)Br₂·2THF with an aqueous solution of pentane-2,4-dione (acetylacetone, Hacac) in THF quantitatively yield In(acac)Br₂·2THF and C₆F₅H. The constitution of this compound is established by a single crystal structure analysis (orthorhombic, Pbcn, Z = 4, a = 1314.9(2), b = 928.5(1), c = 1468.4(2) pm, R_all = 0.0347).

Full text of DOI:10.1016/S0022-328X(03)00322-X

Journal of Organometallic Chemistry 677 (2003) 28Á34
/
www.elsevier.com/locate/jorganchem
On the chemistry of fluoroorgano derivatives of Group 13 elements
Part 3. Syntheses of pentafluorophenylindium dibromide,
In(C6F5)Br2×
/
2D (Dꢀ
/
THF, C5H5N), and related compounds*
/
single
crystal structure analyses of In(C6F5)Br2×
/
2THF and In(acac)Br2×
/
2THFꢀ
Wieland Tyrra *, Mathias S. Wickleder
Institut fur Anorganische Chemie, Universitat zu Koln, Greinstr. 6, D-50939 Cologne, Germany
¨ ¨ ¨
Received 10 February 2003; received in revised form 20 March 2003; accepted 20 March 2003
Abstract
In(C6F5)Br2×
InBr in THF solution or dichloromethaneÁ
crystal structure analysis (monoclinic, P21/c, Zꢀ
Reactions of In(C6F5)Br2×2THF and Mg(C6F5)Br in diethylether after addition of 4-dimethylaminopyridine (DMAP) yield
In(C6F5)3×DMAP. In[SC(S)N(C2H5)2]3 is formed by treatment of In(C6F5)Br2×2THF with NaSC(S)N(C2H5)2 while acidic
hydrolysis with aqueous HBr quantitatively gives InBr3×nH2O and C6F5H. Reactions of In(C6F5)Br2×2THF with an aqueous
solution of pentane-2,4-dione (acetylacetone, Hacac) in THF quantitatively yield In(acac)Br2×2THF and C6F5H. The constitution
of this compound is established by a single crystal structure analysis (orthorhombic, Pbcn, Zꢀ4, aꢀ1314.9(2), bꢀ928.5(1), cꢀ
1468.4(2) pm, Rall 0.0347).
/
2D (Dꢀ
/
THF, pyridine) are selectively and almost quantitatively formed through oxidative addition of C6F5Br to
pyridine mixtures. The constitution of In(C6F5)Br2×2THF is confirmed by a single
4, aꢀ1694.3(2), bꢀ1421.5(2), cꢀ813.42(9) pm, bꢀ100.3(1)8, Rall 0.1072).
/
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ꢀ
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ꢀ
/
# 2003 Elsevier Science B.V. All rights reserved.
Keywords: Acetylacetonate; Crystal structure; Indium; Pentafluorophenyl
1. Introduction
isation and reactions of In(C6F5)Br2×
/2THF are
described.
Pentafluorophenylindium derivatives were first re-
ported in 1965 [3]. In the early 70s of last century,
Deacon and Parrott developed different methods for
2. Results and discussion
their syntheses [4Á8]. In our systematic studies [1,2,9,10]
/
on the synthesis of pentafluorophenylindium com-
pounds, we found that derivatives of the general
2.1. Reactions of bromopentafluorobenzene and
indium(I) bromide and mixtures of
bromopentafluorobenzene, indium and bromine
formula In(C6F5)Br2×
/
2D (DꢀTHF, C5H5N) are con-
/
veniently accessible. In this paper, synthesis, character-
Reactions of C6F5Br and elemental indium at ambient
temperature gave no 19F-NMR spectroscopic for the
formation of InC6F5 derivatives. By contrast, reactions
of C6F5Br and InBr or 2:1 mixtures of elemental indium
and bromine (Eq. (1)) proceeded selectively in THF with
ꢀ For Part 2 see [Z. Anorg. Allg. Chem. 625 (1999) 1287]. This work
was presented in part on the 15th Winter Fluorine Conference, St.
Petersburg, FL, USA, 14-1-2001 to 19-1-2001, cf. [J. Fluorine Chem.
112 (2001) 119].
nearly quantitative formation of In(C6F5)Br2×
Similar results were obtained using 1:4 mixtures of
CH2Cl2 and pyridine. Both derivatives, In(C6F5)Br2×
/2THF.
* Corresponding author. Tel./fax: ꢁ
/
49-221-470-3276.
E-mail address: tyrra@uni-koeln.de (W. Tyrra).
/
0022-328X/03/$ - see front matter # 2003 Elsevier Science B.V. All rights reserved.
doi:10.1016/S0022-328X(03)00322-X

W. Tyrra, M.S. Wickleder / Journal of Organometallic Chemistry 677 (2003) 28Á
/
34
29
2THF and In(C6F5)Br2×
/
2C5H5N, were isolated as pale
yellow, respectively, colourless air and water insensitive
The reaction proceeded to the corresponding substi-
tution product In(C6F5)3. Addition of 4-dimethylami-
nopyridine (DMAP) allowed the isolation of In(C6F5)3×
solids in nearly quantitative yields.
/
(1)
These reactions might be interpreted in terms of an
oxidative addition of C6F5Br to InBr or the formal
DMAP [1] in moderate yield. In contrast, treatment of
In(C6F5)Br2×
(C2H5)3N did not selectively give the expected product,
(C2H5)2InC6F5×N(C2H5)3 [10] but a product mixture of
at least four InC6F5 compounds (19F-NMR control).
Also reactions of 2THF and
In(C6F5)Br2×
NaSC(S)N(C2H5)2×3H2O in aqueous THF did not give
/2THF with (C2H5)2Zn after addition of
insertion of InBr into the carbonÁbromine bond of
/
/
C6F5Br and are best described via the SET mechanistic
approach [11] (Scheme 1).
/
/
the desired complex compounds {In(C6F5)[SC(S)-
N(C2H5)2]}Br or In(C6F5){[SC(S)N(C2H5)2]2} but
In[SC(S)N(C2H5)2]3 and C6F5H (Eq. (3), idealised).
Single crystals of In[SC(S)N(C2H5)2]3 were grown from
toluene solutions of the raw material showing an
identical structure as determined previously [12].
In(C6F5)Br2 ×2THFꢁ3Na[SC(S)N(C2H5)2]ꢁH2O
2
0
THF=H O In[SC(S)N(C2H5)2]3 ꢁ2NaBrꢁNaOH
ꢁC6F5H
(3)
Scheme 1.
Reactions of In(C6F5)Br2×/2THF and aqueous HBr
(48%), the H-acidic compounds acetylacetone (pentane-
2,4-dione, Hacac), 2,2,6,6-tetramethylheptane-3,5-dione
and 1,1,1,5,5,5-hexafluoropentane-2,4-dione proceeded
selectively in the cases of the two former. These
2.2. Reactions of In(C6F5)Br2×
/
2THF
Halide substitution reactions of In(C6F5)Br2×
and Mg(C6F5)Br were carried out in diethylether (Eq.
(2)).
/
2THF
reactions gave InBr3×
/
nH2O (Eq. (4)) and In(acac)Br2×
/
2THF (Eq. (5)) after extended reaction times (up to 1
week at room temperature).
In(C6F5)Br2 ×2THFꢁ2Mg(C6F5)Br (C H ) O
0
2
5 2
ꢂ2MgBr2
THF
0
In(C6F5)Br2 ×2THFꢁHBr
InBr3 ×nH2O
(4)
ꢂC6F5H
0
ꢁDMAP In(C6F5)3 ×DMAP
(2)
ꢂ2THF
(5)

30
W. Tyrra, M.S. Wickleder / Journal of Organometallic Chemistry 677 (2003) 28Á34
/
However, reactions with further a,g-diketones gave
complex product mixtures. 19F-NMR spectra reveal that
C bond had not completely been cleaved even
the Inꢀ
/
after extremely prolonged reaction times of up to 6
weeks.
As mentioned before, the reaction of pentane-2,4-
dione (acetylacetone, Hacac) and In(C6F5)Br2×
/
2THF
proceeded smoothly and selectively to give In(acac)Br2×
/
2THF in good yield. This method offers a third
approach to prepare In(acac)Br2 different from the
previously described pathways starting from indium(I)
halides and pentane-2,4-dione yielding mixtures of
In(acac)3 and In(acac)X2. The In(acac)X2 was converted
into octahedral complexes (InX2O2N2 moieties) after
addition of 2,2?-bipyridine, 1,10-phenantroline, pyridine
or pyridine-D5 [13]. Compounds In(acac)X2×
/
D (XꢀCl,
/
Br; Dꢀ2,2?-bipyridine, 1,10-phenantroline) were alter-
/
natively prepared from InX3, the donor and pentane-
2,4-dione in methanol solutions [14].
Fig. 2. Perspective view of the crystal structure of In(C6F5)Br2×
/
2THF
along [0 1 0].
Single crystals of In(acac)Br2×
/
2THF were grown on
storing the mother liquor for several months at ambient
temperature. The results of single crystal analyses are
given in the following section.
The indium oxygen bond lengths of 229.5 and 233.0
pm are slightly longer than those measured in InBr3×
2THF [16] and shorter than those measured in
(CH3)2CHInBr2×2THF and C6H5CH2InBr2×2THF
[17]. As in InBr3×2THF, the angle O2ꢀInꢀO3 is found
to be 1778. The distances to the bromide ions are also
slightly but not remarkably longer than in InBr3×2THF
and in good agreement with values reported for
(CH3)2CHInBr2×2THF and C6H5CH2InBr2×2THF
[17]. The angles within the equatorial plane vary from
1188 to 1218 and are close to the ideal value of 1208. The
equatorial plane and the plane formed by the atoms of
the C6F5 ligand are tilted with respect to each other by
348 (Fig. 1). It should be noted that the shortest
distances of In to the fluoride atoms of the C6F5 group
are 327 and 330 pm and, hence, are slightly shorter than
the calculated van der Waals contact (350 pm [18]).
/
/
/
2.3. Results of crystal structure analyses
/
/
/
2.3.1. Single crystal structure of In(C6F5)Br2×
/
2THF
/
In the crystal structure of In(C6F5)Br2×2THF, the
/
indium atom is surrounded by one carbon atom of the
C6F5 group, two oxygen atoms of the THF molecules
and two bromine atoms (Fig. 1). The co-ordination
polyhedron is a nearly ideal trigonal bipyramid with the
bromine atoms and the carbon atom forming the
equatorial plane, while the oxygen atoms occupy apical
/
/
sites. The shortest distance is found for the Inꢀ
/C bond
(218.7 pm). This value corresponds well with distances
found for other crystallographically characterised pen-
tafluorophenyl indium compounds, i.e. (C6F5)2-
In(CH2)3N(CH3)2 [15] and [(C6H5)3PNP(C6H5)3][In-
(C6F5)4] [1].
Fig. 1. Molecular structure of In(C6F5)Br2×
/2THF.
Fig. 3. Molecular structure of In(acac)Br2×2THF.
/

W. Tyrra, M.S. Wickleder / Journal of Organometallic Chemistry 677 (2003) 28Á
/
34
31
In the crystal structure (Fig. 2), In(C6F5)Br2×
/
2THF
exhibit octahedrally co-ordinated indium centres. Bond
lengths to the oxygen atom of the chelating pentane-
dionato ligands are of comparable size (212.4 and 216.4
pm [20] and 215.6 pm). In contrast to the structure
described in this paper, the ‘equatorial’ plane in
molecules are arranged in a manner that layers are
formed parallel to [1 0 0]. The C6F5 groups of one layer
are located opposite to the THF molecules of adjacent
layers. The shortest distances of the C atoms of the THF
groups to the F atoms of the C6F5 group (for example
In(acac)Cl2×2,2?-(C5H4N)2 [20] is not built up by the
/
C33ꢀ
/
F14: 316 pm) probably might be interpreted in
terms of a weak hydrogen bonding.
two oxygen atoms of the acetylacetonate and two
halogen atoms but by one halogen and one nitrogen
atom of the donor molecule with one chlorine atom
trans to oxygen and one trans to nitrogen. With respect
2.3.2. Single crystal structure of In(acac)Br2×
The substitution of the monodentate pentafluorophe-
2THF by the bi-dentate
/
2THF
to the angles, the structure of In(acac)Cl2×
deviates more from a ‘regular octahedron’ than that of
In(acac)Br2×2THF.
/
2,2?-(C5H4N)2
nyl group in In(C6F5)Br2×
/
/
chelating acetylacetonate ligand gives a distorted octa-
hedral co-ordination around the indium centre in
Molecules in the crystal structure are orientated in a
manner that in direction [0 1 0] bromine atoms and
acetylacetonate ligands are opposite to each other (Fig.
4).
In(acac)Br2×
/
2THF (Fig. 3). In comparison with
In(C6F5)Br2×
/
2THF, the distances of indium to the
oxygen atoms of the THF ligands standing trans to
each other (224.5 pm, Table 3) are significantly shorter.
Br bond lengths are elongated by
On the other hand, Inꢀ
/
about 6 pm (Table 3). These changes are in good
agreement with observations for other octahedral in-
dium complexes with bromine and oxygen ligands such
3. Experimental
Schlenk techniques were used throughout most of the
manipulations. Indium wire or pellets were purchased
from Strem, InBr from Aldrich, C6F5Br from ABCR.
THF, pyridine, and dichloromethane were purified and
dried by common methods. NMR spectra were recorded
on a Bruker AC 200 spectrometer operating at 200.1
MHz (1H). External standards were used in all cases
(1H, 13C: (CH3)4Si; 19F: CCl3F). Acetone-d6 was used as
an external lock (5 mm tube) in reaction control
measurements, while an original sample of the reaction
mixture was measured in a 4-mm insert. Mass spectra
were run on a Finnigan MAT 95 spectrometer using the
electron impact method (20 eV). Intensities are refer-
enced to the most intensive peak. Decomposition points
were determined using the apparatus HWS Mainz 2000.
as InBr3×
with the trigonal bipyramidal complex InBr3×
[16]. Bromine and oxygen atoms of the acetylacetonate
group form a nearly ideal square plane. The angles Brꢀ
Inꢀ Inꢀ InꢀBr (848Á998) as well as
Br#1, O1ꢀ O1#1, O1ꢀ
Br#1
InꢀO1 (172.568) deviate from the 908 angle and
/
3DMSO [19] or InBr3×
/
3DMF [16] compared
/
2THF
/
/
/
/
/
/
/
ꢀ
/
/
the 1808 angle, respectively, in the expected range. The
O atoms of the THF molecules are shifted away from
O2#2 of
the bromide ions. Therefore, the angle O2ꢀ
/
Inꢀ
/
166.28 significantly deviates from linearity.
The molecular structure is best compared with that of
(2,2?-bipyridine)(2,4-pentanedionato)indium dichloride,
In(acac)Cl2×
/
2,2?-(C5H4N)2 [20]. Both derivatives
In(acac)Cl2×
/
2,2?-(C5H4N)2 [20] and In(acac)Br2×2THF
/
Fig. 4. Perspective view of the crystal structure of In(acac)Br2×2THF along [0 1 0].
/

32
W. Tyrra, M.S. Wickleder / Journal of Organometallic Chemistry 677 (2003) 28Á34
/
Table 1
Crystallographic data and their determination
Table 2
Selected distances (pm) and angles (8) for In(C6F5)Br2×
/2THF
Compound
In(acac)Br2×
/
In(C6F5)Br2×
/
Inꢀ
Inꢀ
Inꢀ
Inꢀ
Inꢀ
/
Br1
Br2
O2
250.0(2)
250.2(2)
229.5(7)
233.0(8)
218.7(11)
C11ꢀ
C11ꢀ
C11ꢀ
C11ꢀ
O2ꢀInꢀ
O2ꢀInꢀ
O2ꢀInꢀ
O3ꢀInꢀ
O3ꢀInꢀ
Br1ꢀ
O2ꢀInꢀ
/
Inꢀ
Inꢀ
Inꢀ
Inꢀ
/
Br1
Br2
O2
121.0(3)
120.8(3)
91.9(3)
91.4(3)
89.3(2)
89.9(2)
176.7(3)
88.8(2)
88.6(2)
118.2(1)
176.6(2)
2THF
2THF
/
/
/
/
/
/
Lattice parameter
a (pm)
b (pm)
/O3
/
/O3
1314.9(2)
928.5(1)
1468.4(2)
1694.3(2)
1421.5(2)
813.42(9)
100.3(1)
290.3
/C11
/
/
Br1
Br2
O3
/
/
c (pm)
C11ꢀ
C11ꢀ
C12ꢀ
C13ꢀ
C14ꢀ
/
C12
C16
C13
C14
C15
138(2)
139(2)
136(2)
139(2)
134(2)
/
/
b (8)
/
/
/
Br1
Br2
Molar volume (cm3 molꢂ1
No. of formula units
Crystal system
Space group
Measure device
Radiation
)
269.9
4
/
/
/
4
/
/
Inꢀ
/Br2
Orthorhombic
Pbcn (Nr. 61)
Stoe IPDS
Monoclinic
P21/c (Nr. 14)
/
/
/
O3
C15ꢀ
C12ꢀ
C13ꢀ
C14ꢀ
C15ꢀ
C16ꢀ
/
C16
F12
F13
F14
F15
F16
136(2)
136(1)
138(1)
137(1)
135(1)
136(1)
O2ꢀ
/
C21
C24
147(2)
150(1)
149(2)
137(2)
150(2)
/
O2ꢀ
/
MoÁ
lꢀ71.07 pm)
293
3B
155
125
195
0B8 B
/
Ka (graphite monochrom.,
/
C21ꢀ
C22ꢀ
C23ꢀ
/
C22
C23
C24
/
/
/
Measuring temperature (K)
Theta range (8)
Index range
170
5B
195
165
85l 5
260; 2.0 0B8 B200; 2.0
/
/
/
2u B
h 5
k 5
l 518
/
48
17,
12,
/
2u B
h 5
k 5
/
48
19,
16,
/
ꢂ
ꢂ
ꢂ
/
/
/
ꢂ
/
/
/
O3ꢀ
O3ꢀ
C31ꢀ
C32ꢀ
C33ꢀ
/
C31
C34
149(1)
143(1)
148(2)
144(2)
146(2)
/
/
/
ꢂ
/
/
/
/
/
/
/
ꢂ/
/
/8
/
C32
C33
C34
Rotation angle (8); 8 incre-
ment (8)
No. of images
/
/
/
/
/
/
130
6
100
5
Exposure time (min)
Detector distance (mm)
Data corrections
60
60
Polarisation and Lorentz factors
Numerical after crystal shape opti-
misation [24]
Absorption correction
Table 3
Selected distances (pm) and angles (8) for In(acac)Br2×
/
2THF
m (cmꢂ1
)
57.8
7877
1405
1058
54.2
Inꢀ
Inꢀ
Inꢀ
/
Br
(2x)
(2x)
(2x)
255.9(1) O1ꢀ
215.6(2) O1ꢀ
224.5(3) O1ꢀ
O1ꢀ
139.2(4) O1ꢀ
150.5(6) O2ꢀ
127.0(4) O2ꢀ
/
Inꢀ
Inꢀ
Inꢀ
Inꢀ
Inꢀ
Inꢀ
Inꢀ
Inꢀ
Inꢀ
/
Br
(2x)
(2x)
(2x)
172.56(7)
Measured reflections
Unique reflections
12 095
2934
1705
/
O1
/
/
Br#1
O2
88.02(7)
86.26(10)
83.56(10)
84.9(1)
/
O2
/
/
Unique reflections with I ꢀ
2s(I)
Rint
/
/
/
O2#2 (2x)
C11ꢀ
C12ꢀ
C12ꢀ
C11ꢀ
C13ꢀ
C13ꢀ
C13ꢀ
/C12
(2x)
/
/
O#1
0.0458
0.1587
/C13
/
/Br
(2x)
(2x)
93.61(7)
95.33(7)
166.2(1)
99.11(2)
Structure solution and refine- SHELXS-86 and SHELXL-93 [25,26]
ment
/O1
/
/
Br#1
O#2
/
H111
H131
H132
H133
92(5)
93(4)
90(5)
97(5)
O2ꢀ
/
/
Scattering factors
Goodness of fit
Intern. Tables, Vol. C
0.917
/
Brꢀ
/
/
Br#1
0.928
/
R1; wR2 [I ꢀ
R1; wR2 (all data)
/2s(I)]
0.0209; 0.0415
0.0347; 0.0435
0.0637; 0.1386
0.1072; 0.1528
/
C21ꢀ
C21ꢀ
145.9(5) C22ꢀ
145.7(6) C22ꢀ
147.8(8) C23ꢀ
150.1(7) C23ꢀ
151.0(8) C24ꢀ
C24ꢀ
/
H211
H212
H221
H222
H231
H232
H241
H242
74(4)
/
118(5)
98(5)
99(6)
92(5)
97(6)
85(6)
101(6)
O2ꢀ
O2ꢀ
C21ꢀ
C22ꢀ
C23ꢀ
/C21
/
/C22
/
CHN analyses were carried out with a Heraeus CHN
Rapid apparatus. Elemental analyses were performed by
literature procedures: In [21], F [22], Br [23].
/
C23
C24
C24
/
/
/
/
/
/
zꢁ/12; #2: x, ꢂy, zꢁ/12/
:
/
3.1. Crystal structure analyses
#1: ꢂ
/
x, y, ꢂ
/
hydrogen atoms in the crystal structure of In(C6F5)Br2×
/
Both compounds easily form colourless to pale yellow
single crystals which were sealed in glass capillaries and
the suitability checked with the help of an IP-diffract-
ometer (STOE IPDS) [24]. The same device was used to
collect the reflection data of the respective best speci-
men. The positions of the heavy atoms were extracted
from these data using the direct methods provided by
the program SHELXS-86 [25]. The light atoms were
localised during the refinement (SHELXL-93) by differ-
2THF could not be detected although the measurement
was carried out at low temperature. Details of data
aquisition and the crystallographic data are summarised
in Tables 1Á3 [28].
/
3.2. Syntheses of (pentafluorophenyl)indium dibromide
adducts
3.2.1. bis(tetraHydrofuran)(pentafluorophenyl)indium
ence Fourier syntheses [26]. For In(acac)Br2×
hydrogen atom positions were found in the difference
Fourier map and refined without constraints [27]. The
/
2THF the
dibromide, In(C6F5)Br2×
/
2THF
Two gram (10.27 mmol) of InBr was suspended and
partly dissolved in 15 ml of THF. 1.50 ml (12.03 mmol)

W. Tyrra, M.S. Wickleder / Journal of Organometallic Chemistry 677 (2003) 28Á
/
34
33
of C6F5Br was added. The reaction mixture was stirred
for 16 h at ambient temperature. During this period red
InBr completely vanished giving a nearly colourless
solution. 19F-NMR control revealed that the mixture
13C-NMR data of the ligand did not significantly differ
from those of neat pyridine.
Colourless solid; m.p. 240 8C (dec.).
EIMS 20 eV (125 8C), m/z (rel. int.): [C18F15In]ꢁ (1);
528 [C12BrF10In]ꢁ and [C17H5F10BrInN]ꢁ (10); 449
[C12F10In]ꢁ (51); 442 [C11H5BrF5InN]ꢁ (40); 361
[C6BrF5In]ꢁ (69); 354 [Br3In]ꢁ (24); 275 [Br2In]ꢁ
(19); 194 [BrIn]ꢁ (14); 168 [C6HF5]ꢁ (9); 115 [In]ꢁ
(72); 79 [C5H5N]ꢁ and [Br]ꢁ (100).
contained In(C6F5)Br2×
/
2THF, excess C6F5Br besides
minor amounts of C6F5H. All volatile compounds
were distilled off in vacuo at ambient temperature giving
In(C6F5)Br2×
/
2THF in nearly quantitative yield (5.91 g,
98%). The product is a pale yellow solid with an
intensive characteristic smell (‘honey melon like’) being
insensitive to air and water-soluble.
Anal. Calc. for C16H10Br2F5InN2: Br, 26.6; F, 15.8;
In, 19.1%. Found: Br, 26.5; F, 14.9; In, 18.7%. Sufficient
results of a CHN analysis cannot be provided due to
incomplete combustion of the samples.
Instead of InBr, elemental indium and bromine (Br2)
in a molar ratio of 2:1 may alternatively be used in a
similar procedure as described above. Reactions were
terminated after all indium had been consumed. Isolated
yields were nearly quantitative in all cases.
3.3. Reactions of In(C6F5)Br2×
/
2THF
Pale yellow solid; m.p. 68Á
19F-NMR (188.3 MHz, CD3CN): dꢀ
F-2,6); ꢂ154.0 (tt, 1F, F-4); ꢂ161.1 (m, 2F, F-3,5);
(D2O) ꢂ121.3 (m, 2F, F-2,6); ꢂ154.1 (tt, 1F, F-4); ꢂ
161.5 (m, 2F, F-3,5).
1H-NMR (200.1 MHz, CD3CN): dꢀ
/
69 8C.
3.3.1. Synthesis of (4-dimethylaminopyridine)tris-
(pentafluorophenyl)indium, In(C6F5)3×DMAP
Four gram (6.82 mmol) of In(C6F5)Br2×2THF was
added to a freshly prepared solution of 17.00 mmol of
Mg(C6F5)Br (0.43 g Mg, 2.12 ml C6F5Br) in diethyl-
ether. The reaction mixture was stirred for 24 h at 30 8C.
0.82 g (6.71 mmol) of DMAP was added and the
mixture stirred for additional 24 h at ambient tempera-
ture. After filtration of the solid residue, all volatile
compounds were removed in vacuo leaving an ochre
/
ꢂ119.1 (m, 2F,
/
/
/
/
/
/
/
/
/3.74 (m, 4H,
CH2O); 1.82 (m, 4H, CH2).
13C-NMR (50.3 MHz, CD3CN): dꢀ
/
149.2 (dm,
250 Hz, C-
1
241 Hz, C-2,6); 142.7 (dm, JF,C
1JF,C
4); 137.9 (dm, JF,C
ꢀ
/
ꢀ
/
1
ꢀ246 Hz, C-3,5); 119.8 (br, C-1);
/
1
1
69.3 (t, JC,H
CH2); (CH3NO2/C6D6ꢀ
237 Hz, C-2,6); 142.4 (dm, JF,C
ꢀ
/
148 Hz, CH2O); 26.0 (t, JC,H
3:1): dꢀ148.4 (dm, JF,C
251 Hz, C-4); 137.3
256 Hz, C-3,5); 115.8 (br, C-1); 69.2 (t,
ꢀ
/
133 Hz,
residue from which In(C6F5)3×/DMAP was extracted
1
/
/
ꢀ
/
with CH2Cl2 in a Soxhlet-apparatus in 74% yield (3.72
g). Analytic and spectroscopic data agreed well with
those reported earlier [1].
1
ꢀ
/
1
(dm, JF, C
1JC,H
150 Hz, CH2O); 25.2 (t, JC,H
(D2O): dꢀ
(dm, 1JF,C
3,5); 119.3 (t, JF,C
ꢀ
/
1
ꢀ
/
ꢀ
/
133 Hz, CH2);
231 Hz, C-2,6); 140.6
267 Hz, C-4); 136.5 (dm, 1JF,C
246 Hz, C-
1
/
148.2 (dm, JF,C
ꢀ
/
3.3.2. Synthesis of indium tris(diethyldithiocarbamate),
In[SC(S)N(C2H5)2]3
ꢀ
/
ꢀ
/
2
1
ꢀ
/
54.6 Hz, C-1); 68.0 (t, JC,H
ꢀ146
/
1
Two gram (3.41 mmol) of In(C6F5)Br2×
/
2THF and
Hz, CH2O); 25.1 (t, JC, H
ꢀ135 Hz, CH2).
/
0.60 g (2.66 mmol) of NaSC(S)N(C2H5)2×3H2O were
/
EIMS 20 eV (150 8C), m/z (rel. int.): 975
[C24Br3F20In2]ꢁ (3); 890 [C18Br2F15In2]ꢁ (8); 803
[C12Br3F15In2]ꢁ (6); 616 [C18F15In]ꢁ (4); 528
[C12BrF10In]ꢁ (9); 449 [C12F10In]ꢁ (100); 361
[C6BrF5In]ꢁ (58); 168 [C6HF5]ꢁ (55); 115 [In]ꢁ (85);
71 [C4H7O]ꢁ.
Anal. Calc. for C14H16Br2F5InO2: C, 28.7; H, 2.8; Br,
27.3; F, 16.2; In, 19.6%. Found: C, 28.2; H, 2.9; Br, 27.1;
F, 16.0; In, 19.8%.
dissolved in a mixture of 15 ml of THF and 5 ml of H2O.
The reaction was terminated when C6F5H was detected
as the only fluorine-containing component in the 19F-
NMR spectra of the reaction mixture. All volatile
compounds were distilled off in vacuo. The remaining
residue was extracted with toluene. Evaporation of
toluene under a ventilated hood for several days yielded
colourless crystals of In[SC(S)N(C2H5)2]3 which were
identified by a single crystal structure analysis [12] and
an elemental analysis.
The results of the crystal structure analysis are
summarised in Tables 1 and 2.
3.3.3. Reaction of In(C6F5)Br2×
/
2THF with aqueous HBr
3.2.2. bis(Pyridine)(pentafluorophenyl)indium
Two gram (3.41 mmol) of In(C6F5)Br2×
/2THF was
dibromide, In(C6F5)Br2×
/
2C5H5N
In a similar manner as described for the THF
dissolved in 20 ml of THF at ambient temperature. One
milliliter of aqueous HBr (48%) was added. The mixture
was diluted with 2 ml water. After a total reaction time
of 2 d, exclusive formation of C6F5H was detected in the
19F-NMR spectra. After vacuum-drying, an extremely
hygroscopic colourless solid was obtained (1.67 g) which
complex, the pyridine adduct was obtained using 1:4
mixtures of CH2Cl2 and pyridine. In(C6F5)Br2×
was obtained in approximately quantitative yield as a
colourless solid. NMR data of the C6F5 group matched
1
well with those reported for the THF complex. H- and
/2C5H5N
was identified as InBr3×/nH2O.

34
W. Tyrra, M.S. Wickleder / Journal of Organometallic Chemistry 677 (2003) 28Á34
/
[4] G.B. Deacon, J.C. Parrott, Aust. J. Chem. 24 (1971) 1771.
[5] G.B. Deacon, J.C. Parrott, Inorg. Nucl. Chem. Lett. 7 (1970) 329.
[6] G.B. Deacon, J.C. Parrott, Inorg. Nucl. Chem. Lett. 8 (1972) 271.
[7] G.B. Deacon, J.C. Parrott, Aust. J. Chem. 25 (1972) 1169.
[8] G.B. Deacon, J.C. Parrott, J. Organomet. Chem. 22 (1970) 287.
[9] W. Tyrra, M.S. Wickleder, Z. Anorg. Allg. Chem. 628 (2002)
1841.
3.3.4. Synthesis of bis(tetrahydrofuran)(2,4-
pentanedionato)indium dibromide, In(acac)Br2×
/2THF
Four gram (6.82 mmol) of In(C6F5)Br2×2THF were
/
suspended and partly dissolved in 15 ml of THF. 1.20 ml
(11.39 mmol) of Hacac and 1 ml of water were added.
The reaction mixture was stirred for 5 d at ambient
temperature. Crystals were grown from the mother
liquor at room temperature over a period of several
weeks. After decanting the covering liquid phase,
[10] Z.-H. Choi, W. Tyrra, Z. Anorg. Allg. Chem. 624 (1998) 2015.
[11] M. Smith, in: M.B. Smith, J. March (Eds.), March’s Advanced
Organic Chemistry: Reactions, Mechanisms, and Structure, fifth
ed. (and literature cited therein), Wiley, 2001, p. 806.
[12] K. Dymock, G.J. Palenik, J. Slezak, C.L. Raston, A.H. White, J.
Chem. Soc. Dalton Trans. (1976) 28.
In(acac)Br2×/2THF was isolated in 80% yield (2.82 g)
as a colourless crystalline solid which was dried in
vacuo. Results of the single crystal analysis are sum-
marised in Tables 1 and 3.
[13] J.G. Contreras, D.G. Tuck, J. Chem. Soc. Dalton Trans. (1974)
1249.
[14] D. Dembicka, A. Bartecki, W. Bogacs, Mater. Sci. (Wroclaw) 9
(1983) 245.
[15] H. Schumann, O. Just, Th.D. Seuß, F.H. Gorlitz, R. Weimann, J.
¨
Colourless crystalline solid; m.p. 81Á
/
82 8C.
1H-NMR (200.1 MHz, CD3CN): dꢀ
/
5.58 (s, 1H,
Organomet. Chem. 466 (1994) 5.
[16] G.R. Willey, D.R. Aris, J.V. Haslop, W. Errington, Polyhedron
20 (2001) 423.
CCHC(acac)); 3.78 (m, 8H, CH2O (THF)); 2.00 (s, 6H,
CCH3 (acac)); 1.82 (m, 8H, CH2 (THF)).
13C{1H}-NMR (50.3 MHz, CD3CN): dꢀ
/
196.7 (s,
O); 69.6 (s,
[17] B. Werner, T. Krauter, B. Neumuller, Z. Anorg. Allg. Chem. 621
¨
¨
(1995) 346.
Cꢀ
/
O); 101.8 (s, Cꢀ
/
OCHCꢀ
/
CH2O(THF)); 28.5 (s, CH3C); 25.9 (s, CH2(THF)).
EIMS 20 eV (110 8C), m/z (rel. int.): 374
[C5H7Br2InO2]ꢁ (38); 359 [C4H4Br2InO2]ꢁ (20); 313
[C10H14InO4]ꢁ (6); 293 [C5H7BrInO2]ꢁ (100); 275
[Br2In]ꢁ (9); 214 [C5H7InO2]ꢁ (7); 199 [C4H4InO2]ꢁ
(6); 115 [In]ꢁ (42); 72 [C4H8O]ꢁ (46).
Anal. Calc. for C13H23Br2InO4: C, 30.2; H, 4.5; Br,
30.9; In, 22.2%. Found: C, 29.8; H, 4.6; Br, 30.6; In,
22.1%.
[18] A. Bondi, J. Phys. Chem. 68 (1964) 441.
[19] W.T. Robinson, C.J. Wilkins, Z. Zeying, J. Chem. Soc. Dalton
Trans. (1990) 219.
[20] J.G. Contreras, F.W.B. Einstein, D.G. Tuck, Can. J. Chem. 52
(1974) 3793.
[21] R. Pribil, Komplexone in der chemischen Analyse, VEB
Deutscher Verlag der Wissenschaften, Berlin, 1961.
[22] A.D. Campbell, P.A. Dawson, Mikrochim. Acta [Wien] I (1983)
489.
[23] G. Jander, K.F. Jahr, H. Knoll, Maßanalyse, de Gruyter, Berlin,
1973, p. 227.
[24] (a) Fa. STOE & Cie, X-RED 1.07, Data Reduction for STADI4
and IPDS, Darmstadt, 1996.;
Acknowledgements
(b) Fa. STOE & Cie, X-SHAPE 1.01, Crystal Optimisation for
Numerical Absorption Correction, Darmstadt, 1996.
[25] G.M. Sheldrick, SHELXS-86, Programme zur Rontgenstruktura-
¨
Generous support of this work by Prof. Dr. Dieter
Naumann is gratefully acknowledged.
nalyse, Gottingen, 1986.
¨
[26] G.M. Sheldrick, SHELXL-93, Program for the Refinement of
Crystal Structures, Gottingen, 1993.
¨
[27] R.X. Fischer, E. Tillmanns, Acta Crystallogr. C44 (1988) 775.
[28] Crystallographic data for the structures have been deposited with
the Cambridge Crystallographic Data Centre as supplementary
References
publication nos. CCDC 196920 for In(C6F5)Br2×
CCDC 196919 for In(acac)Br2×2THF. Copies of the data can be
obtained, free of charge, on application to CCDC, 13 Union
Road, Cambridge CB2 1EZ, UK (Fax: ꢁ44-1323-336033 or e-
mail: deposit@ccdc.cam.ac.uk).
/
2THF and
[1] Z.-H. Choi, W. Tyrra, A. Adam, Z. Anorg. Allg. Chem. 625
(1999) 1287.
/
[2] W.E. Tyrra, J. Fluorine Chem. 112 (2001) 149.
[3] J.L.W. Pohlmann, F.E. Brinckmann, Z. Naturforsch. 20b (1965)
5.
/