Trialkyl borate assisted amination of fluorinated 1,3-diketones for synthesis of N,N′-1,2-phenylen-bis(β-aminoenones) and their Ni(II), Cu(II) and Pd(II) complexes

Article abstract of DOI:10.1016/j.jfluchem.2011.03.018

An effecient synthetic method for fluorinated tridentate β-aminoenones and tetradentate bis(β-aminoenones) via amination of fluorinated 1,3-diketones with o-phenylenediamine in the presence of trialkyl borates was developed. Ni(II), Cu(II) and Pd(II) comp

Full text of DOI:10.1016/j.jfluchem.2011.03.018

Journal of Fluorine Chemistry 132 (2011) 394–401
Contents lists available at ScienceDirect
Journal of Fluorine Chemistry
journal homepage: www.elsevier.com/locate/fluor
Trialkyl borate assisted amination of fluorinated 1,3-diketones for synthesis of
N,N0-1,2-phenylen-bis(
b-aminoenones) and their Ni(II), Cu(II) and Pd(II)
complexes
*
Dmitrii L. Chizhov , Marina G. Pervova, Mariya A. Samorukova, Ekaterina F. Khmara,
Vera I. Filyakova, Viktor I. Saloutin, Valery N. Charushin
I.Ya. Postovsky Institute of Organic Synthesis of RAS (Ural Division), S. Kovalevskoy/Akademicheskaya St. 22/20, 620990, GSP-147, Ekaterinburg, Russia
A R T I C L E I N F O
A B S T R A C T
Article history:
An effecient synthetic method for fluorinated tridentate
b-aminoenones and tetradentate bis(b-
Received 30 November 2010
Received in revised form 19 March 2011
Accepted 26 March 2011
Available online 1 April 2011
aminoenones) via amination of fluorinated 1,3-diketones with o-phenylenediamine in the presence of
trialkyl borates was developed. Ni(II), Cu(II) and Pd(II) complexes with tetradentate bis( -aminoenones)
b
were obtained. Their gaschromatographic behaviour and main fragmentation paths in the electron
ionization mass spectra were described.
ß 2011 Elsevier B.V. All rights reserved.
Keywords:
Amination
Fluorinated ligands
Complexes
Gas-chromatography–mass-spectrometry
1. Introduction
benzodiazepines or the acidic cleavage products are usually formed
[5]. Meanwhile, coordination compounds based on fluorinated
The modification of known ligand systems, such as 1,3-
diketones and their hetero-analogues, provides a considerable
contribution to the chemistry of coordination compounds [1].
Introduction of fluorine in 1,3-dicarbonyl compounds or their
derivatives substantially changes the electron density distribution
that greatly affects their chemical and physical properties [2].
Thus, stability and volatility of diketonate complexes with ions of
transition metals usually increase, which has been used for
quantitative gaschromatographic determination of many transi-
tion and rare earth metals [3] and for obtaining of coats by means
of metal organic chemical vapour deposition (MOCVD) [4].
Replacement of an oxygen atom by a NR-group in fluorinated
tetradentate bis(
be of significant practical interest, likewise non-aromatic ones. For
example, transition metal complexes of N,N0-alkylene-bis(
-ami-
b
-aminoenones) with N,N0-1,2-arylene bridge can
b
noenones) are less volatile, but much more stable and possess
improved gaschromatographic (GC) behaviour in comparison with
b
-aminoenonate [7]. Ni(II), Cu(II) and Pd(II) complexes with
fluorinated N,N0-ethylene-bis(
-aminoenones) were considered as
effective organic optical filters [8]. Moreover, complexes of these
bis(
-aminoenones) are similar to Salphen (N,N0-1,2-phenylene-
b
b
bis(salicylideneiminato)) complexes that catalytic [9], optic [10] and
magnetic [11] properties have been extensively studied.
It was previously found that the reaction of o-phenylenediamine
1,3-dicarbonyl compounds yields enamino-ketones (
b
-aminoe-
(benzene-1,2-diamine) with fluorinated
chemoselectively to yield fluorinated tridentate
and tetradentate bis(
-aminoenones) with an N,N0-1,2-phenylene
bridge [12]. Ni(II), Cu(II) and Pd(II) complexes with tetradentate
bis( -aminoenones) bearing CF3 and CH3 terminal groups were
b
-alkoxyenones occurred
none, -aminovinylketone). These chelating agents are of consid-
b
b-aminoenones
erable interest for designing tailored coordination compounds due
to the possibility to change the steric and electronic envelope of the
main chelate site NO.
b
b
Generally, the reaction of fluorinated 1,3-diketones with diamine
obtained and structurally characterized as well [13].
occurs with
a
comparative ease to afford mono- or bis(
b-
Despite the fact that the above-mentioned tri- and tetradentate
aminoenones) [5,6] depending on reagents ratio. However, when
1,2-diaminoarenes were applied in this reaction, fluorinated 1,5-
ligands can be obtained starting from fluorinated b-alkoxyenones,
availability of various fluorinated 1,3-diketones promotes their
usage for the construction of these chelating ligands. Nevertheless,
information on such syntheses is scarce. It was shown that 2-
polyfluoroacylcycloalkanones react with o-phenylenediamine
* Corresponding author. Tel.: +7 963 038 7059; fax: +7 343 369 30 58.
E-mail address: dlchizhov@ios.uran.ru (D.L. Chizhov).
under mild conditions affording tridentate
b-aminoenones [14].
0022-1139/$ – see front matter ß 2011 Elsevier B.V. All rights reserved.
doi:10.1016/j.jfluchem.2011.03.018

D.L. Chizhov et al. / Journal of Fluorine Chemistry 132 (2011) 394–401
395
Table 1
Synthesis of
b-aminoenones 2a-c and bis(b .
-aminoenones) H2L1-5
Entry
Compounds
R
Rf
Time
Yield (%)a
1
2
3
4
5
6
7
8
2a
Me
Et
CF3
10 minb
15 minb
10 minb
1 dayc
78
82
79
76
65
78
70
74
2b
CF3
2c
Me
Me
Et
C3F7
CF3
H2L1
H2L2
H2L3
H2L4
H2L5
CF3
3 daysc
1dayc
Me
Et
C3F7
CF3
Scheme 1. B(OEt)3 catalyzed synthesis of tridentate
b-aminoenones.
2 daysd
2 dayse
Me
C3F7
There were only two reports [15] where authors declared the
formation of bis( -aminoenones) by reaction of fluorinated 1,3-
diketones with o-phenylenediamine. However, neither elemental
analysis nor spectroscopic data were reported for the obtained
compounds. Moreover, the melting point (97 8C) of a product from
a
Isolated yields.
b
c
b
B(OEt)3 was used.
B(OBu)3 was used.
d
e
From 2b and
From 2c and
b
b
-alkoxyenone 3.
-alkoxyenone 3.
trifluoroacetylacetone [15a] corresponds to tridentate
b-aminoe-
none (96–97 8C) rather than to the claimed bis( -aminoenone)
b
(122–124 8C), both structures being strongly proved [12c].
Herein we report on an efficient synthesis of tridentate
aminoenones and tetradentate bis(b-aminoenones) by reaction of
irreversibly reacts with B(OEt)3. Thus, when less than one
equivalent of B(OEt)3 was used, the reaction was not completed
within 15–20 h (R55Me).
b-
fluorinated 1,3-diketones with o-phenylenediamine in the pres-
ence of trialkyl borate, and on the preparation of Cu(II), Ni(II) and
While triethyl borate was used to obtain tetradentate ligands
H2L1–3 via the reaction of o-phenylenediamine with two equiva-
Pd(II) complexes of tetradentate bis(
matographic behaviour and electron impact ionization mass
spectra of bis( -aminoenones) and their complexes were investi-
gated to estimate their volatility, thermal stability and behaviour
under conditions favourable to ionization (high temperature,
photoirradiation, etc.).
b
-aminoenones). Gaschro-
lents of the fluorinated diketones 1a–c, only bis(b-aminoenones)
H2L1,3 were isolated in ꢀ30% yield. Side products of this reaction
were determined by means of GC–MS analysis. Thus, the analysis
of the hydrolyzed reaction mixture from trifluoroacetylacetone 1a
showed the content of the target compound H2L1 ꢀ27%, unreacted
b
diketone 1a ꢀ25%, tridentate -aminoenones 2a ꢀ2% and ꢀ36% of
b
2-methyl-4-(trifluoromethyl)-3H-1,5-benzodiazepine as a result
of intramolecular cyclization of 2a. The use of a large excess of
triethyl borate (10 equiv.) increased the yield of H2L1,3 up to ꢀ40%.
However, when B(OEt)3 was replaced by a large excess of B(OBu)3,
2. Results and discussion
2.1. Trialkyl borate assisted amination of fluorinated 1,3-diketones
bis(b
-aminoenones) H2L1–3 were obtained in 65–78% yields
(Scheme 2; Table 1, entry 4–6).
We found that amination of the fluorinated diketones 1a–c with
one equivalent of o-phenylenediamine in the presence of one
Some unidentified coloured impurities were formed in course
of the last reaction. Therefore, the crude bis(b-aminoenones) were
equivalent of triethyl borate gave the tridentate
b-aminoenones
reacted with an excess of Cu(CH3COO)2, and the obtained copper
complexes were purified by column chromatography. Treatment
of the latter with oxalic acid afforded analytically pure bis(b-
aminoenones) in almost quantitative yields (based on copper
complexes).
2a–c in good yields (Scheme 1, Table 1; entry 1–3).
The positive effect of B(OEt)3 on the selectivity of this reaction
can arise from two main factors. At first, similarly to BF3,
triethylborate is able to form a borate complex with 1,3-diketones,
thus activating one of two carbonyl groups of the dicarbonyl
moiety. Secondly, water, formed in the course of amination,
This approach was not suitable for the preparation of pure
unsymmetrical tetradentate ligands by reaction of
2b,c with trifluoroacetylacetone 1a. While the expected bis(
b-aminoenones
Rf
R
b
-
NH2
NH2
aminoenones) H2L4,5 were formed, minor amounts (10–20%) of the
symmetrical compounds H2L2,3 appeared. The presence of ligand
H2L1 was observed in these cases as well. Probably, this is a result
of the competitive intermolecular re-amination of 2b,c followed by
the reaction of trifluoroacetylacetone with the liberated o-
phenylenediamine (Scheme 3).
1/2
Rf
R
O
O
HN
HN
, B(OAlk)3 (excess)
RT
H2L1-3
O
O
65-78%
1a-c
Rf
R
R, Rf = Me, CF3 (1a, H2L1); Et, CF3 (1b, H2L2); Me, C3F7 (1c, H2L3)
Because of non-selective preparation of unsymmetrical bis(
aminoenones) H2L4,5 from diketones, they were obtained by the
reaction of -aminoenones 2b,c with -methoxyenone 3 in the
b-
Alk = Et, Bu
b
b
Scheme 2. B(OAlk)3 catalyzed synthesis of tetradentate bis(
b
-aminoenones).
Rf
Rf
R
R
O
O
HN
F3C
F3C
F3C
H2N
O
O
O
O
HN
HN
H2N
1a
H2L1
-H2L2,3
H2N
HN
2b,c
H2N
Scheme 3. Plausible mechanism of side-product-formation in course of the unsymmetrical bis(b-aminoenones) synthesis.

396
D.L. Chizhov et al. / Journal of Fluorine Chemistry 132 (2011) 394–401
Table 2
Relative retention times of bis(
Pd(II) complexes.
b
-aminoenones) H2L1-5 and their Cu(II), Ni(II) and
0
Entry
Ligand
R/R0
Rf/Rf
Relative retention timea
H2L
NiL
CuL
PdL
1
2
3
4
5
H2L1
H2L2
H2L3
H2L4
H2L5
Me/Me
Et/Et
CF3/CF3
CF3/CF3
C3F7/C3F7
CF3/CF3
CF3/C3F7
0.787
0.817
0.802
0.801
0.797
1.172
1.187
1.093
1.182
1.125
1.177
1.183
1.091
1.179
1.122
1.480
1.480
1.293
1.482
1.359
Me/Me
Me/Et
Me/Me
Scheme 4. Synthesis of unsymmetrical bis(b-aminoenones).
a
Relative to dioctyl phtalate.
presence of pyridine [12c] (Scheme 4; Table 1, entry 7 and 8) and
purified via copper complexes.
The aminoenones 2b,c and H2L2–5 were characterized by the
elemental analysis, IR and NMR 1H, 19F and 13C spectroscopy.
Comparison of compounds 2a and H2L1 with authentic samples
[12c] confirmed their structures (Table 1, entries 1 and 4).
The presence of aminoenone fragments was confirmed by
column 5). This is in agreement with general rules of chro-
matographic retention. The detection limit was 0.02 mg/mL in
CHCl3 solution.
Retention times of NiL and CuL with equal L were similar
whereas the times of the corresponding PdL complexes were
longer (Table 2). In contrast to the free ligands, elongation of Rf in
the complexes increases their volatility (Table 2, entries 1, 3 and 5).
This is in accordance with the known influence of fluorinated
substituents on the complexes volatility. Non-fluorinated R did not
affect the retention times of PdL but slightly enhanced those for
NiL and CuL (Table 2, entries 1, 2 and 4). All complexes had regular-
shaped symmetrical peaks, which were close to the normal
distribution. Detection limits of NiL, CuL and PdL in the CHCl3
solution were 0.005 mg/ml, 0.02 mg/ml and 0.05 mg/ml corre-
spondingly. Observed differences of the GC behaviour for these
complexes are likely to be due to the different d-shells of the
corresponding metals (d3 for Ni and Cu, and d4 for Pd).
signals of olefinic protons at dH 5.58–5.72 ppm and NH-protons at
dH 11.70–12.60 ppm in the 1H NMR spectra. Singlets at dC 167.6–
173.7 ppm and multiplets (quartets or triplets) at dC 177.7–
178.8 ppm in the 13C NMR spectra were assigned to the carbon
atoms of 55C(NHAr) and RfC55O fragments, respectively. The high-
frequency shifts of the N–H groups suggest U-configuration of the
aminoenone fragments stabilized by a strong N–Hꢁ ꢁ ꢁO intramo-
lecular hydrogen bond [16]. Double-proton broadened singlets at
dH 3.71–3.80 ppm in the case of 2b,c were attributed to the NH2-
group. For unsymmetrical bis(b
-aminoenones) H2L4,5 double-sets
of peaks of NH and olefinic protons together with terminal group
signals were observed in the 1H spectra.
Low intensive molecular ions for all ligands H2L1-5 appeared in
the mass-spectra. The fragmentation paths of the molecular ions
M+ are similar. In all cases one alkyl group R was eliminated. The
peak intensity of these fragments was higher in case of R55C2H5.
Elimination of CF3 and C3F7, and CF3CO, and C3F7CO groups also
afforded low intensity peaks. Peaks with 100% intensity corre-
sponded to fragment ions [MꢂRfCOCH2]+. We did not observe
cleavage of the Ar–N bond, whereas in the case of derivatives with
an N,N0-alkylene bridge elimination of [RfCOCH2C(R)NH] frag-
ments usually occurs [7d,17]. Additionally, a number of peaks with
identical m/z values 213, 199, 186, 171, 159, 145, 133 were found
2.2. Synthesis of Cu(II), Ni(II) and Pd(II) complexes with tetradentate
bis(
b-aminoenones)
The reaction of tetradentate bis(
b
-aminoenones) H2L1–5 with
Cu(II), Ni(II) and Pd(II) acetates resulted in corresponding com-
plexes. The elemental analysis and IR-spectroscopy data confirm
their structure. NMR 1H and 19F spectroscopy was used in case of
Ni(II) and Pd(II) complexes. Melting points and IR-spectral data of
NiL1, CuL1 and PdL1 corresponded to authentic samples [13].
Noteworthy, the majority of signals of complexes NiL2–5 and
PdL2–5 in the NMR 1H and 19F spectra were shifted significantly
with respect to signals of free ligands. Thus, signals of the aromatic
in the mass-spectra of bis(
the similar fragmentation of ions after elimination of the groups
varied depending on bis( -aminoenones).
b
-aminoenones) H2L1–5. This is due to
protons were shifted upfield (
D
for the center of aromatic
b
multiplets was 0.33–0.38 ppm for NiL2–5 and 0.16–0.24 ppm for
PdL2–5), while protons of CH3 and CH2 groups were shifted
Base peaks of complexes NiL, CuL and PdL in the mass-spectra
were molecular ions M+ with an isotopic pattern identical to
isotope distribution of the metal. Mass-spectra showed a wide
variety of peaks with highest intensities for PdL and lowest
intensities for NiL. Generally, the elimination of RfCO-groups is
typical for all investigated complexes in the course of their
fragmentation. This group can be eliminated either itself or with a
metal cation and other fluorinated group, e.g., RfCOR, RfCOCCR. In
addition, low intensity peak clusters of metal cations (up to 10%)
were observed in all spectra. Previously, the presence of cation
metal peaks was shown for tetradentate chelate complexes [18].
downfield (
0.55 ppm, respectively). The signals of the olefinic protons were
slightly shifted downfield (
= 0.06–0.17 ppm). In the 19F NMR
D
for NiL2–5 and PdL2–5 is 0.34–0.49 ppm and 0.49–
D
spectra, the signals of the CF3 groups of complexes NiL and PdL
were shifted downfield to 3.38–4.51 ppm and 4.27–5.78 ppm,
respectively. The values of these shifts are similar to the values of
NiL1 and PdL1 [13].
The number of absorption bands of the main structural units
and their position in the IR spectra were similar for all obtained
complexes. Recently we have shown that complexes NiL1, CuL1
and PdL1 have the saddle-shape configuration, which is much
All that distinguishes the fragmentation of bis(b-aminoenones)
H2L1–5 and their Cu(II), Ni(II) and Pd(II) complexes from the
fragmentation of their N,N0-alkylene analogues [7d,15a,17].
different from the bis(b
-aminoenone) H2L1 configuration [13].
Therefore, the same configuration can be attributed for all
complexes obtained in this work.
Schemes 5 and 6 show a plausible fragmentation paths of bis(b-
aminoenones) H2L1 (as an example of investigated ligands) and
CuL1 (as an example of investigated complexes) respectively. The
formed neutral molecules can give various products via transfer
proton arrangement.
2.3. Gas-chromatography–mass-spectrometry of bis(
aminoenones) and their complexes
b-
It is noteworthy that bonds cleavage in ligands H2L and their
complexes under electron impact ionization occurs mainly by
analogous paths. However, while the ligands have main ion peaks
It was found that elongation of terminal substituent R and Rf
slightly increases the retention time of ligand H2L1–5 (Table 2,

D.L. Chizhov et al. / Journal of Fluorine Chemistry 132 (2011) 394–401
397
m/z 365(15.0 %)
F3C
-CH3
-F
-
CF3COC CCH3
m/z 229(8.9 %)
-CF3COC=CH2
m/z 361(1.3 %)
O
O
HN
HN
m/z 213(3.1 %)
-CF3H
m/z 171(6.1 %)
m/z 256(6.0 %)
-CF3CO
F3C
-CH3
m/z 186(2.4 %)
-CF3CO
m/z 283(2.8 %)
-CF3, -CH3
M+, m/z 380(12.6 %)
-CF3COCH2
-
CF3COCH CHCH3
CF3COCH CH2
m/z 159(9.5 %)
-
CF3COC CCH3
-CF3H
m/z 133
(20.0 %)
m/z 269(100 %)
m/z 145(5.3 %)
-CH3
m/z 199(11.0 %)
m/z 199(11.0 %)
m/z 130(5.0 %)
Scheme 5. Plausible fragmentation paths of bis(b
-aminoenones) H2L1.
m/z 426(0.3 %)
-CH3
m/z 422(2.9 %)
F3C
-F
-
CF3COC CCH3
-CF3
m/z 372(4.4 %)
m/z 305(19.0 %)
O
O
N
N
-CH3
Cu
-CF3COCH3
-Cu
-CF3CO
m/z 357(13.1 %)
-CF3COCH2
F3C
M+, m/z 441(100 %)
-CF3COCH3
m/z 208(8.9 %)
-Cu
m/z 130(6.5 %)
m/z 330(0.3 %)
-Cu
-CF3CO
-CF3
m/z 145(10.0 %)
m/z 261(8.6 %)
m/z 267(6.3 %)
m/z 329(20.1 %)
m/z 344(7.4 %)
-CF3COH
-Cu
-CF3CO
-Cu
-Cu
m/z 169(10.6 %)
m/z 232(10.5 %)
m/z 183(6.7 %)
m/z 281(5.3 %)
Scheme 6. Probable fragmentation paths of CuL1.
[MꢂRfCOCH2]+ in the mass-spectra, peaks of similar fragments are
intensive only in the case of copper complexes. The low intensity
cluster [MꢂRfCOCH2]+ was fixed for PdL1 only among other
palladium complexes. In the case of complexes NiL, analogous
fragments were not observed. Nevertheless, there were peaks that
can be attributed to fragment ions of a cooperative elimination of
RfCOCH2 (or RfCOCH3) together with other characteristic groups.
Therefore, the fragmentation paths of H2L, CuL, and PdL hold for
nickel complexes.
4. Experimental
4.1. General remarks
Melting points were measured on a Stuart SMP3 melting points
apparatus and are not corrected. The NMR 1H and 19F spectra were
recorded on a Bruker DRX-400 spectrometer at 400 and 367 MHz
respectively in CDCl3 solution. Chemical shifts (d) are given in ppm
relative to Me4Si (1H) and C6F6 (19F). IR spectra were recorded on a
Spectrum One FTIR spectrometer with using a diffuse reflectance
accessory. GC–MS investigations were carried out on an Agilent GS
7890A MSD 5975C inert XL (USA) gas-chromatography–mass
spectrometer with a quadrupole mass spectrometric detector at
an electron energy of 70 eV, using scanning in the total ion current
mode in the m/z range 30–1000 amu. A fused silica capillary
3. Conclusions
In conclusion, we developed efficient methods for the synthesis
of fluorinated tridentate
b-aminoenones and tetradentate bis(b-
aminoenones) via a direct borate assisted reaction of fluorinated
1,3-diketones with o-phenylenediamine. Cu(II), Ni(II) and Pd(II)
column HP-5MS (30 m; 0.25 mm; 0.25 mm) was used. The initial
complexes based on tetradentate bis(
synthesized. Gas chromatography–mass-spectrometry of bis(
aminoenones) and their complexes showed a reasonable thermal
stability of the investigated compounds and the obvious differ-
ences of fragmentation paths under electron impact ionization (at
70 eV) as compared to N,N0-alkylene analogues.
b
-aminoenones) were
temperature of column was 100 8C (storage for 3 min); rate 10 8C/
min to 300 8C (storage for 30 min). The temperature of the injector
was 250 8C. The carrier gas was helium. The split ratio was 1:50,
and the gas flow rate through the column was 1.0 mL/min. Course
of reactions was monitored by TLC (Silufol UV-254, eluent CHCl3).
Methoxyenone 3 was obtained by known method [19].
b
-

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D.L. Chizhov et al. / Journal of Fluorine Chemistry 132 (2011) 394–401
4.2. General procedure for synthesis of tridentate
b
-aminoenones 2a–c
d d 11.98 (s, CH2CH3), 25.67
84.88 (s). 13C NMR (100 MHz, CDCl3):
(s, CH2CH3), 89.80 (q, 3J = 0.8 Hz, 55CH–), 117.25 (q, 1J = 288.4 Hz,
CF3), 127.80 (s, CH, Ar), 128.72 (s, CH, Ar), 133.22 (s, Ar), 173.58 (s,
55C(NHAr)–), 178.03 (q, 2J = 33.7 Hz, CF3C55O). EIMS (probe)
70 eV, m/z (rel. int.): 408 [M]+ (6), 389 [MꢂF]+ (2), 379 [MꢂC2H5]+
o-Phenylenediamine (0.55 g, 5.1 mmol), B(OEt)3 (0.75 g,
5.14 mmol) and 1,3-diketone 1a–c (5.0 mmol) in CH3CN (20 mL)
were stirred 10–15 min, diluted with water (50 mL) and stirred
until solidification of a precipitated oil. The solid was collected,
washed with water, dried in the air, dissolved in CHCl3 (3 mL), and
passed through silica gel bed (2 cm). Silica gel was washed with
CHCl3 (3 ꢃ 5 mL). Combined chloroform solutions were evaporat-
ed. The residue was recrystallized from hexane–CH2Cl2 (3:1)
solution. Yields of 2a–c are collected in the Table 1.
+
(100), 369 [MꢂFꢂHF]+ (1), 339 [MꢂCF3]+ (4), 311 [MꢂCF3CO]+
(2), 297 [MꢂCF3COCH2]+ (92), 229 [C10H8N2OF3]+ (25). Anal. Calcd
for C18H18N2F6O2: C, 52.99; H, 4.39; N, 6.87; F, 27.94. Found C,
53.08; H, 4.69; N, 6.79; F, 28.05.
(Z)-5,5,6,6,7,7,7-Heptafluoro-2-(2-{[(Z)-4,4,5,5,6,6,6-hepta-
fluoro-1-methyl-3-oxo-1-hexenyl]amino}anilino)-2-hepten-4-
one (compound H2L3). Yellow crystals: mp 85–86 8C. IR (DRA):
n
(Z)-4-(2-aminoanilino)-1,1,1-trifluoro-3-penten-2-one (com-
pound 2a). Pale-yellow crystals: mp 96-97 8C [96-97 8C, ref. [12c].
(Z)-4-(2-aminoanilino)-1,1,1-trifluoro-3-hexen-2-one (com-
3123 (NH. . .O55), 1618, 1604, 1582, 1517 (O55C–C55C, Ar), 1481,
1434 ( 2.05 (6H, s,
CH). 1H NMR spectral data (400 MHz, CDCl3):
2CH3), 5.64 (2H, s, 2 = CH), 7.31–7.33 (2H, m, Ar), 7.41–7.44 (2H, m,
Ar), 12.47 (2H, br. s, 2NH). 19F NMR (376 MHz, CDCl3):
34.57 (s,
d
d
pound 2b). Pale-yellow crystals: mp 98–99 8C. IR (DRA):
3358 (NH2), 3225 (NH. . .O55), 1629, 1619, 1596, 1500 (O55C–C55C,
Ar). 1H NMR spectral data (CDCl3,
/ppm, J/Hz) 1.10 (t, 3H, J = 7.5,
n 3455,
d
d
d
4F, 2CF2CF2CF3), 40.29 (q, 4F, J = 8.8 Hz, 2CF2CF2CF3), 80.96 (t, 6F,
J = 8.8 Hz, 2CF2CF2CF3). 13C NMR (100 MHz, CDCl3): 19.89 (s, CH3),
93.34 (t, 3J = 1.0 Hz, 55CH–), 108.71 (tq, 1J = 265.9, 2J = 38.3 Hz,
CF3CF2CF2), 109.37 (tt, 1J = 264.9, 2J = 31.0 Hz, CF3CF2CF2), 117.73
(qt, 1J = 287.8, 2J = 34.1 Hz, CF3CF2CF2), 127.59 (s, CH, Ar), 128.74 (s,
CH, Ar), 133.12 (s, Ar), 167.64 (s, 55C(NHAr)–), 178.73 (t,
2J = 24.4 Hz, CF3C55O). EIMS (probe) 70 eV, m/z (rel. int.): 580
[M]+ (4), 561 [MꢂF]+ (1), 565 [MꢂCH3]+ (12), 541 [MꢂFꢂHF]+ (1),
383 [MꢂC3F7CO]+ (4), 369 [MꢂC3F7COCH2]+ (100), 356
[MꢂC3F7COCH55CH2]+ (6), 329 [C12H8N2OF7]+ (7). Anal. Calcd for
CH3), 2.30 (2H, q, J = 7.5, CH2), 3.80 (2H, br.s, NH2), 5.60 (1H, s,
55CH), 6.75–6.81 (2H, m, Ar), 6.99–7.01 (m, 1H, Ar), 7.15–7.19 (m,
1H, Ar), 12.05 (1H, br.s, NH). 19F NMR (376 MHz, CDCl3):
d 84.88 (s).
Anal. Calcd for C12H13N2F3O: C, 55.81; H, 5.07; N, 10.85; F, 22.07.
Found: C, 55.58; H, 5.06; N, 10.74; F, 22.20.
(Z)-2-(2-aminoanilino)-5,5,6,6,7,7,7-heptafluoro-2-hepten-4-
one (compound 2c). Pale-yellow crystals: mp 80–81 8C. IR (DRA):
3469, 3374 (NH2), 1612, 1585, 1567, 1518, 1500, 1429 (O55C–C55C,
Ar). 1H NMR spectral data (CDCl3,
/ppm, J/Hz) 2.02 (s, 3H, CH3),
n
d
d
3.80 (2H, br. s, NH2), 5.62 (1H, s,55CH), 6.76–6.82 (2H, m, Ar), 7.00–
7.02 (1H, m, Ar), 7.14–7.19 (1H, m, Ar), 12.12 (1H, br. s, NH). 19F
C20H14N2F14O2: C, 41.42; H, 2.43; N, 4.83; F, 45.86. Found C, 41.38;
H, 2.44; N, 4.90; F, 45.91.
NMR (376 MHz, CDCl3):
d 34.93 (s, 2F, CF2CF2CF3), 40.83 (q, 2F,
J = 8.8 Hz, CF2CF2CF3), 81.16 (t, 3F, J = 8.8 Hz, CF2CF2CF3). Anal.
Calcd for C13H11N2F7O: C, 45.36; H, 3.22; N, 8.14; F, 38.63. Found: C,
45.43; H, 2.81; N, 8.22; F, 38.72.
4.4. General procedure for synthesis of unsymmetrical bis(b-
aminoenones) H2L4,5
A
solution of
b-methoxyenone 3 (0.20 g, 1.2 mmol) and
4.3. General procedure for synthesis of symmetrical bis(
b
-
corresponding -aminoenone 2b,c (1.0 mmol) in pyridine (2 mL)
b
aminoenones) H2L1–3
was stirred for 2 days (TLC control), dried in vacuum and purified
via a copper complex as described above. Yields of H2L4,5 are given
in the Table 1.
To a solution of o-phenylenediamine (0.162 g, 1.5 mmol) in
B(OBu)3 (3.5 g, 15.2 mmol) 1,3-diketone 1a–c (3.2 mmol) was
added and stirred 1–3 days until disappearance of an aminoenone
2 (TLC). Then CHCl3 (10 mL) and water (20 mL) were added and
stirred 5 min. Water layer was separated and extracted with
CHCl3 (3 ꢃ 5 mL). The combined organic solution were evaporated
and stirred with suspension of copper acetate (1.5 g) in CH3CN
(20 mL) for 3 h. Then water (50 mL) was added, a precipitation
was filtered off, washed with water, dried in the air, and
chromatographed (eluent CHCl3). The obtained solution was
concentrated to ca. 10 mL, and oxalic acid (1.0 g) was added. The
suspension was stirred until the green colour disappeared and
then passed through a silica gel bed (2 cm). Silica gel was washed
with CHCl3 (3 ꢃ 5 mL) and combined chloroform solutions were
evaporated to afford analytically pure product. Yields of H2L1–3
are shown in the Table 1.
(Z)-1,1,1-Trifluoro-4-(2-{[(Z)-4,4,4-trifluoro-1-methyl-3-oxo-
1-butenyl]amino}anilino)-3-penten-2-one (compound H2L1). Yel-
low crystals: mp 123–124 8C [122–124 8C, ref. [12c]. EIMS (probe)
70 eV, m/z (rel. int.): 380 [M]+ (13), 361 [MꢂF]+ (1), 365 [MꢂCH3]+
(16), 341 [MꢂFꢂHF]+ (1), 311 [MꢂCF3]+ (4), 283 [MꢂCF3CO]+ (3),
269 [MꢂCF3COCH2]+ (100), 256 [MꢂCF3COCHCH2]+ (6), 229
[C10H8N2OF3]+ (9).
(Z)-1,1,1-Trifluoro-4-(2-{[(Z)-4,4,4-trifluoro-1-methyl-3-oxo-
1-butenyl]amino}anilino)-3-hexen-2-one
(compound
H2L4).
Light-yellow crystals: mp 61–62 8C. IR (DRA):
n
3153 (N–
Hꢁ ꢁ ꢁO55), 1606, 1586, 1562, 1515 (O55C–C55C, Ar), 1485, 1436 (
d
CH). 1H NMR spectral data (400 MHz, CDCl3):
d
1.13 (3H, t,
J = 7.5 Hz, CH3), 2.07 (3H, s, CH3), 2.32 (2H, q, J = 7.5 Hz, CH2), 5.60
and 5.62 (every 1H, two s, 2 = CH), 7.26–7.32 (2H, m, Ar), 7.41–7.43
(2H, m, Ar), 12.31 and 12.33 (every 1H, two br. s, 2NH). 19F NMR
(376 MHz, CDCl3):
(100 MHz, CDCl3):
d
d
84.79 (s, 3F, CF3), 84.88 (s, 3F, CF3). 13C NMR
11.96 (s, CH2CH3), 19.95 (s, CH3), 25.64 (s,
CH2CH3), 89.84 (q, 3J = 1.3 Hz, 55CH–), 91.95 (q, 3J = 1.3 Hz, 55CH–),
117.21 (q, 1J = 288.2 Hz, CF3), 117.28 (q, 1J = 288.2 Hz, CF3), 127.41,
127.9, 128.56, 128.74 (four singlets, CH, Ar), 132.93, 133.46 (two
singlets, Ar), 167.80 (s,55C(NHAr)–), 173.65 (s,55C(NHAr)–), 177.70
(q, 2J = 33.7 Hz, CF3C55O), 178.11 (q, 2J = 33.7 Hz, CF3C55O). EIMS
(probe) 70 eV, m/z (rel. int.): 394 [M]+ (10), 375 [MꢂF]+ (2), 379
[MꢂCH3]+ (8), 365 [MꢂC2H5]+ (61), 355 [MꢂFꢂHF]+ (1), 325
[MꢂCF3]+ (4), 297 [MꢂCF3CO]+ (2), 283 [MꢂCF3COCH2]+ (100), 270
[MꢂCF3COCH55CH2]+ (2), 256 [C12H11N2OF3]+ (2), 229
[C10H8N2OF3]+ (16). Anal. Calcd for C17H16N2F6O2: C, 51.82; H,
4.09; N, 7.08; F, 28.93. Found C, 51.79; H, 4.04; N, 7.11; F, 28.99.
(Z)-5,5,6,6,7,7,7-Heptafluoro-2-(2-{[(Z)-4,4,4-trifluoro-1-
(Z)-4-(2-{[(Z)-1-ethyl-4,4,4-trifluoro-3-oxo-1-butenyl]ami-
no}anilino)-1,1,1-trifluoro-3-hexen-2-one (compound H2L2). Yel-
methyl-3-oxo-1-butenyl]amino}anilino)-2-hepten-4-one (com-
pound H2L5). Yellow viscous oil. IR (DRA):
n
3149 (NH. . .O55),
1614, 1599, 1583, 1519 (O55C–C55C, Ar), 1484, 1436 (
CH). 1H NMR
spectral data (400 MHz, CDCl3): 2.05 and 2.07 (every 3H, two s,
low crystals: mp 73–74 8C. IR (DRA):
1585, 1513 (O55C–C55C, . . .Ar), 1489, 1452 (
data (400 MHz, CDCl3): 1.13 (6H, t, J = 7.5 Hz, 2CH3), 2.32 (4H, q,
n
3145 (NH. . .O55), 1600,
d
d
CH). 1H NMR spectral
d
d
2CH3), 5.59 and 5.66 (every 1H, two s, 2 = CH), 7.30–7.33 (2H, m,
Ar), 7.41–7.43 (2H, m, Ar), 12.35 and 12.47 (every 1H, two br. s,
2NH). 19F NMR (376 MHz, CDCl3):
d 34.61 (s, 2F, CF2CF2CF3), 40.35
J = 7.5 Hz, 2CH2), 5.62 (2H, s, 2 = CH), 7.30–7.33 (2H, m, Ar), 7.41–
7.44 (2H, m, Ar), 12.31 (2H, br. s, 2NH). 19F NMR (376 MHz, CDCl3):

D.L. Chizhov et al. / Journal of Fluorine Chemistry 132 (2011) 394–401
399
(q, 2F, J = 8.8 Hz, CF2CF2CF3), 81.02 (t, 3F, J = 8.8 Hz, CF2CF2CF3),
84.65 (s, 3F, CF3). 13C NMR (100 MHz, CDCl3):
19.93 (s, CH3), 19.99
for C17H14N2F6O2Cu: C, 44.9; H, 3.1; N, 6.2; F, 25.1. Found: C, 44.8;
H, 3.1; N, 6.1; F, 25.0.
d
(s, CH3), 91.90 (q, 3J = 0.8 Hz, 55CH–), 93.47 (t, 3J = 1.0 Hz, 55CH–),
108.75 (tq, 1J = 265.9, 2J = 38.3 Hz, CF3CF2CF2), 109.44 (tt,
1J = 264.9, 2J = 30.7 Hz, CF3CF2CF2), 117.77 (qt, 1J = 287.8,
2J = 33.7 Hz, CF3CF2CF2), 117.27 (q, 1J = 288.2 Hz, CF3), 127.54,
127.58, 128.67, 128.77 (four singlets, CH, Ar), 133.07, 133.16 (two
singlets, Ar), 167.80 (s,55C(NHAr)–), 167.95 (s,55C(NHAr)–), 177.78
(q, 2J = 33.7 Hz, CF3C55O), 178.64 (t, 2J = 24.4 Hz, C3F7C55O). EIMS
(probe) 70 eV, m/z (rel. int.): 480 [M]+ (19), 461 [MꢂF]+ (3), 465
[MꢂCH3]+ (30), 441 [MꢂFꢂHF]+ (2), 411 [MꢂCF3]+ (5), 383
CuL5. Yield 87%. Deep-green crystals: mp 170–171 8C (hexane).
IR (DRA):
n 1610, 1598, 1579, 1500, 1490, 1429 (O55C–C55C–N, Ar).
EIMS (probe) 70 eV, m/z (rel. int.): 541 [M]+ (100), 526 [MꢂCH3]+
(0.2), 522 [MꢂF]+ (5), 502 [MꢂFꢂHF]+ (0.8), 472 [MꢂCF3]+ (2), 457
[MꢂCF3ꢂCH3]+ (3), 444 [MꢂCF3CO]+ (3), 429 [MꢂCF3COꢂCH3]+
(4), 405 [MꢂCF3COCꢄCCH3]+ (6), 367 [MꢂC3F7]+ (7), 372
[MꢂC3F7COꢂCu]+ (5), 367 [MꢂCF3COCH2ꢂCu]+ (2), 357
[MꢂC3F7ꢂCH3]+
(19),
344
[MꢂC3F7CO]+
(6),
305
[MꢂC3F7COCꢄCCH3]+ (11), 233 [C11H9N2Cu]+ (7), 208
[C9H9N2OCu]+ (6), 195 [C8H8N2Cu]+ (8), 63 [Cu]+ (8). Anal. Calcd
for C18H12N2F10O2Cu: C, 40.1; H, 2.2; N, 5.2; F, 35.1. Found: C, 40.0;
H, 2.4; N, 5.2; F, 35.2.
[MꢂCF3CO]+
(3),
369
(6),
(90),
[MꢂCF3COCH2]+
(100),
(4),
356
269
(6),
[MꢂCF3COCH55CH2]+
[MꢂC3F7COCH2]+
283
256
[MꢂC3F7CO]+
[MꢂC3F7COCH55CH2]+
229 [C12H8N2OF7]+ (7). Anal. Calcd for C18H12N2F10O2: C,
45.04; H, 2.94; N, 5.84; F, 39.58. Found C, 45.07; H, 2.69; N,
5.85; F, 39.54.
NiL1. Yield 90%. IR (DRA):
n 1607, 1597, 1577, 1511, 1489 (O55C–
C55C–N, Ar). Dark-red crystals: mp 284–285 8C (CH3CN) [284–
285 8C, Ref. [13]]. EIMS (probe) 70 eV, m/z (rel. int.): 436 [M]+
(100), 421 [MꢂCH3]+ (2), 417 [MꢂF]+ (4), 367 [MꢂCF3]+
4.5. General procedure for synthesis of Ni(II) and Cu(II) complexes
with H2L1–5
(6),
351
[MꢂCF3HꢂCH3]+
(3),
339
[MꢂCF3CO]+
(15), 300 [MꢂCF3COCꢄCCH3]+ (6), 269 [C13H11N2ONi]+ (6), 58
[Ni]+ (4).
A
solution of bis(
b
-aminoenones) H2L1–5 (0.5 mmol) in
NiL2. Yield 94%. Dark-red crystals: mp 212–213 8C (CH3CN). IR
methanol (5 mL) were added to a solution of Ni(CH3COO)2ꢁ4H2O
(0.124 g, 0.5 mmol) or Cu(CH3COO)2ꢁH2O (0.100 g, 0.5 mmol) in
methanol (ca. 10 mL). The reaction mixture was stirred for 4 h,
diluted with water (20 mL). The resulting precipitate was
collected, washed with water, dried in the air, and crystallized
from an appropriate solvent.
(DRA):
spectral data (400 MHz, CDCl3):
(4H, q, J = 7.5 Hz, 2CH2), 5.78 (2H, s, 2 = CH), 6.92–6.95 (2H, m, Ar),
7.04–7.06 (2H, m, Ar). 19F (376 MHz, CDCl3):
89.36 (s). EIMS
n
1600, 1513, 1489, 1452 (O55C–C55C–N, Ar). 1H NMR
d
1.30 (6H, t, J = 7.5 Hz, 2CH3), 2.73
d
(probe) 70 eV, m/z (rel. int.): 464 [M]+ (100), 445 [MꢂF]+ (4), 435
[MꢂC2H5]+ (4), 395 [MꢂCF3]+ (4), 367 [MꢂCF3CO]+ (11), 58 [Ni]+
(3). Anal. Calcd for C18H16N2F6O2Ni: C, 46.6; H, 3.5; N, 6.0; F, 24.6.
Found: C, 46.6; H, 3.6; N, 6.1; F, 24.4.
CuL1. Yield 93%. Deep-green crystals: mp 244–245 8C (CHCl3)
[244–246 8C, ref. [13]]. IR (DRA):
n 1608, 1597, 1581, 1514, 1489
(O55C–C55C–N, Ar). EIMS (probe) 70 eV, m/z (rel. int.): 441 [M]+
(100), 426 [MꢂCH3]+ (0.3), 422 [MꢂF]+ (3), 402 [MꢂFꢂHF]+ (0.1),
372 [MꢂCF3]+ (4), 357 [MꢂCF3ꢂCH3]+ (13), 344 [MꢂCF3COꢂCH3]+
(8), 329 [MꢂCF3COꢂCH3]+ (20), 305 [MꢂCF3COCꢄCCH3]+ (19), 267
[MꢂCF3COCH2ꢂCu]+ (6), 232 [MꢂCF3COꢂCF3COCH3]+ (11), 232
[C11H9N2Cu]+ (11), 208 [C9H9N2OCu]+ (9), 195 [C8H8N2Cu]+ (8), 63
[Cu]+ (10).
NiL3. Yield 85%. Dark-red crystals: mp 168–169 8C (hexane). IR
(DRA):
spectral data (400 MHz, CDCl3):
2 = CH), 6.94–6.97 (2H, m, Ar), 7.13–7.15 (2H, m, Ar). 19F
(376 MHz, CDCl3): 35.01 (s, 4F, 2CF2CF2CF3), 43.84 (q, 4F,
n
1596, 1503, 1483, 1429 (O55C–C55C–N, Ar). 1H NMR
d
2.40 (6H, s, 2CH3), 5.71 (2H, s,
d
J = 8.8 Hz, 2CF2CF2CF3), 81.04 (t, 6F, J = 8.8 Hz, 2CF2CF2CF3). EIMS
(probe) 70 eV, m/z (rel. int.): 636 [M]+ (100), 621 [MꢂCH3]+ (1),
617 [MꢂF]+ (4), 597 [MꢂFꢂHF]+ (2), 467 [MꢂC3F7]+ (5), 439
[MꢂC3F7CO]+ (7), 58 [Ni]+ (3). Anal. Calcd for C20H12N2F14O2Ni:
C, 37.8; H, 1.9; N, 4.4; F, 41.8. Found: C, 37.8; H, 1.8; N, 4.5;
F, 42.0.
CuL2. Yield 91%. Deep-green crystals: mp 230–231 8C (CHCl3).
IR (DRA):
n 1610, 1600, 1587, 1515, 1490 (O55C–C55C–N, Ar). EIMS
(probe) 70 eV, m/z (rel. int.): 469 [M]+ (100), 450 [MꢂF]+ (3), 440
[MꢂC2H5]+ (0.6), 400 [MꢂCF3]+ (3), 371 [MꢂCF3CO]+ (11), 357
[MꢂCF3COꢂCH3]+ (8), 343 [MꢂCF3COꢂC2H5]+ (15), 319
[MꢂCF3COCꢄCC2H5]+ (22), 295 [MꢂCF3COCH2ꢂCu]+ (7), 260
[MꢂCF3COꢂCF3COCH3]+ (4), 233 [C11H9N2Cu]+ (3), 208
[C9H9N2OCu]+ (2), 195 [C8H8N2Cu]+ (2), 63 [Cu]+ (5). Anal. Calcd
for C18H16N2F6O2Cu: C, 46.1; H, 3.4; N, 5.8; F, 24.3. Found: C, 46.1;
H, 3.4; N, 5.8; F, 24.2.
NiL4. Yield 91%. Dark-red crystals: mp 239–240 8C (CH2Cl2–
hexane, 1:1). IR (DRA):
n
1602, 1512, 1488, 1429 (O55C–C55C–N,
1.30 (t, 3H,
Ar). 1H NMR spectral data (400 MHz, CDCl3):
d
J = 7.5 Hz, CH3), 2.56 (3H, s, CH3), 2.74 (4H, q, J = 7.5 Hz, CH2), 5.70
(1H, s, 55CH), 5.79 (1H, s, 55CH), 6.93–6.96 (2H, m, Ar), 7.12–7.14
(1H, m, Ar), 7.04–7.06 (1H, m, Ar). 19F (376 MHz, CDCl3):
d 89.30 (s,
CuL3. Yield 84%. Deep-green crystals: mp 174–175 8C (hexane).
3F, CF3), 89.35 (s, 3F, CF3). EIMS (probe) 70 eV, m/z (rel. int.): 450
[M]+ (100), 435 [MꢂCH3]+ (3), 431 [MꢂF]+ (4), 421 [MꢂC2H5]+ (1),
381 [MꢂCF3]+ (6), 365 [MꢂCF3HꢂCH3]+ (2), 353 [MꢂCF3CO]+ (14),
314 [MꢂCF3COCꢄCCH3]+ (2), 58 [Ni]+ (4). Anal. Calcd for
IR (DRA):
n 1609, 1598, 1581, 1504, 1488, 1432 (O55C–C55C–N, Ar).
EIMS (probe) 70 eV, m/z (rel. int.): 641 [M]+ (100), 626 [MꢂCH3]+
(0.1), 622 [MꢂF]+ (6), 602 [MꢂFꢂHF]+ (1), 472 [MꢂC3F7]+ (9), 457
[MꢂC3F7ꢂCH3]
(16),
444
[MꢂC3F7CO]+
(8),
405
C17H14N2F6O2Ni: C, 45.4; H, 3.1; N, 6.2; F, 25.3. Found: C, 45.3;
[MꢂC3F7COCꢄCCH3]+ (4), 233 [C11H9N2Cu]+ (11), 208
[C9H9N2OCu]+ (6), 195 [C8H8N2Cu]+ (10), 63 [Cu]+ (10). Anal.
Calcd for C20H12N2F14O2Cu: C, 37.5; H, 1.9; N, 4.7; F, 41.5. Found: C,
37.4; H, 1.8; N, 4.4; F, 41.4.
H, 3.0; N, 6.1; F, 25.1.
NiL5. Yield 89%. Dark-red crystals: mp 188–189 8C (hexane). IR
(DRA):
spectral data (400 MHz, CDCl3):
n
1599, 1504, 1486, 1429 (O55C–C55C–N, Ar). 1H NMR
d
2.39 (3H, s, CH3), 2.41 (3H, s,
CuL4. Yield 95%. Deep-green crystals: mp 243–244 8C (CH2Cl2–
CH3), 5.69 (1H, s, 55CH), 5.72 (1H, s, 55CH), 6.94–6.96 (2H, m, Ar),
hexane, 1:4). IR (DRA):
n
1613, 1602, 1580, 1513, 1490, 1427
7.12ꢂ7.15 (2H, m, Ar). 19F (376 MHz, CDCl3):
d 35.05 (s, 2F,
(O55C–C55C–N, Ar). EIMS (probe) 70 eV, m/z (rel. int.): 455 [M]+
(100), 453 [MꢂCH3]+ (0.3), 436 [MꢂF]+ (4), 426 [MꢂC2H5]+ (0.6),
416 [MꢂFꢂHF]+ (0.1), 386 [MꢂCF3]+ (4), 371 [MꢂCF3, –CH3]+ (5),
358 [MꢂCF3CO]+ (10), 343 [MꢂCF3COꢂCH3]+ (18), 329
[MꢂCF3COꢂC2H5]+ (7), 319 [MꢂCF3COCꢄCCH3]+ (13), 305
[MꢂCF3COCꢄCC2H5]+ (9), 281 [MꢂCF3COCH2ꢂCu]+ (7), 246
[MꢂCF3COꢂCF3COCH3]+ (7), 233 [C11H9N2Cu]+ (4), 207
[C9H9N2OCu]+ (7), 195 [C8H8N2Cu]+ (5), 63 [Cu]+ (10). Anal. Calcd
CF2CF2CF3), 43.73 (q, 2F, J = 8.8 Hz, CF2CF2CF3), 81.27 (t, 3F,
J = 8.8 Hz, CF2CF2CF3), 88.92 (s, 3F, CF3). EIMS (probe) 70 eV, m/z
(rel. int.): 536 [M]+ (100), 521 [MꢂCH3]+ (1), 517 [MꢂF]+ (4), 497
[MꢂFꢂHF]+ (1), 467 [MꢂCF3]+ (1), 451 [MꢂCF3HꢂCH3]+ (1), 439(2)
[MꢂCF3CO], 400 [MꢂCF3COCꢄCCH3]+ (1), 367 [MꢂC3F7]+ (7), 339
[MꢂC3F7CO]+ (7), 268 [C13H11N2ONi]+ (10), 58 [Ni]+ (3). Anal. Calcd
for C18H12N2F10O2Ni: C, 40.3; H 2.3; N, 5.2; F, 35.4. Found: C, 40.4;
H, 2.3; N, 5.1; F, 35.5.

400
D.L. Chizhov et al. / Journal of Fluorine Chemistry 132 (2011) 394–401
4.6. General procedure for synthesis of Pd(II) complexes with H2L1–5
A cold solution of bis(
-aminoenones) H2L1–5 (0.22 mmol) in
Organic Synthesis, Ural Division of the RAS, Ekaterinburg, Russian
Federation.
b
CH3CN (2 mL) was added slowly to a cold solution of Pd(CH3COO)2
(0.050 g, 0.22 mmol) in CH3CN (5 mL), kept for 3 h, and dried in the
vacuum. The residue was crystallized from an appropriate solvent.
References
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PdL1. Yield 78%. IR (DRA):
n 1598, 1576, 1506, 1486 (O55C–
(b) A.S. Burlov, L.I. Kuznetsova, A.I. Uraev, V.P. Kurbatov, G.I. Bondarenko, I.S.
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C55C–N, Ar). Yellow-orange crystals: mp 329–331 8C (CH3CN)
[330–331 8C, ref. [13]]. EIMS (probe) 70 eV, m/z (rel. int.): 484 [M]+
(100), 469 [MꢂCH3]+ (5), 465 [MꢂF]+ (4), 445 [MꢂFꢂHF]+ (0.1),
415 [MꢂCF3]+ (4), 413 [MꢂCF3ꢂCH3]+ (2), 387 [MꢂCF3CO]+ (6),
281 [MꢂCF3ꢂPd]+ (37), 212 [C13H12N2O]+ (8), 105 [Pd]+ (9).
PdL2. Yield 77%. Yellow-orange crystals: mp 298–299 8C
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and Commercial Applications, Plenum Press, New York, 1994;
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(b) R. Belcher, R.J. Martin, W.I. Stephen, D.E. Henderson, A. Kamalizad, P.C. Uden,
Anal. Chem. 45 (1973) 1197–1203;
(CH3CN). IR (DRA):
1H NMR spectral data (400 MHz, CDCl3):
2CH3), 2.87 (4H, q, J = 7.5 Hz, 2CH2), 5.72 (2H, s, 2 = CH), 7.04–7.06
(2H, m, Ar), 7.20–7.25 (2H, m, Ar). 19F (376 MHz, CDCl3):
90.65 (s).
n
1596, 1509, 1485, 1453 (O55C–C55C–N, Ar).
d
1.40 (6H, t, J = 7.5 Hz,
(c) D.N. Sokolov, Gaschromatography of Volatile Metal Complexes, Nauka, Mos-
cow, 1981 (Russian edition);
d
EIMS (probe) 70 eV, m/z (rel. int.): 512 [M]+ (100), 497 [MꢂCH3]+
(2), 493 [MꢂF]+ (4), 483 [MꢂC2H5]+ (8), 473 [MꢂFꢂHF]+ (0.1), 443
[MꢂCF3]+ (2), 415 [MꢂCF3CO]+ (7), 386 [MꢂCF3COꢂC2H5]+ (5), 309
[MꢂCF3ꢂPd]+ (13), 212 [C13H12N2O]+ (8), 105 [Pd]+ (7). Anal. Calcd
for C18H16N2F6O2Pd: C, 42.2; H, 3.2; N, 5.5; F, 22.3. Found: C, 42.3;
H, 3.1; N, 5.3; F, 22.2.
(d) L.N. Bazhenova, K.I. Pashkevich, V.E. Kirichenko, A.Ja. Ajzikovich, Zhurn.
Analit. Khimii. 36 (1981) 410–414 (Russian edition);
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Khimii. 37 (1982) 289–295 (Russian edition);
(f) K.I. Pashkevich, L.N. Bazhenova, V.E. Kirichenko, I.G. Busygin, Zhurn. Analit.
Khimii. 40 (1985) 1694–1698 (Russian edition).
[4] (a) J.A. Daar, M. Poljakov, Chem. Rev. 99 (1999) 495–541;
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Kaloyeros, Chem. Mater. 4 (1992) 912–916;
PdL3. Yield 71%. Yellow-orange crystals: mp 178–179 8C
(hexane). IR (DRA):
1H NMR spectral data (400 MHz, CDCl3):
(2H, s, 2 = CH), 7.05–7.08 (2H, m, Ar), 7.32–7.35 (2H, m, Ar). 19F
(376 MHz, CDCl3):
35.16 (s, 4F, 2CF2CF2CF3), 45.23 (q, 4F, 4J = 8.8,
n
1597, 1499, 1483, 1431(O55C–C55C–N, Ar).
(d) A.C. Jones, J. Mater. Chem. 12 (2002) 2576–2590;
(e) P.L. Franceschini, M. Morstein, H. Berke, H.W. Schmalle, Inorg. Chem. 42
(2003) 7273–7282;
(f) R.L. Nigro, G. Malandrino, R.G. Toro, I.L. Fragal, Topics Appl. Phys. 106 (2007)
33–51.
d
2.55 (6H, s, 2CH3), 5.65
d
2CF2CF2CF3), 81.19 (t, 6F, J = 8.8 Hz, 2CF2CF2CF3). EIMS (probe)
70 eV, m/z (rel. int.): 684 [M]+ (100), 669 [MꢂCH3]+ (4), 665 [MꢂF]+
(7), 645 [MꢂFꢂHF]+ (0.4), 515 [MꢂC3F7]+ (6), 409 [MꢂC3F7ꢂPd]+
(39), 381 [MꢂC3F7COꢂPd]+ (55), 212 [C13H12N2O]+ (22), 105 [Pd]+
(8). Anal. Calcd for C20H12N2F14O2Pd: C, 35.1; H, 1.8; N, 4.1; F, 38.9.
Found: C, 35.2; H, 1.7; N, 4.0; F, 38.8.
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(c) W.N. Wallis, S.C. Cummings, Inorg. Chem. 13 (1974) 988–991;
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Nucl. Chem. 35 (1973) 1127–1144;
PdL4. Yield 80%. Yellow-orange crystals: mp 289–290 8C
(CH2Cl2–hexane, 1:1). IR (DRA):
n 1598, 1508, 1485, 1427
(d) P.C. Uden, K. Bessel, Inorg. Chem. 12 (1973) 352–356;
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1625–1628 (Russian edition).
(O55C–C55C–N, Ar). 1H NMR spectral data (400 MHz, CDCl3):
d
1.40 (3H, t, J = 7.5 Hz, CH3), 2.56 (3H, s, CH3), 2.88 (4H, q, J = 7.5 Hz,
2CH2), 5.67 (1H, s, 55CH), 5.73 (1H, s, 55CH), 7.04–7.06 (2H, m, Ar),
7.33–7.35 (2H, m, Ar). 19F (376 MHz, CDCl3):
d 90.61 (s, 3F, CF3),
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Inorg. Chem. 21 (1982) 1226–1232;
90.66 (s, 3F, CF3). EIMS (probe) 70 eV, m/z (rel. int.): 498 [M]+ (100),
483 [MꢂCH3]+ (8), 479 [MꢂF]+ (3), 469 [MꢂC2H5]+ (2), 459
[MꢂFꢂHF]+ (0.1), 429 [MꢂCF3]+ (3), 427 [MꢂCF3ꢂCH3]+ (2), 401
[MꢂCF3CO]+ (8), 373 [MꢂCF3COꢂC2H5]+ (1), 295 [MꢂCF3ꢂPd]+
(23), 212 [C13H12N2O]+ (3), 105 [Pd]+ (10). Anal. Calcd for
(b) W. Ru¨ttinger, G.Ch. Dismukes, Chem. Rev. 97 (1997) 1–24;
(c) C.J. Chang, J.A. Labinger, H.B. Gray, Inorg. Chem. 36 (1997) 5927–5930;
(d) R. Ramnauth, S.Al-Ju.M. Motevalli, B.C. Parkin, A.C. Sullivan, Inorg. Chem. 43
(2004) 4072–4079;
(e) M. Kuil, P.E. Goudriaan, P.W.N.M. Leeuwen, J.N.H. Reek, Chem. Commun.
(2006) 4679–4681.
C
17H14N2F6O2Pd: C, 41.0; H, 2.8; N, 5.6; F, 22.9. Found: C, 40.9;
[10] (a) S. Di Bella, I. Fragala´, I. Ledoux, T.J. Marks, J. Am. Chem. Soc. 117 (1995) 9481–
9485;
H, 2.6; N, 5.8; F, 22.6.
PdL5. Yield 72%. Yellow-orange crystals: mp 194–195 8C
(b) S.M. Kim, J.S. Kim, B.C. Sohn, Y.K. Kim, Y.Y. Ha, Mol. Cryst. Liq. Cryst. 371
(2001) 321–324;
(c) F. Averseng, P.G. Lacroix, I. Malfant, G. Lenoble, P. Cassoux, K. Nakatani, I.
Maltey-Fanton, J.A. Delaire, A. Aukauloo, Chem. Mater. 11 (1999) 995–1002.
[11] (a) E. Koenig, G. Ritter, J. Dengler, L.F. Larkworthy, Inorg. Chem. 31 (1992) 1196–
1202;
(hexane). IR (DRA):
1H NMR spectral data (400 MHz, CDCl3):
(3H, s, CH3), 5.65 (1H, s,55CH), 5.66 (1H, s,55CH), 7.05–7.09 (2H, m,
Ar), 7.33–7.36 (2H, m, Ar). NMR 19F (376 MHz, CDCl3):
35.50 (s,
n
1595, 1501, 1482, 1426 (O55C–C55C–N, Ar).
d
2.56 (3H, s, CH3), 2.57
d
2F, CF2CF2CF3), 45.39 (q, 2F, J = 8.8 Hz, CF2CF2CF3), 81.33 (t, 3F,
J = 8.8 Hz, CF2CF2CF3), 90.40 (s, 3F, CF3). EIMS (probe) 70 eV, m/z
(rel. int.): 584 [M]+ (100), 569 [MꢂCH3]+ (5), 565 [MꢂF]+ (6), 545
[MꢂFꢂHF]+ (0.2), 515 [MꢂCF3]+ (2), 513 [MꢂCF3ꢂCH3]+ (0.6), 487
[MꢂCF3CO]+ (2), 415 [M-CF3COCH55CCH3]+ (5), 381 [MꢂCF3ꢂPd]+
(12), 309 [MꢂC3F7ꢂPd]+ (30), 281 [MꢂC3F7COꢂPd]+ (39), 212
[C13H12N2O]+ (14), 105 [Pd]+ (9). Anal. Calcd for C18H12N2F10O2Pd:
C, 37.0; H 2.1; N, 4.8; F, 32.5. Found: C, 37.0; H, 2.0; N, 4.6, F, 32.4.
´
´
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Acknowledgements
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Chem. 51 (2010) 288–295.
The study was supported by the Ural Division of the RAS
(programs 09-M-23-2006 and 09-P-3-1013). Spectroscopic inves-
tigations and elemental analysis have been made in the Institute of
[14] K.I. Pashkevich, D.V. Sevenard,O.G. Khomutov,Russ.Chem. Bull. 48(1999) 557–560.

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