New enamine ligands derived from ethyl 2-ethoxymethylidene-3-oxo-3- polyfluoroalkylpropionates and o-phenylenediamine

Article abstract of DOI:10.1007/s11172-010-0281-2

Diethyl 2,2′-[1,2-phenylenebis(aminomethylidene)]bis(3-oxo-3- polyfluoroalkylpropionates) were synthesized by the condensation of a double excess of ethyl 2-ethoxymethylidene- 3-oxo-3-polyfluoroalkylpropionates with o-phenylenediamine. The use of equimola

Full text of DOI:10.1007/s11172-010-0281-2

Russian Chemical Bulletin, International Edition, Vol. 59, No. 8, pp. 1582—1593, August, 2010
1582
New enamine ligands derived from ethyl
2ꢀethoxymethylideneꢀ3ꢀoxoꢀ3ꢀpolyfluoroalkylpropionates
and oꢀphenylenediamine
Yu. S. Kudyakova, M. V. Goryaeva, Ya. V. Burgart, P. A. Slepukhin, and V. I. Saloutin
I. Ya. Postovsky Institute of Organic Synthesis, Ural Branch of the Russian Academy of Sciences,
22/20 ul. S. Kovalevskoi/Akademicheskaya, 620041 Ekaterinburg, Russian Federation.
Fax: +7 (343) 374 5954. Eꢀmail: saloutin@ios.uran.ru
Diethyl 2,2´ꢀ[1,2ꢀphenylenebis(aminomethylidene)]bis(3ꢀoxoꢀ3ꢀpolyfluoroalkylpropionꢀ
ates) were synthesized by the condensation of a double excess of ethyl 2ꢀethoxymethylideneꢀ
3ꢀoxoꢀ3ꢀpolyfluoroalkylpropionates with oꢀphenylenediamine. The use of equimolar ratios
of the starting reactants affords ethyl 2ꢀ[(2ꢀaminophenyl)aminomethylidene]ꢀ3ꢀoxoꢀ
3ꢀpolyfluoroalkylpropionates from which nonsymmetric biscondensation products were synꢀ
thesized by the reaction with related reactants containing different polyfluoroalkyl substituent.
The copper(II), nickel(II), and cobalt(II) complexes were obtained on the basis of new ligands.
Key words: βꢀketo acids, oꢀphenylenediamine, enamines, ligands, copper(II) complexes,
nickel(II) complexes, cobalt(II) complexes, organofluorine compounds.
Interest in synthesis of metal complexes based on
room temperature afforded the monoadducts, viz., ethyl
2ꢀ[(2ꢀaminophenyl)aminomethylidene]ꢀ3ꢀfluoroalkylꢀ
3ꢀoxopropionates 2a—с, as a result of the nucleophilic
attack of the amino group at the ethoxymethylidene
moiety (Scheme 1). The use of a double excess of esters
1a—c results in the formation of symmetric products 3a—c
due to the condensation of two molecules of ester 1a—c
with one diamine molecule.
Monosubstitution products 2а—c contain free NH2
groups, which makes it possible to carry out their further
transformations. The condensation of compounds 2а,с
with the corresponding substrates 1a,b (see Scheme 1)
azomethine compounds is caused by their catalytic activity
in polymerization reactions1—3 and magnetic4—7 and
luminescence8,9 properties. Nonꢀfluorinated 2ꢀethoxyꢀ
methylideneꢀ1,3ꢀdicarbonyl compounds in reactions
with 1,2ꢀdiamines form biscondensation products at the
ethoxymethylidene moiety10—12 and related metal comꢀ
plexes.13—16 It is possible to obtain monocondensation
products17—19 from which symmetric and asymmetric
ligands20 were synthesized, including the macrocyclic
ligands15,17—20 used in the synthesis of the metallocomplex
compounds.17—20 Schiff bases obtained by transformations
of 2ꢀethoxymethylideneꢀ3ꢀoxoꢀ3ꢀfluoroalkylpropionates
with different diamines can also serve as organic molꢀ
ecules forming the ligand shell. It is known21 that the
introduction of the fluorine atom into organic molecules
changes their physicochemical properties, reactivity, bioꢀ
logical activity and other characteristics caused by the
presence of electronegative fluorine atoms and important
in practical and theoretical aspects. However, published
data on the participation of polyfluorinated analogs in
similar polycondensation reactions are lacking.
F(3)
F(4)
C(5)
O(3)
F(1)
2.008
N(2)
C(4)
C(2)
C(1)
C(3)
F(2)
C(10)
N(1)
C(8)
C(11)
C(12)
C(9)
C(14)
O(1)
In the present work, we studied the reactions of ethyl
2ꢀethoxymethylideneꢀ3ꢀoxoꢀ3ꢀpolyfluoroalkylpropionꢀ
ates 1 with oꢀphenylenediamine with the purpose to synꢀ
thesize new ligands and analyzed a possibility of the prepaꢀ
ration of related metallocomplex compounds with a series
of transition metals.
C(13)
O(2)
C(6)
C(7)
It was found that the reaction of compounds 1a—c
with 1 equiv. of oꢀphenylenediamine in diethyl ether at
Fig. 1. Crystal structure of compound 2b.
Published in Russian in Izvestiya Akademii Nauk. Seriya Khimicheskaya, No. 8, pp. 1544—1554, August, 2010.
1066ꢀ5285/10/5908ꢀ1582 © 2010 Springer Science+Business Media, Inc.

Fluorinated (O)N2O ligands
Russ.Chem.Bull., Int.Ed., Vol. 59, No. 8, August, 2010
1583
Scheme 1
1: RF = CF3 (a), (CF2)2H (b), C3F7 (c); 2: RF = CF3 (a), (CF2)2H (b), C3F7 (c); 3: RF = RF´ = CF3 (a), (CF2)2H (b), C3F7 (c);
F = CF3, RF´ = (CF2)2H (d); RF = CF3, RF´ = C3F7 (e); RF = (CF2)2H, RF´ = C3F7 (f)
R
Conditions: i. Et2O, ~20 °C, 30 min; ii. Et2O, ~20 °C, 4—5 h.
affords nonsymmetric tetradentate ligands 3d—f conꢀ
taining two different polyfluorinated substituents.
The structures of synthesized compounds 2a—с
parameters: the intramolecular distance O(1)...H(1)
is 2.00(8) Å, and the angles N(1)—H(1)...O(3) and
C(3)—O(3)...H(1) are 131.52 and 101.79°. The main
chelate moiety of the molecule has the approximately
planar structure, because the maximum shifts of atoms
from the hexagon H(1)N(1)C(8)C(2)C(3)O(3) are
0.06(4) Å (C(3) atom). The benzene moiety is turned
out relative to the chelate unit: the dihedral angle beꢀ
tween the H(1)N(1)C(8)C(2)C(3)O(3) planes and the
benzene ring is 54.3°.
1
and 3a—f were determined by IR spectroscopy, H and
19F NMR spectroscopy, and elemental analysis. The
Xꢀray diffraction study was also carried out for ester 2b
(Fig. 1).
According to the Xꢀray diffraction data, ester 2b exists
in crystal as the sꢀtrans,sꢀcisꢀconformer of the Еꢀisomer
of the aminoketone tautomer (see Fig. 1, Table 1). The
molecule contains the intramolecular hydrogen bond
O(3)...H(1)N(1), which is characterized by the following
A comparative analysis of the IR spectra of compounds
2a—с revealed no substantial differences between them.
Table 1. Selected bond lengths (d) and bond angles (ω) for compounds 2b and 4b
Parameter
Value
Parameter
Value
Parameter
Value
ω/deg
113.10(13)
123.92(12)
126.30(15)
120.30(13)
Bond length
d/Å
Bond length
N(1)—C(1)
O(2)—C(7)
C(7)—C(8)
N(2)—C(2)
C(9)—C(8)
C(12)—C(8)
C(1)—C(2)
Angle
d/Å
Angle
2b
1.424(2
1.204(2)
1.484(3)
1.449(3)
1.383(3)
1.432(3)
1.392(3)
ω/deg
O(3)—C(3)—C(4)
C(2)—C(3)—C(4)
N(1)—C(8)—C(2)
N(2)—C(10)—C(9)
4b
O(1)—Cu(1)—N(1)
O(1)—Cu(1)—N(2) 176.38(7)
N(1)—Cu(1)—N(2)
O(1)—Cu(1)—Cl(2)
N(1)—Cu(1)—Cl(2) 175.31(5)
N(2)—Cu(1)—Cl(2)
C(9)—O(1)—Cu(1)
C(12)—N(1)—C(1)
C(12)—N(1)—Cu(1) 125.09(14)
C(1)—N(1)—Cu(1) 112.31(12)
C(2)—N(2)—Cu(1) 109.38(12)
N(1)—С(8)
N(1)—C(9)
N(1)—H(1)
O(1)—C(1)
C(1)—O(2)
C(1)—C(2)
C(2)—C(8)
C(2)—C(3)
N(2)—C(10)
O(3)—C(3)
C(3)—C(4)
1.3229(17)
1.4279(18)
0.849(17)
1.2094(17)
1.3395(18)
1.473(2)
1.400(2)
1.428(2)
1.384(2)
1.2449(16)
1.544(2)
92.04(6)
85.31(6)
90.19(5)
2b
C(8)—N(1)—C(9)
C(8)—N(1)—H(1)
C(9)—N(1)—H(1)
O(1)—C(1)—O(2)
O(1)—C(1)—C(2)
O(2)—C(1)—C(2)
C(8)—C(2)—C(3)
C(8)—C(2)—C(1)
C(3)—C(2)—C(1)
O(3)—C(3)—C(2)
124.02(14)
116.6(10)
119.1(10)
122.55(13)
125.04(14)
112.32(12)
119.00(12)
118.70(14)
122.30(13)
122.89(13)
92.63(5)
127.28(14)
122.57(16)
4b
Cu(1)—O(1)
Cu(1)—N(1)
Cu(1)—N(2)
Cu(1)—Cl(2)
O(1)—C(9)
1.9213(14)
1.9504(15)
1.9855(17)
2.2541(6)
1.263(2)
C(9)—C(8)—C(12)
C(9)—C(8)—C(7)
121.65(17)
121.86(18)
N(1)—C(12)
1.289(2)

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Kudyakova et al.
In each case, the presence of intense absorption bands of
stretching vibrations corresponding to two carbonyl groups
(1710—1697 and 1673—1647 cm–1) and NH and NH2
groups (3254—3177 cm–1) also indicates that they exist
are the Еꢀisomer of the aminoketone tautomer stabilized
by the intramolecular hydrogen bond between the oxygen
atom of the polyfluoroacyl moiety and the hydrogen atom
of the NH group.
The IR spectrum of compound 2a in a 3% solution of
CHCl3 exhibits a considerable broadening of absorption
bands of vibrations of almost all characteristic groups.
1
It was established by H and 19F NMR spectroscopy
that esters 2a—с in a СDCl3 solution exist as an equilibrium
mixture of Zꢀ and Eꢀisomers. For example, the 1Н NMR
spectra of compounds 2a—с in СDCl3 contains two sets
of signals in which the signals of the NHꢀ and CHꢀproꢀ
tons of the methylidene moiety are observed in the lowꢀ
frequency region (δCH ~8.29—8.55, δNH ~11.14—12.18)
as doublets with the spinꢀspin coupling constant (SSCC)
~14 Hz. The 19F NMR spectra of compounds 2a—с are
also characterized by doubling of the resonance signals of
the fluorine nuclei. The signals were assigned to the Zꢀ or
Eꢀisomeric form according to the principles established
earlier.22 According to this, the shifts of the protons of
1
In fact, the Н and 19F NMR spectra of compounds
3a—с in CDCl3 contain three sets of signals correspondꢀ
ing to the E,Eꢀ, Z,Zꢀ, and E,Zꢀisomeric forms, whereas
the spectra of compounds 3d—f exhibit four sets correꢀ
sponding to the E,Eꢀ, E,Zꢀ, Z,Eꢀ, and Z,Z forms (see
Experimental, Table 2). The signals were assigned to the
E,Eꢀ, E,Zꢀ, Z,Eꢀ, and Z,Z forms using the data obtained
by us earlier.22
1
the СН and NH groups are determining in the Н NMR
spectra: for the Еꢀisomer the signals of these groups are
observed in a weaker field compared to the signals of the
protons corresponding to the Zꢀisomer. In the 19F spectra,
the signals of the fluorine atoms of the αꢀCF3 and αꢀCF2
groups of the Z form are characterized by a more downfield
shift compared to the corresponding signals of the fluorine
atoms of the Еꢀisomer.
Based on the structure of ligands 2a—c, one may
assume that they are able to form metallocomplex comꢀ
pounds due to coordination involving the tridentate N2O
moiety. However, the treatment of ester 2b with copper(II)
and nickel(II) acetates gave no desirable metal complexes,
unlike the transformations of the nonꢀfluorinated
analog.17 Nevertheless, the use of copper(II) chloride made
it possible to obtain complex 4b (Scheme 2), being a
crystalline dark green powder. The elemental analysis data
for compound 4b correspond to the composition CuLCl,
where L is the monodeprotonated ligand. In its IR specꢀ
trum characteristic bands are the highꢀfrequency absorpꢀ
tion bands at 1708 cm–1 corresponding to vibrations
of the carbonyl groups of the ester moiety, the bands at
1615 and 1593 cm–1 caused by vibrations of the С=О and
С=С chelate node, and the absorption bands at 3282
and 3190 cm–1 corresponding to symmetric and antisymꢀ
metric stretching vibrations of the NH2 group. A comꢀ
parative analysis of the IR spectra of ligand 2b and comꢀ
plex 4b revealed their substantial differences. The abꢀ
sorption bands of the carbonyl group of the fluoroacyl
substituent of complex 4b are characterized by the shift to
the lowꢀfrequency region compared to the analogous band
Easiness of isomerization of the С=С bonds in esters
2а—с is due to the fact that, being neighbors of functional
groups of different electronegativity, they are a part of the
polarized pushꢀpull conjugated system in which the rotaꢀ
tion barrier about the С=С double bonds is substantially
decreased.23 We have earlier22 found that the tendency
to undergo isomerization of the Eꢀisomer to a mixture of
Zꢀ and Eꢀisomers upon dissolution is general for ethyl
esters of 2ꢀ(Rꢀaminomethylidene)ꢀ3ꢀoxoꢀ3ꢀpolyfluoroꢀ
alkylpropionic acids (R is alkyl, aryl, or hetaryl).
The IR spectra of diesters 3a—f contain two highꢀfreꢀ
quency absorption bands (1726—1698, 1703—1638 cm–1) corꢀ
responding to vibrations of two different carbonyl groups
and the broadened absorption band at 3210—3177 cm–1
caused by stretching vibrations of the NH group. These
data indicate the existence of diesters 3a—f as an aminoꢀ
ketone tautomer analogous to monosubstitution products
2a—с.
Three isomeric forms (E,E, Z,Z, and E,Z) are possible
for symmetric diesters 3a—c containing two С=С bonds,
whereas four isomeric forms, viz., E,E, Z,Z, E,Z, and
Z,E, are possible for asymmetric diesters 3d—f having two
С=С bonds and two different fluorinated substituents.

Fluorinated (O)N2O ligands
Russ.Chem.Bull., Int.Ed., Vol. 59, No. 8, August, 2010
1585
Table 2. Chemical shifts (δ) of the NHꢀ and CHꢀprotons of the E,Eꢀ, Z,Zꢀ, E,Zꢀ, and Z,Eꢀisomers of compounds 3а—f
1
according to the data of H NMR spectroscopy (in СDCl3)
Comꢀ
pound
E,E
Z,Z
E,Z
Z,E
3a
3b
3c
3d
8.51 (СH(E));
12.15 (NH(E))
8.40 (СH(E));
12.17 (NH(E))
8.65 (СH(E));
12.00 (NH(E))
8.40 (СH(E));
8.50 (СH(E));
12.15 (NH(E))
8.41 (СH(E));
8.49 (СH(E));
12.17 (NH(E))
8.36 (СH(Z));
11.58 (NH(E))
8.29 (СH(Z));
11.45 (NH(E))
8.42 (СH(Z));
11.62 (NH(E))
8.28 (СH(Z));
8.35 (СH(Z));
11.48 (NH(E))
8.22 (СH(Z));
8.35 (СH(Z));
12.02 (NH(E));
12.17 (NH(E))
8.22 (СH(Z));
8.29 (СH(Z));
11.45 (NH(E));
11.48 (NH(E))
8.37 (СH(Z)); 8.51 (СH(E));
11.59 (NH(Z)); 12.11 (NH(E))
8.29 (СH(Z); 8.40 (СH(E));
11.46 (NH(Z)); 12.15 (NH(E))
8.43 (СH(Z)); 8.66 (СH(E));
11.60 (NH(Z)); 12.01 (NH(E))
8.36 (СH(Z)); 8.39 (СH(E));
11.62 (NH(Z)); 12.11 (NH(E))
—
—
—
8.29 (СH(Z)); 8.49 (СH(E));
11.43 (NH(Z)); 12.12 (NH(E))
3e
3f
8.34 (СH(Z)); 8.41 (СH(E));
11.60 (NH(Z)); 11.99 (NH(E))
8.22 (СH(Z)); 8.50 (СH(E));
11.44 (NH(Z)); 12.10 (NH(E))
8.39 (СH(E));
8.40 (СH(E));
11.45 (NH(E));
11.48 (NH(E))
8.28 (СH(Z)); 8.41 (СH(E));
11.31 (NH(Z)); 12.03 (NH(E))
8.21 (СH(Z)); 8.38 (СH(E));
11.34 (NH(Z)); 11.99 (NH(E))
of free ligand 2b, and the vibrations of the ethoxycarbonyl
group in ligand 2b and in complex 4b are observed in
almost the same ranges. In addition, the IR spectra of
metal complex 4b are characterized by a decrease in the
intensity of the absorption bands corresponding to stretchꢀ
ing vibrations of the NH groups.
The steric structure of complex 4b was studied by
Xꢀray diffraction analysis (Fig. 2, see Table 1). According
to the Xꢀray diffraction data, the copper(II) cation has a
distorted planar square environment of two nitrogen
atoms of the phenylenediamine moiety, the oxygen atom
of the fluoroacyl group, and the chlorine atom. The maxiꢀ
mum shifts from the plane of atoms surrounding the copꢀ
per ion are 0.06(7) Å (N(1) atom). The maximum difꢀ
ference in the bond lengths forming the square environꢀ
ment of the NiII ion reaches 0.40(5) Å. As a result of the
tridentate coordination of the ligand, two conjugated metal
cycles, viz., fiveꢀ and sixꢀmembered, are formed in the
molecule. The crystal packing of complex 4b is formed
due to the formation of polymeric stacks with shortened
intermolecular contacts between the copper and chlorine
atoms of the adjacent molecules with the measured disꢀ
tances d(Cu(1)...Cl(2)[1.5 – х, –0.5 + у, 0.5 – z]) =
= 3.030 Å and d(Cl(2)...Cu(1)[1.5 – х, –0.5 + у, 0.5 – z]) =
Scheme 2
C(14)
C(13)
O(2)
C(7)
O(3)
C(11)
F(3)
F(2)
C(10)
C(8)
C(9)
O(1)
C(12)
C(6)
F(4)
F(1)
C(5)
C(4)
N(1)
N(2)
C(1)
C(2)
Cu(1)
Cl(2)
C(3)
Fig. 2. Crystal structure of compound 4b.
Conditions: i. EtOH, b.p.

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Kudyakova et al.
= 3.170 Å. In addition, the structure contains the interꢀ
molecular hydrogen bond between the hydrogen atom of
the amino group and the oxygen atom of the fluoroacyl
moiety of the adjacent molecule (N(2)—H(2A)...O(1)
[–x + 3/2, y – 1/2, –z + 1/2]), which is characterized
by the following parameters: d(N(2)—H) = 0.900 Å,
d(H...O(1)) = 2.585(2) Å, d(N(2)...O(1)) = 3.432(2) Å,
and ω(N(2)—H(2A)...O(1)) = 156.9(2)°.
Our further attempts to synthesize the N4ꢀtetradentate
macrocyclic ligand from esters 2а—с by analogy to
the nonꢀfluorinated derivatives15,17—20 were unsuccessful:
neither template nor direct syntheses did not allow us
to obtained a macrocycle of the A type (see Scheme 2).
Upon the treatment with nickel(II), cobalt(II), and
copper(II) salts, compounds 3a,d—f readily form metal
complexes 5a—j (Scheme 3). Symmetric chelates 5
can also be synthesized by the template method. Metal
complex 5a was synthesized on the nickel(II) ion matrix
from ester 1a and oꢀphenylenediamine.
Scheme 3
complexes 5a,d,g,i contain a downfield shift of the signals
of the αꢀfluorine atoms (δCF ~94 (5a,d,g), δα
~43
ꢀCF
3
2
(5d,i), and δαꢀ
~51 (5g,i)) compared to analogous
CF
2
values for free ligands 3a,d—f (δCF ~88—89 (3a,d,e),
3
δα
~40—41 (3d,f), and δα
~48—49 (3e,f)), which
ꢀCF
2
ꢀCF
2
is explained by the participation of the polyfluoroacyl
groups in coordination with the nickel(II) cation, which is
observed in structure B.
Using the Xꢀray diffraction study, we determined the
spatial structure of complexes 5a—j for compounds 5a,d
as an example (Figs 3—6). The crystal packing of comꢀ
pound 5a is formed by two crystallographically indeꢀ
pendent molecules (I and Ia) with different spatial orienꢀ
tations of one ethoxycarbonyl group (see Fig. 3).
5: RF = RF´= CF3, M = Ni (a), Co (b), Cu (c); RF = RF´ = C3F7,
M = Ni (d), Cu (e), Co (f); RF = CF3, RF´ = C3F7, M = Ni (g), Cu (h);
R
F = (CF2)2H, RF´ = C3F7, M = Ni (i), Cu (j)
Conditions: i. EtOH, M(OAc)2, Δ, 5 min; ii. EtOH, Ni(OAc)2,
~20 °C, 2 days.
The atoms of molecule I in compound 5a are enumerꢀ
ated with figures, whereas the atoms of molecule Ia are
designated with figures added by letter "A". The general
organization of the chelate node (bond lengths, bond
angles) of the both molecules is similar (Table 3). The
atoms Ni(1)—N(1)—N(2)—O(6)—O(3) and Ni(1А)—
N(1А)—N(2А)—O(6А)—O(3А) forming the chelate nodes
of molecules I and Iа lie in almost the same plane (the
shift from the rootꢀmeanꢀsquare plane is not more than
0.01(4) Å). The aryl and amino enone moieties are
arranged in the same plane (the maximum deviation of
the carbon atoms of the aryl substituent reaches 0.07(8) Å
(С(10) and С(7А) atoms), whereas the shift of the amino
enone substituent is 0.15(1) Å (С(2А) atom). The nickel
atoms in molecules I and Iа have the coordination mode
of a distorted square. A slight distortion of the chelate
The structures of complexes 5 were determined by
1H and 19F NMR spectroscopy, IR spectroscopy, elemenꢀ
tal analysis, and Xꢀray diffraction. In metal complexes
5a—j coordination with the metal ion can occur by three
different ways: due to the nitrogen atom and the oxygen
atom at the fluoroalkyl substituent (structure B), involvꢀ
ing the nitrogen atom and the oxygen atom of the ester
group (structure C), or due to the oxygen atoms of the
1,3ꢀdicarbonyl moiety (structure D).
The IR spectra of compounds 5a—j contain two highꢀ
frequency absorption bands at 1726—1698 cm–1 assigned
to vibrations of the carbonyl groups, which may correꢀ
spond to structures B and C. The 1Н and 19F NMR specꢀ
tra of nickel complexes 5a,d,g,i detected in CDCl3 soluꢀ
tions exhibit one set of signals. The 19F NMR spectra of

Fluorinated (O)N2O ligands
Russ.Chem.Bull., Int.Ed., Vol. 59, No. 8, August, 2010
1587
C(9A)
C(8A)
C(9)
C(10)
C(8)
C(7)
C(10A)
C(7A)
C(11A)
N(2A)
C(6A)
C(18A)
O(2A)
C(20)
C(11)
N(2)
C(6)
O(5)
C(16)
C(13)
C(18)
N(1A)
C(16A)
O(2)
N(1)
C(17)
C(5)
C(12A)
C(5A)
C(2A)
C(13A)
Ni(1A)
C(17A)
O(1A)
O(19A)
O(4)
C(2)
C(1)
O(1)
O(5A)
C(14A)
Ni(1)
C(1A)
C(3A)
C(12)
C(14)
F(6)
O(6A)
C(3)
C(20A)
F(5A)
O(3A)
C(4A)
O(6)
C(15A)
O(3)
C(4)
F(2A)
C(15)
F(5)
F(3)
F(4A)
F(6A)
F(3A)
F(4)
F(2)
F(1)
F(1A)
Ia
I
Fig. 3. General view of molecules I and Ia in compound 5a.
b
C(3)
3.432
C(4)
C(5)
C(2)
3.432
3.432
C(1)
N(1)
3.560
3.432
C(21)
C(6)
N(2)
O(3)
C(12)
3.432
C(19)
C(18)
O(6)
C(20)
C(15)
3.432
C(8)
C(9)
F(2)
C(7)
O(4)
Ni(1)
C(14)
C(16)
a
c
C(13)
O(5)
4.462
3.432
O(1)
O(2)
3.432
C(10)
C(11)
F(4)
F(1)
3.432
C(17)
F(7)
F(6)
F(3)
F(5)
Fig. 4. Molecular packing along the а axis of molecules 5а
Fig. 5. General view of molecule 5d.
(hydrogen atoms are omitted).
b
0
a
c
Fig. 6. Molecular packing along the vector а + b of molecules 5d (hydrogen atoms are omitted).

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Kudyakova et al.
Table 3. Selected bond lengths (d) and bond angles (ω) for compounds 5a and 5d
Parameter
5a
Parameter
5d
I
Ia
Bond length
d/Å
Bond length
d/Å
Ni(1)—N(1)
Ni(1)—N(2)
Ni(1)—O(6)
Ni(1)—O(3)
N(1)—C(5)
N(1)—C(6)
N(2)—C(16)
N(2)—C(11)
C(6)—C(11)
O(3)—C(3)
O(6)—C(14)
C(13)—C(14)
C(13)—C(16)
C(2)—C(3)
C(2)—C(5)
C(1)—O(1)
1.807(3)
1.822(4)
1.824(3)
1.841(3)
1.299(5)
1.431(5)
1.286(5)
1.419(5)
1.369(6)
1.252(5)
1.269(5)
1.394(6)
1.403(6)
1.384(6)
1.405(6)
1.177(5)
1.169(5)
1.485(6)
1.485(6)
1.823(3)
1.839(3)
1.817(3)
1.817(3)
1.318(5)
1.421(5)
1.316(5)
1.406(5)
1.384(6)
1.262(5)
1.277(5)
1.368(6)
1.395(6)
1.369(6)
1.399(6)
1.185(6)
1.179(6)
1.503(6)
1.485(6)
Ni(1)—N(1)
Ni(1)—N(2)
Ni(1)—O(2)
Ni(1)—O(1)
N(1)—C(12)
N(1)—C(1)
N(2)—C(15)
N(2)—C(6)
C(6)—C(1)
O(1)—C(9)
O(2)—C(16)
C(16)—C(14)
C(15)—C(14)
C(8)—C(9)
C(8)—C(12)
O(3)—C(7)
1.8403(19)
1.8315(19)
1.8395(17)
1.8398(16)
1.300(3)
1.421(3)
1.302(3)
1.426(3)
1.393(3)
1.281(3)
1.266(3)
1.386(3)
1.423(3)
1.378(3)
1.410(3)
1.197(3)
1.195(3)
1.490(4)
1.476(3)
ω/deg
O(4)—C(12)
C(1)—C(2)
C(12)—C(13)
Angle
O(5)—C(13)
C(8)—C(7)
C(14)—C(13)
Angle
ω/deg
N(1)—Ni(1)—N(2)
O(6)—Ni(1)—O(3)
N(2)—Ni(1)—O(6)
N(1)—Ni(1)—O(3)
C(5)—N(1)—Ni(1)
C(16)—N(2)—Ni(1)
C(6)—N(1)—Ni(1)
C(11)—N(2)—Ni(1)
C(3)—O(3)—Ni(1)
C(14)—O(6)—Ni(1)
86.86(16)
87.14(13)
93.12(15)
92.87(15)
127.0(3)
126.8(3)
113.9(3)
112.7(3)
129.7(3)
129.6(3)
86.41(16)
85.07(13)
94.51(15)
93.99(14)
126.2(3)
124.1(3)
113.4(3)
114.0(3)
128.8(3)
128.6(3)
120.3(4)
121.9(4)
N(2)—Ni(1)—N(1)
O(2)—Ni(1)—O(1)
N(2)—Ni(1)—O(2)
O(1)—Ni(1)—N(1)
C(12)—N(1)—Ni(1)
C(15)—N(2)—Ni(1)
C(1)—N(1)—Ni(1)
C(6)—N(2)—Ni(1)
C(16)—O(2)—Ni(1)
C(9)—O(1)—Ni(1)
C(9)—C(8)—C(12)
C(16)—C(14)—C(15)
86.61(8)
85.38(7)
93.69(8)
94.30(8)
125.28(18)
125.75(17)
113.29(14)
113.15(15)
128.28(16)
127.82(16)
120.7(2)
119.2(2)
C(14)—C(13)—C(16) 119.6(4)
C(3)—C(2)—C(5) 119.6(4)
node is due to nonꢀequivalency of the bonds that form the
square. The chelate node is characterized by the strong
delocalization of the electron density of the sixꢀmemꢀ
bered metallocycles, which is observed in the equaliꢀ
zation of groups of the Ni—X bond lengths (X = N, O),
С—Х (X = N, O) and the С—С bond lengths of the
metallocycle (see Table 3). In particular, the measured
difference in the С—С bond length in the metallocycle
does not exceed 0.04 Å, whereas that in the С—О and
C—N bond lengths is 0.03 Å. It is impossible to choose
unambiguously between the imino enol and amino enone
forms of the chelate moiety. At the same time, the
С—СО2Еt and N—Ar bond lengths close to standard
values for ordinary bonds indicate the absence of a conꢀ
siderable conjugation between these moieties and the elecꢀ
tron system of sixꢀmembered metallocycles.
distance 3.43 Å (see Fig. 4), which suggests intermolecuꢀ
lar contacts inside the stack. The cavities between the
stacks are occupied by acetonitrile molecules. The packꢀ
ing in the stack can be described by the alternation of the
Ni—Niꢀbonded dimers of molecules I and Ia in the seꢀ
quence —I—I—Ia—Ia— in such a way that the Ni—Ni
distance in the stack varies from 3.43 Å for Ni(1)—Ni(1A) to
3.56 Å for Ni(1)—Ni(1) and 4.46 Å for Ni(1А)—Ni(1A).
According to the Xꢀray diffraction data, the spatial
structure of molecules of nonsymmetric complex 5d (see
Fig. 5) resembles the structure of symmetric metal comꢀ
plex 5a (see Fig. 3). The molecule is slightly convex, the
dihedral angle between the planes Ni(1)N(1)C(1)C(6)ꢀ
N(2) and Ni(1)O(1)C(9)C(8)C(12)N(1) is 4.5°, that
between Ni(1)N(1)C(1)C(6)N(2) and Ni(1)O(2)C(14)ꢀ
C(15)C(16)N(2) is 7.1°, and the angle between the
Ni(1)O(2)C(14)C(15)C(16)N(2) and Ni(1)O(1)C(9)ꢀ
C(8)C(12)N(1) planes is 10.7°. The deviation of the parꢀ
The molecular packing of 5а is formed by zigzag alterꢀ
nation of stacks of molecules I and Iа with the interplanar

Fluorinated (O)N2O ligands
Russ.Chem.Bull., Int.Ed., Vol. 59, No. 8, August, 2010
1589
ticular atoms of the chelate cycles from the rootꢀmean
square plane that passes through these cycles reaches
0.2 Å. The coordination mode of the nickel atom is a
distorted square. The distortions made by nonequivalence
of the substituted are insignificant and compared with the
distortions observed for compound 5a (see Table 3).
The molecular packing is formed by splay stacks of
molecules, and centrosymmetric Ni—Niꢀbonded dimers
with of interplanar distance of 3.45(6) Å can be distinꢀ
guished inside the stacks, where the interplanar distance
between the dimers is somewhat longer, being 3.52 Å
(see Fig. 6).
Thus, we showed a possibility of preparing triꢀ and
tetradentate ligands 2 and 3 based on the reactions
of ethyl 2ꢀethoxymethylideneꢀ3ꢀoxoꢀ3ꢀpolyfluoroalkylꢀ
propionates 1 with oꢀphenylenediamine. Depending on
the ratio of the reactants, one can synthesize products of
both monoꢀ and disubstitution, being triꢀ or tetradentate
ligands 2 and 3, respectively. Metal complexes 4 of the
composition (L = H)CuCl and complexes 5 of the comꢀ
position (L = 2H)M (M = NiII, CuII, CoII) were syntheꢀ
sized from tridentate ligands 2 and tetradentate ligands 3,
respectively. The spatial structure of the synthesized
complexes was studied by Xꢀray diffraction analysis.
Experimental
Melting points were measured in open capillaries with a
Stuart SMP3 apparatus for melting temperature determination.
IR diffuse reflectance spectra were recorded on a Perkin—Elmer
Spectrum One FTIR spectrometer (suspension with Nujol).
NMR spectra were obtained on a Bruker DRXꢀ400 spectrometer
(1Н, 400 MHz, relative to Me4Si; 19F, 376 MHz, relative to
С6F6) (solutions in CDCl3). Elemental analysis was carried out
with a Perkin—Elmer PE 2400 series II CHNSꢀO elemental
analyzer. The reaction course was monitored by TLC on Sorbfil
PTSKhꢀAFꢀVꢀUF plates.
The starting ethyl 2ꢀethoxymethylideneꢀ3ꢀoxoꢀ3ꢀpolyfluoroꢀ
alkylpropionates 1a—c were synthesized according to a procedure
described earlier.22
The Xꢀray diffraction studies of compounds 2b, 4b, and 5а,d
were performed on an Xcalibur 3 diffractometer equipped with a
CCD detector (λ(MoꢀКα) = 0.71073 Å, graphite monochroꢀ
mator, 295(2) K (120(2) K for 2b), ω scan mode, scan increment
1°, time of frame measurement 20 s). A fragment of the red
Table 4. Crystallographic data and parameters of Xꢀray experiment for compounds 2b, 4b, and 5a,d
Parameter
2b
4b
5a
5d
Molecular formula
Molecular weight
Crystal system
Space group
C14H14F4N2O3
334.27
Monoclinic
С2/с
C14H13ClCuF4N2O3
432.25
C42H35F12N5Ni2O12
1147.17
C21H17F7N2NiO6
585.08
Monoclinic
P21/n
Monoclinic
P21/n
Triclinic
Pꢀ1
a/Å
b/Å
c/Å
α/deg
14.2258(19)
10.9485(15)
18.883(3)
90
96.250(11)
90
2923.5(7)
8
1.519
14.8456(12)
6.1422(6)
19.5709(19)
90
110.895(8)
90
1667.2(3)
4
1.722
14.4067(12)
14.1185(8)
22.458(3)
90
90.030(9)
90
4567.9(7)
4
1.668
8.9249(14)
11.3653(16)
13.0296(17)
97.183(11)
107.600(13)
111.082(14)
1134.1(3)
2
β/deg
γ/deg
Volume/Å3
Z
dcalc/g cm–3
1.713
0.955
μ/mm–1
0.140
1.528
0.941
F(000)
1376
868
2328
592
Scan angle, θ/deg
Number of collected reflections
Number of independent
reflections
3.09 < θ < 26.37
5218
2965 (Rint = 0.0231)
2.94 < θ < 26.38
5580
3341 (Rint = 0.0147)
2.71 < θ < 26.36
26028
9055 (Rint = 0.0934)
2.80 < θ < 26.37
9923
4617 (Rint = 0.0240)
Number of reflections
with I > 2σ(I)
Collection completeness (%)
(for θ/deg)
1916
2345
4564
2899
98.9% (26.37)
97.8% (26.00)
97.3% (26.00)
99.4% (26.37)
Number of calculated parameters
Goodnessꢀofꢀfit S on F2
R1 [I > 2σ (I)]
wR2 [I > 2σ (I)]
R1 (for all reflections)
wR2 (for all reflections)
Residual electron density
220
1.006
0.0335
0.0755
0.0573
226
1.001
0.0273
0.0672
0.0454
658
1.001
0.0566
0.1278
0.1144
334
1.001
0.0366
0.0778
0.0672
0.0787
0.0714
0.1394
0.0822
0.211/–0.179
0.286/–0.338
0.584/–0.368
0.730/–0.235
/e•Å3, ρmax/ρ
min

1590
Russ.Chem.Bull., Int.Ed., Vol. 59, No. 8, August, 2010
Kudyakova et al.
filament crystal 0.29Ѕ0.15Ѕ0.06 mm in size was used for the
study of compound 5a, and a fragment of the red filament crystal
0.22Ѕ0.13Ѕ0.06 mm in size was used for studying compound 5d.
An absorption correction was applied analytically by the polyꢀ
hedral crystal model.24 The structure was solved by a direct
method using the SHELXS97 program25 and refined using
the SHELXL97 program26 by the leastꢀsquares method in the
anisotropic fullꢀmatrix approximation for nonꢀhydrogen atoms.
Hydrogen atoms were added to the geometrically calculated
positions and included into refinement in the isotropic approxiꢀ
mation with the dependent thermal parameters in the riding
model. The main parameters of structural experiments are given
in Table 4. The bond lengths and bond angles characterizing
compounds 2b and 4b are listed in Table 1, and those for
compound 5а,d are presented in Table 3.
The full array of crystallographic data for compounds 2b,
4b, and 5а,d was deposited with the Cambridge Crystallographic
Data Centre (CCDC Nos 772 368, 751 317, 751 318, and
751 319, respectively) and is available at www.ccdc.cam.ac.uk/
conts/retrieving.html (or from the CCDC, 12 Union Road,
Cambridge CB2 1EZ, UK; fax: +44 1223 336033; eꢀmail:
deposit@ccdc.cam.ac.uk).
Ethyl 2ꢀ[Nꢀ(2ꢀaminophenyl)aminomethylidene]ꢀ3ꢀoxoꢀ4,4,4ꢀ
trifluorobutanoate (2a). A mixture of ester 1a (0.96 g, 4 mmol)
and oꢀphenylenediamine (0.43 g, 4 mmol) in diethyl ether
(10 mL) was stirred for 30 min at ~20 °C. Then the reaction
mixture was evaporated, and the oil formed was triturated in
hexane until precipitation. The yield was 1.08 g (89%), yellow
powder, m.p. 76—78 °С. IR, ν/cm–1: 3454, 3346 (NH2); 3196
(ν(NH)); 3047, 2981 (C—H); 1710 (СО2Et); 1647 (C=O); 1625,
1595, 1577 (C=C, δ(NH)); 1182—1011 (C—F). 1Н NMR, δ:
E + Z: 7.10—7.19 (m, 3 Н, CH, NH2); 6.85—6.92 (m, 3 Н,
C6H4); E (66%): 1.34 (t, 3 Н, ОСН2СН3, 3J = 7.2 Hz); 4.29 (q,
2 Н, ОСН2СН3, 3J = 7.2 Hz); 8.55 (d, 1 H, CH, 3J = 13.9 Hz);
12.13 (d, 1 H, NH, 3J = 13.9 Hz); Z (34%): 1.37 (t, 3 Н,
ОСН2СН3, 3J = 7.1 Hz); 4.33 (q, 2 Н, ОСН2СН3, 3J = 7.1 Hz);
8.40 (d, 1 H, CH, 3J = 13.9 Hz); 11.29 (d, 1 H, NH, 3J = 13.9 Hz).
19F NMR, δ: E (66%): 89.13 (s, 3 F, CF3); Z (34%): 90.04 (s,
3 F, CF3). Found (%): C, 51.73; H, 4.17; F, 19.05; N, 9.02.
С13Н13F3N2O3. Calculated (%): С, 51.66; H, 4.34; F, 18.86;
N, 9.27.
Ethyl 2ꢀ[Nꢀ(2ꢀaminophenyl)aminomethylidene]ꢀ3ꢀoxoꢀ
4,4, 5,5,6,6,6ꢀheptafluorohexanoate (2c) was synthesized similarly
to compound 2a from 1c (1.36 g, 4 mmol). The yield was 1.38 g
(86%), yellow powder, m.p. 69—70 °С. IR, ν/cm–1: 3410, 3346
(NH2); 3254 (ν(NH)); 3054, 2989 (C—H); 1697 (СО2Et); 1649
(C=O); 1639, 1623, 1568 (C=C, δ(NH)); 1228—1130 (C—F).
1Н NMR, δ: E + Z: 7.11—7.19 (m, 3 Н, CН, NH2); 6.84—6.92
(m, 3 Н, С6Н4); E (56%): 1.33 (t, 3 Н, ОСН2СН3, 3J = 7.1 Hz);
4.29 (q, 2 Н, ОСН2СН3, 3J = 7.1 Hz); 8.45 (d, 1 H, CH,
3J = 13.8 Hz); 11.99 (d, 1 H, NH, 3J = 13.8 Hz); Z (44%):
1.36 (t, 3 Н, ОСН2СН3, 3J = 7.1 Hz); 4.33 (q, 2 Н, ОСН2СН3,
3J = 7.1 Hz); 8.29 (d, 1 H, CH, 3J = 13.8 Hz); 11.16 (d, 1 H,
NH, 3J = 13.8 Hz). 19F NMR, δ: E (56%): 38.34 (m, 2 F,
βꢀCF2); 48.66 (m, 2 F, αꢀCF2); 81.51 (t, 3 F, CF3, J = 9.9 Hz);
Z (44%): 37.51 (m, 2 F, βꢀCF2); 49.25 (m, 2 F, αꢀCF2); 81.68
(t, 3 F, CF3, J = 9.5 Hz). Found (%): C, 44.97; H, 3.11;
F, 33.12; N, 6.94. С15Н13F7N2O3. Calculated (%): С, 44.79;
H, 3.26; F, 33.06; N, 6.96.
Diethyl 2,2´ꢀ[1,2ꢀphenylenebis(aminomethylidene)]bis(4,4,4ꢀ
trifluoroꢀ3ꢀoxobutanoate) (3а). A mixture of ester 1a (1.20 g,
5 mmol) and oꢀphenylenediamine (0.27 g, 2.5 mmol) in diethyl
ether (20 mL) was stirred for 3 h at ~20 °C. Then the reaction
mixture was concentrated, and the precipitate formed was filtered
off, washed with hexane, and recrystallized from ethanol. The
yield was 1.39 g (56%), light yellow powder, m.p. 117—119 °С.
IR, ν/cm–1: 3196 (ν(NH)); 2971, 2959 (C—H); 1724 (СО2Et);
1698 (C=O); 1651, 1628, 1607, 1583 (C=C, δ(NH)); 1279—1130
(C—F). 1Н NMR, δ: all isomers: 7.39—7.46 (m, 4 H, C6H4);
E,E (28%): 1.33 (t, 6 Н, 2 ОСН2СН3, 3J = 7.2 Hz); 4.28
(q, 4 Н, 2 ОСН2СН3, 3J = 7.2 Hz); 8.51 (d, 2 H, 2 CH,
3J = 13.3 Hz); 12.15 (br.d, 2 Н, 2 NН, 3J = 13.3 Hz); E,Z
(54%): 1.36, 1.33 (both t, 3 Н each, 2 ОСН23СН3, 3J = 7.2 Hz);
4.29, 4.32 (both q, 2 Н each, 2 ОСН2СН3, J = 7.2 Hz); 8.36,
8.51 (both d, 1 H each, 2 CH, 3J = 13.3 Hz); 11.59, 12.11
(both d, 1 Н each, 2 NН, 3J = 13.3 Hz); Z,Z (18%): 1.36 (t,
6 Н, 2 ОСН2СН3, 3J = 7.2 Hz); 4.32 (q, 4 Н, 2 ОСН2СН3,
3J = 7.2 Hz); 8.36 (d, 2 H, 2 CH, 3J = 13.3 Hz); 11.59 (br.d,
2 Н, 2 NН, 3J = 13.3 Hz). 19F NMR, δ: E,E (28%): 88.92 (s,
2 CF3); E,Z (54%): 88.95, 89.73 (both s, 2 CF3); Z,Z (18%):
89.79 (s, 2 CF3). Found (%): C, 48.35; H, 3.43; F, 22.76;
N, 5.64. C20H18F6N2O6. Calculated (%): C, 48.40; H, 3.66;
F, 22.96; N, 5.64.
Ethyl 2ꢀ[Nꢀ(2ꢀaminophenyl)aminomethylidene]ꢀ3ꢀoxoꢀ
4,4, 5,5,6,6,6ꢀheptafluorohexanoate (2b) was synthesized similarly
to compound 2a from ester 1b (1.09 g, 4 mmol). The yield was
1.22 g (91%), yellow powder, m.p. 89—90 °С. IR, ν/cm–1: 3459,
3360 (NH2); 3200, 3177 (ν(NH)); 3023, 2982 (C—H); 1707
(СО2Et); 1673 (C=O); 1629, 1604, 1588 (C=C, δ(NH));
1245—1079 (C—F). 1Н NMR, δ: E + Z: 6.87—6.94 (m, 3 Н,
С6Н4); 7.10—7.19 (m, 3 Н, CН, NH2); E (72%): 1.34 (t, 3 Н,
ОСН2СН3, 3J = 7.1 Hz); 4.28 (q, 2 Н, ОСН2СН3, 3J = 7.1 Hz);
6.73 (tt, 2 Н, 2 (CF2)2H, 2J = 53.8 Hz, 3J = 5.8 Hz); 8.46 (d,
1 H, CH, 3J = 13.7 Hz); 12.18 (d, 1 H, NH, 3J = 13.7 Hz);
Z (28%): 1.37 (t, 3 Н, ОСН2СН3, 3J = 7.1 Hz); 4.32 (q, 2 Н,
ОСН2СН3, 3J = 7.1 Hz); 6.36 (tt, 2 Н, 2 (CF2)2H, 2J = 53.2 Hz,
3J = 5.8 Hz); 8.34 (d, 1 H, CH, 3J = 13.9 Hz); 11.14 (d, 1 H,
NH, 3J = 13.9 Hz). 19F NMR, δ: E (72%): 24.18 (dm, 2 F,
CF2H, 2J = 53.2 Hz); 39.75 (m, 2 F, CF2); Z (28%): 22.05 (dm,
2 F, CF2H, 2J = 53.8 Hz); 41.38 (m, 2 F, CF2). Found (%):
C, 50.19; H, 4.18; F, 22.60; N, 8.29. С14Н14F4N2O3. Calculꢀ
ated (%): С, 50.30; H, 4.22; F, 22.73; N, 8.38.
Diethyl 2,2´ꢀ[1,2ꢀphenylenebis(aminomethylidene)]bisꢀ
(4,4,5,5ꢀtetrafluoroꢀ3ꢀoxopentanoate) (3b) was synthesized similarly
to compound 3а from ester 1b (1.36 g, 5 mmol). The yield was
1.82 g (65%), creamꢀcolored powder, m.p. 133—135 °С. IR,
ν/cm–1: 3206 (ν(NH)); 3009, 2958 (C—H); 1698 (CO2Et);
1638 (C=O); 1619, 1588, 1545 (C=C, δ(NH)); 1266—1079
(C—F). 1Н NMR, δ: all isomers: 7.44—7.36 (m, 4 H, С6Н4);
E,E (30%): 1.35 (t, 6 Н, 2 ОСН2СН3, 3J = 7.2 Hz); 4.30 (q,
4 Н, 2 ОСН2СН3, 3J = 7.2 Hz); 6.59 (tt, 2 Н, 2 H(CF2)2,
2J = 53.5 Hz, 3J = 5.87 Hz); 8.40 (d, 2 H, 2 CH, 3J = 13.1 Hz);
12.17 (br.d, 2 Н, 2 NН, 3J = 13.1 Hz); E,Z (52%): 1.35, 1.36
(both t, 3 Н each, 2 ОСН2СН3, 3J = 7.0 Hz); 4.30, 4.34 (both q,
2 Н each, 2 ОСН2СН3, 3J = 7.2 Hz); 6.34, 6.67 (both tt, 1 Н
each, 2 H(CF2)2, 2J = 53.0 Hz, 3J = 5.87 Hz); 8.29, 8.40
(both d, 1 H each, 2 CH, 3J = 13.1 Hz); 11.45, 12.15 (both
br.d, 1 Н each, 2 NН, 3J = 13.1 Hz); Z,Z (18%): 1.36 (t, 6 Н,
2 ОСН2СН3, 3J = 7.2 Hz); 4.34 (q, 4 Н, 2 ОСН2СН3,
3J = 7.2 Hz); 6.34 (tt, 2 Н, 2 H(CF2)2, 2J = 53.5 Hz, 3J = 5.87 Hz);

Fluorinated (O)N2O ligands
Russ.Chem.Bull., Int.Ed., Vol. 59, No. 8, August, 2010
1591
8.29 (d, 2 H, 2 CH, 3J = 13.1 Hz); 11.45 (br.d, 2 Н, 2 NН,
3J = 13.1 Hz). 19F NMR, δ: E,E (30%): 23.45 (dt, 4 F, 2 HCF2,
CF2); 89.71 (s, 3 F, CF3); Z,E (25%): 22.21 (dm, 2 F, HCF2,
2J = 53.1 Hz); 41.29 (m, 2 F, CF2); 88.87 (s, 3 F, CF3).
Found (%): C, 47.72; H, 3.50; F, 25.43; N, 5.62. С21Н19F7N2O6.
Calculated (%): С, 47.74; H, 3.62; F, 25.17; N, 5.30.
3
2J = 53.4 Hz, J = 7.9 Hz); 39.54 (m, 4 F, 2 CF2); E,Z (52%):
22.24 (dm, 2 F, HCF2, 2J = 53.1 Hz); 23.89 (dt, 2 F, HCF2,
2J = 53.4 Hz, 3J = 7.9 Hz); 39.64 (m, 2 F, CF2); 41.33 (m, 2 F,
Ethyl
2ꢀ({2ꢀ[Nꢀ(2ꢀethoxycarbonylꢀ3ꢀoxoꢀ3,3,3ꢀtriꢀ
2
CF2); Z,Z (18%): 22.19 (dm, 4 F, 2 HCF2, J = 52.9 Hz); 41.33
fluorobutꢀ1ꢀenꢀ1ꢀyl)amino]phenyl}aminomethylidene)ꢀ3ꢀoxoꢀ
4,4,5,5,5,6,6,6ꢀheptafluorohexanoate (3e) was synthesized
similarly to compound 3d from ester 2c (1.21 g, 3 mmol) and
ester 1a (0.72 g, 3 mmol). The yield was 1.13 g (63%), milkꢀ
white powder, m.p. 80—83 °С. IR, ν/cm–1: 3207 (ν(NH)); 3043,
2989 (C—H); 1699 (СО2Et); 1659 (C=O); 1633, 1586, 1562
(C=C, δ(NH)); 1230—1119 (C—F). 1Н NMR, δ: all isomers:
1.31—1.39 (m, 6 H, OCH2CH3); 4.28—4.73 (m, 4 H, OCH2CH3);
7.30—7.45 (m, 4 H, C6H4); E,E (19%): 8.41 (d, 1 Н, СH,
3J = 13.2 Hz); 8.49 (d, 1 Н, СH, 3J = 13.2 Hz); 12.02 (d, 1 Н, NH,
3J = 13.2 Hz); 12.17 (d, 1 Н, NH, 3J = 13.2 Hz); Z,Z (20%): 8.22
(d, 1 Н, СH, 3J = 13.1 Hz); 8.35 (d, 1 Н, СH, 3J = 13.3 Hz);
11.34 (d, 1 Н, NH, 3J = 13.3 Hz); 11.64 (d, 1 Н, NH, 3J = 13.1 Hz);
(m, 4 F, 2 CF2). Found (%): C, 47.32; H, 3.43; F, 27.21;
N, 4.89. C22H20F8N2O6. Calculated (%): C, 47.15; H, 3.60;
F, 27.12; N, 5.00.
Diethyl 2,2´ꢀ[1,2ꢀphenylenebis(aminomethylidene)]bisꢀ
(4,4,5,5,6,6,6ꢀheptafluoroꢀ3ꢀoxopentanoate) (3с) was synthesized
similarly to compound 3а from 1c (1.70 g, 5 mmol). The yield
was 1.43 g (72%), milkꢀwhite powder, m.p. 140—142 °С. IR,
ν/cm–1: 3210 (ν(NH)); 3015, 2953 (C—H); 1710 (CO2Et);
1660 (C=O); 1621, 1580 (C=C, δ(NH)); 1269—1057 (C—F).
1Н NMR, δ: all isomers: 7.40—7.43 (m, 4 H, C6H4); E,E (35%):
1.31 (t, 6 Н, 2 ОСН2СН3, 3J = 7.1 Hz); 4.27 (q, 4 Н,
3
3
2 ОСН2СН3, J = 7.1 Hz); 8.65 (d, 2 H, 2 CH, J = 13.3 Hz);
12.00 (br.d, 2 Н, 2 NН, 3J = 13.3 Hz); E,Z (45%): 1.35, 1.32
(both t, 3 Н each, 2 ОСН2СН3, 3J =7.1 Hz); 4.29, 4.34 (both q,
2 Н each, 2 ОСН2СН3, J = 7.1); 8.65, 8.42 (both d, 1 H each,
2 CH, 3J = 13.3 Hz); 11.60, 12.00 (both d, 1 Н each, 2 NН,
3J = 13.3 Hz); Z,Z (20%): 1.35 (t, 6 Н, 2 ОСН2СН3, 3J = 7.1 Hz);
4.34 (q, 4 Н, 2 ОСН2СН3, 3J = 7.1 Hz); 8.42 (d, 2 H, 2 CH,
3J = 13.3 Hz); 11.60 (br.d, 2 Н, 2 NН, 3J = 13.3 Hz). 19F NMR,
δ: E,E (35%): 38.31 (m, 4 F, 2 βꢀCF2); 48.44 (m, 4 F, 2 αꢀCF2);
81.52 (t, 6 F, 2 CF3, 3J = 9.8 Hz); E,Z (45%): 37.55, 38.31
(both m, 2 F each, 2 βꢀCF2); 48.44, 48.93 (both m, 2 F each,
2 αꢀCF2); 81.52, 81.63 (both t, 3 F each, 2 CF3, 3J = 9.8 Hz);
Z,Z (20%): 37.55 (m, 4 F, 2 βꢀCF2); 48.93 (m, 4 F, 2 αꢀCF2);
81.65 (t, 6 F, 2 CF3, 3J = 9.8 Hz). Found (%): C, 36.22; H, 2.23;
F, 33.45; N, 3.50. C24H18F14N2O6. Calculated (%): C, 36.37;
H, 2.27; F, 33.58; N, 3.54.
3
E,Z (25%): 8.34 (d, 1 Н, СH, J = 13.2 Hz); 8.41 (d, 1 Н, СH,
3J = 13.2 Hz); 11.60 (d, 1 Н, NH, 3J = 13.2 Hz); 11.99 (d, 1 Н,
NH, 3J = 13.2 Hz); Z,E (36%): 8.22 (d, 1 Н, СH, 3J = 13.1 Hz);
8.50 (d, 1 Н, СH, 3J = 13.1 Hz); 11.44 (1 Н, NH, 3J = 13.1 Hz);
12.10 (d, 1 Н, NH, 3J = 13.1 Hz). 19F NMR, δ: E,E (19%):
38.09 (m, 2 F, βꢀCF2); 48.26 (m, 2 F, αꢀCF2); 81.64 (t, 3 F,
CF3, 3J = 9.9 Hz); 88.73 (s, 3 F, CF3); Z,Z (20%): 37.47 (m, 2 F,
βꢀCF2); 48.95 (m, 2 F, αꢀCF2); 81.59 (t, 3 F, CF3, 3J = 9.6 Hz);
89.71 (s, 3 F, CF3); E,Z (25%): 38.02 (m, 2 F, βꢀCF2); 48.18
(m, 2 F, αꢀCF2); 81.61 (t, 3 F, CF3, 3J = 9.8 Hz); 89.79 (s, 3 F,
CF3); Z,E (36%): 37.46 (m, 2 F, βꢀCF2); 48.89 (m, 2 F, αꢀCF2);
81.60 (t, 3 F, CF3, 3J = 9.6 Hz); 88.89 (s, 3 F, CF3). Found (%):
C, 44.41; H, 3.03; F, 31.75; N, 4.70. С22Н18F10N2O6. Calculꢀ
ated (%): С, 44.31; H, 3.04; F, 31.86; N, 4.70.
Ethyl 2ꢀ({2ꢀ[Nꢀ(2ꢀethoxycarbonylꢀ3ꢀoxoꢀ4,4,5,5ꢀtetraꢀ
fluoropentꢀ1ꢀenꢀ1ꢀyl)amino]phenyl}aminomethylidene)ꢀ3ꢀoxoꢀ
4,4,5,5,6,6,6ꢀheptafluorohexanoate (3f) was synthesized similarly
to compound 3d from ester 2c (1.21 g, 3 mmol) and ester 1b
(0.82 g, 3 mmol). The yield was 1.23 g (65%), milkꢀwhite powder,
m.p. 98—100 °С. IR, ν/cm–1: 3177 (ν(NH)); 3004, 2984 (C—H);
1725 (СО2Et); 1703 (C=O); 1631, 1546, 1517 (C=C, δ(NH));
1263—1084 (C—F). 1Н NMR, δ: all isomers: 1.31—1.39 (m,
6 H, 2 OCH2CH3); 4.27—4.38 (m, 4 H, 2 OCH2CH3); 7.32—7.44
(m, 4 H, C6H4); E,E (30%): 6.66 (tt, 1 H, H(CF2)2, 2J = 53.8 Hz,
3J = 5.6 Hz); 8.39 (d, 1 Н, СH, 3J = 13.1 Hz); 8.40 (d, 1 Н,
СH, 3J = 13.1 Hz); 12.20 (d, 1 Н, NH, 3J = 13.1 Hz); 12.15
(d, 1 Н, NH, 3J = 13.1 Hz); Z,Z (29%): 6.34 (tt, 1 H, CF2H,
2J = 53.0 Hz, 3J = 6.0 Hz); 8.22 (d, 1 Н, СH, 3J = 13.0 Hz); 8.29
Ethyl 2ꢀ({2ꢀ[Nꢀ(2ꢀethoxycarbonylꢀ3ꢀoxoꢀ3,3,3ꢀtrifluorobutꢀ
1ꢀenꢀ1ꢀyl)amino]phenyl}aminomethylidene)ꢀ3ꢀoxoꢀ4,4,5,5ꢀtetraꢀ
fluoropentanoate (3d). A mixture of ester 2a (0.91 g, 3 mmol)
and ester 1b (0.82 g, 3 mmol) in diethyl ether (15 mL) was
stirred for 4 h at ~20 °C. Then the reaction mixture was
evaporated, and the precipitate that formed was filtered off
and recrystallized from hexane. The yield was 0.95 g (60%),
milkꢀwhite powder, m.p. 115—118 °C. IR, ν/cm–1: 3205
(ν(NH)); 3030, 2994 (C—H); 1726 (СО2Et); 1700 (C=O); 1619,
1594, 1553 (C=C, δ(NH)); 1222—1027 (C—F). 1Н NMR, δ:
all isomers: 1.33—1.39 (m, 6 H, 2 OCH2CH3); 4.38—4.27 (m,
4 H, 2 OCH2CH3); 7.32—7.45 (m, 4 H, C6H4); E,E (25%): 6.60
(tt, 1 Н, (CF2)2H, 2J = 53.5 Hz, 3J = 5.8 Hz); 8.40 (d, 1 Н, СH,
3J = 13.1 Hz); 8.50 (d, 1 Н, СH, 3J = 13.1 Hz); 12.15 (br.d, 2 Н,
2 NH, 3J = 13.1 Hz); Z,Z (20%): 6.34 (tt, 1 Н, (CF2)2H,
2J= 52.9 Hz, 3J = 5.8 Hz); 8.28 (d, 1 Н, СH, 3J = 13.2 Hz); 8.35
3
3
(d, 1 Н, СH, J = 13.1 Hz); 11.45 (d, 1 Н, NH, J = 13.0 Hz);
11.48 (d, 1 Н, NH, 3J = 13.1 Hz); E,Z (15%): 6.58 (tt, 1 H, H(CF2)2,
2J= 53.6 Hz, 3J = 6.0 Hz); 8.21 (d, 1 Н, СH, 3J = 12.9 Hz); 8.38
(d, 1 Н, СH, 3J = 13.0 Hz); 11.34 (1 Н, NH, 3J = 13.0 Hz);
11.99 (1 Н, NH, 3J = 12.9 Hz); Z,E (26%): 6.59 (tt, 1 H, H(CF2)2,
2J = 53.1 Hz, 3J = 6.0 Hz); 8.28 (d, 1 Н, СH, 3J = 13.2 Hz); 8.41
(d, 1 Н, СH, 3J = 13.1 Hz); 11.31 (1 Н, NH, 3J = 13.1 Hz);
3
(d, 1 Н, СH, 3J = 13.2 Hz); 11.33 (d, 1 Н, NH, J = 13.2 Hz);
11.48 (d, 1 Н, NH, 3J = 13.2 Hz); E,Z (30%): 6.66 (tt, 1 Н,
(CF2)2H, 2J = 53.7 Hz, 3J = 6.0 Hz); 8.36 (d, 1 Н, СH, 3J = 13.3 Hz);
8.39 (d, 1 Н, СH, 3J = 13.3 Hz); 11.62 (d, 1 Н, NH, 3J = 13.3 Hz);
12.11 (d, 1 Н, NH, 3J = 13.3 Hz); Z,E (25%): 6.33 (tt, 1 Н, (CF2)2H,
2J = 53.3 Hz, 3J = 6.0 Hz); 8.29 (d, 1 Н, СH, 3J = 13.2 Hz); 8.49
3
12.03 (1 Н, NH, J = 13.2 Hz). 19F NMR, δ: Z,Z (29%): 22.34
(dm, 2 F, HCF2CF2, 2J = 53.0 Hz); 37.98 (m, 2 F, βꢀCF2);
41.36 (m, 2 F, HCF2CF2); 48.18 (m, 2 F, αꢀCF2); 81.61 (t,
3
3
(d, 1 Н, СH, J= 13.2 Hz); 11.43 (d, 1 Н, NH, J = 13.2 Hz);
12.12 (d, 1 Н, NH, 3J = 13.2 Hz). 19F NMR, δ: E,E (25%):
23.54 (dt, 2 F, HCF2, 2J = 53.5 Hz, 3J = 7.7 Hz); 39.58 (m, 2 F,
CF2); 88.89 (s, 3 F, CF3); Z,Z (20%): 22.16 (dm, 2 F, HCF2,
2J = 53.2 Hz); 41.34 (m, 2 F, CF2); 89.78 (s, 3 F, CF3); E,Z (30%):
23.88 (dt, 2 F, HCF2, 2J = 53.6 Hz, 3J = 7.9 Hz); 39.63 (m, 2 F,
3
3 F, CF3, J = 9.8 Hz); Z,E (26%): 22.18 (dm, 2 F, HCF2CF2,
2J = 53.1 Hz); 38.10 (m, 2 F, βꢀCF2); 41.32 (m, 2 F, HCF2CF2);
48.27 (m, 2 F, αꢀCF2); 81.59 (t, 3 F, CF3, 3J = 9.2 Hz); E,E
(30%): 23.88 (dt, 2 F, HCF2CF2, 3J = 53.8 Hz); 37.47 (m, 2 F,
βꢀCF2); 39.63 (m, 2 F, HCF2CF2); 48.89 (m, 2 F, αꢀCF2);

1592
Russ.Chem.Bull., Int.Ed., Vol. 59, No. 8, August, 2010
Kudyakova et al.
81.60 (t, 3 F, CF3,3J = 9.9 Hz); E,Z (15%): 23.89 (dt, 2 F,
HCF2CF2, 2J = 53.6 Hz); 37.45 (m, 2 F, βꢀCF2); 39.54 (m,
2 F, HCF2CF2); 48.94 (м, 2 F, αꢀCF2); 81.58 (t, 3 F, CF3,
3J = 9.9 Hz). Found (%): C, 44.25; H, 3.17; F, 33.57; N, 4.62.
С23Н19F11N2O6. Calculated (%): С, 43.96; H, 3.05; F 33.26;
N, 4.46.
Chloro{ethyl 2ꢀ[(2ꢀaminophenyl)aminatomethylidene]ꢀ3ꢀoxoꢀ
4,4,5,5ꢀtetrafluoropentanoate}copper(II) (4b). A mixture of
ester 2b (0.67 g, 0.002 mol) and copper(II) chloride (0.40 g,
0.003 mol) in ethanol (10 mL) was refluxed with stirring for 2 h,
and the precipitate formed was filtered off and recrystallized
from ethanol. The yield was 0.69 g (80%), dark green powder,
m.p. 205—207 °С. IR, ν/cm–1: 3093—2943 (ν(C—H)), 1704
(CO2Et), 1660 (CORF), 1615 (C=N), 1591 (C=C), 1292—1058
(C—F). Found (%): C, 39.11; H, 2.95; N, 6.50; F, 17.65.
С14Н13ClCuF4N2O3. Calculated (%): С, 38.90; H, 3.03;
N, 6.48; F, 17.58.
2 CF2); 51.48 (m, 4 F, 2 CF2); 81.43 (t, 6 F, 2 CF3). Found (%):
C, 38.32; H, 1.98; F, 34.86; N, 3.37. C26H16F14N2NiO6.
Calculated (%): C, 38.28; H, 2.14; F, 35.32; N, 3.72.
{1ꢀ[Nꢀ(3ꢀOxoꢀ3,3,3ꢀtrifluoroꢀ2ꢀethoxycarbonylbutꢀ1ꢀenꢀ
1ꢀyl)aminato]ꢀ2ꢀ[Nꢀ(3ꢀoxoꢀ4,4,5,5ꢀtetrafluoroꢀ2ꢀethoxycarꢀ
bonylpentꢀ1ꢀenꢀ1ꢀyl)aminato]benzene}nickel(II) (5e). The yield
by method A was 2.19 g (75%), red crystals, m.p. 163—164 °С.
IR, ν/cm–1: 3075, 3017, 2986 (C—H); 1726 (СО2Et); 1701
(C=O); 1606, 1584 (C=C, NH); 1300—1045 (C—F). 1Н NMR,
δ: 1.36 (t, 3 Н, ОСН2СН3, 3J = 7.1 Hz); 1.37 (t, 3 Н, ОСН2СН3,
3J = 7.1 Hz); 4.32 (q, 2 Н, ОСН2СН3, 3J = 7.1 Hz); 4.33
(q, 2 Н, ОСН2СН3, 3J = 7.1 Hz); 6.41 (tt, 1 Н, H(CF2)2,
3
2JH,F = 53.4 Hz, JH,F = 5.5 Hz); 7.24—7.25 (m, 2 H, C6H4);
7.63—7.66 (m, 2 H, C6H4); 8.35 (s, 1 H, CH); 8.44 (s, 1 H,
2
CH). 19F NMR, δ: 23.02 (dm, 2 F, HCF2, JF,H = 53.4 Hz);
42.90 (m, 2 F, CF2); 93.85 (s, 3 F, CF3). Found (%): C, 43.21;
H, 3.23; F, 23.01; N, 4.62. С21Н17F7N2NiO6. Calculated (%):
С, 43.11; H, 2.93; F, 22.73; N, 4.79.
Synthesis of metal complexes
5 (general procedure).
A. A mixture of compound 3 (2 mmol) and nickel(II) acetate
(copper(II) or cobalt(II)) (2 mmol) in ethanol (30 mL) was
refluxed for 5 min. The hot mixture was then filtered, the filtrate
was cooled down, and the precipitate formed was filtered off
and recrystallized from ethanol.
B. A mixture of ester 1 (4 mmol), oꢀphenylenediamine
(2 mmol), and nickel(II) acetate (2 mmol) in ethanol (30 mL)
was stirred for 2 days at ~20 °C. The precipitate formed was
filtered off and recrystallized from ethanol.
{1ꢀ[Nꢀ(3ꢀOxoꢀ3,3,3ꢀtrifluoroꢀ2ꢀethoxycarbonylbutꢀ1ꢀenꢀ
1ꢀyl)aminato]ꢀ2ꢀ[Nꢀ(3ꢀoxoꢀ4,4,5,5ꢀtetrafluoroꢀ2ꢀethoxycarꢀ
bonylpentꢀ1ꢀenꢀ1ꢀyl)aminato]benzene}copper(II) (5f). The
yield by method B was 2.05 g (70%), dark green powder,
m.p. 160—162 °С. IR, ν/cm–1: 2997, 2909 (C—H); 1708 br
(СО2Et, С=О); 1605, 1584 (C=C, NH); 1238—1093 (C—F).
Found (%): C, 43.08, H, 3.00; N, 4.57; F, 23.01. С21Н17СuF7N2O6.
Calculated (%): С, 42.76; H, 2.90; N, 4.75; F, 22.54.
{1ꢀ[Nꢀ(3ꢀOxoꢀ3,3,3ꢀtrifluoroꢀ2ꢀethoxycarbonylbutꢀ1ꢀenꢀ
1ꢀyl)aminato]ꢀ2ꢀ[Nꢀ(3ꢀoxoꢀ4,4,5,5,6,6,6ꢀheptafluoroꢀ2ꢀethoxyꢀ
carbonylhexꢀ1ꢀenꢀ1ꢀyl)aminato]benzene}nickel(II) (5g). The yield
by method A was 2.12 g (65%), dark red crystals, m.p. 160—162 °С.
IR, ν/cm–1: 3074, 2992, 2948 (C—H); 1723 br (СО2Et, C=O);
1604, 1581 (C=C, NH); 1220—1044 (C—F). 1Н NMR, δ:
1.34 (t, 3 Н, ОСН2СН3, 3J = 7.1 Hz); 1.36 (t, 3 Н, ОСН2СН3,
3J = 7.1 Hz); 4.31 (q, 2 Н, ОСН2СН3, 3J = 7.1 Hz); 4.32 (q,
2 Н, ОСН2СН3, 3J = 7.1 Hz); 7.24—7.26 (m, 2 H, C6H4);
7.63—7.67 (m, 2 H, C6H4); 8.29 (s, 1 H, CH); 8.43 (s, 1 H,
CH). 19F NMR, δ: 38.37 (m, 2 F, CF2); 51.49 (m, 2 F, CF2);
82.00 (t, 3 F, CF3, 3J = 9.5 Hz); 93.69 (s, 3 F, CF3). Found (%):
C, 40.63; H, 2.35; F, 29.27; N, 4.17. С22Н16F10N2NiO6.
Calculated (%): С, 40.46; H, 2.47; F, 29.09; N, 4.29.
1,1´ꢀ(1,2ꢀPhenylenebisaminato)bis(3ꢀoxoꢀ4,4,4ꢀtrifluoroꢀ
2ꢀethoxycarbonylbutꢀ1ꢀene)nickel(II) (5а). The yield by method A
was 0.94 g (85%), The yield by method B was 0.70 g (64%),
redꢀorange crystals, m.p. 166—168 °С. IR, ν/cm–1: 2957, 2932
(C—H); 1699 (СО2Et, C=O); 1607, 1584 (C=C); 1287—1154
(C—F). 1Н NMR, δ: 1.36 (t, 6 Н, 2 ОСН2СН3, 3J = 7.0 Hz);
3
4.32 (q, 4 Н, 2 ОСН2СН3, J = 7.0 Hz); 7.25 (m, 2 Н, С6Н4);
7.63 (m, 2 Н, С6Н4); 8.43 (s, 2 Н, 2 СН). 19F NMR, δ: 94.04
(s, CF3). Found (%): C, 43.46; H, 2.74; F, 20.53; N, 5.05.
C20H16F6N2NiO6. Calculated (%): C, 43.44; H, 2.92; F, 20.60;
N, 5.07.
1,1´ꢀ(1,2ꢀPhenylenebisaminato)bis(3ꢀoxoꢀ4,4,4ꢀtrifluoroꢀ
2ꢀethoxycarbonylbutꢀ1ꢀene)cobalt(II) (5b). The yield by
method A was 0.82 g (75%), orange powder, m.p. 176—178 °С.
IR, ν/cm–1: 2984, 2939 (C—H); 1725 (СO2Et); 1703 (C=O);
1607, 1582 (C=C); 1276—1103 (C—F). Found (%): C, 43.72;
H, 2.84; F, 20.42; N, 4.83. C20H16CoF6N2O6. Calculated (%):
C, 43.42; H, 2.91; F, 20.60; N, 5.06.
1,1´ꢀ(1,2ꢀPhenylenebisaminato)bis(3ꢀoxoꢀ4,4,4ꢀtrifluoroꢀ
2ꢀethoxycarbonylbutꢀ1ꢀene)copper(II) (5c). The yield by
method A was 0.76 g (68%), brown powder, m.p. 170—175 °С.
IR, ν/cm–1: 2959, 2925 (C—H); 1726 (СО2Et); 1709 (C=O);
1611, 1583 (C=C); 1281—1130 (C—F). Found (%): C, 42.97;
H, 2.80; F, 20.15; N, 5.10. C20H16CuF6N2O6. Calculated (%):
C, 43.06; H, 2.89; F, 20.43; N, 5.02.
{1ꢀ[Nꢀ(3ꢀOxoꢀ3,3,3ꢀtrifluoroꢀ2ꢀethoxycarbonylbutꢀ1ꢀenꢀ
1ꢀyl)aminato]ꢀ2ꢀ[Nꢀ(3ꢀoxoꢀ4,4,5,5,6,6,6ꢀheptafluoroꢀ2ꢀethoxyꢀ
carbonylhexꢀ1ꢀenꢀ1ꢀyl)aminato]benzene}copper(II) (5h). The
yield by method B was 2.24 g (68%), dark green powder,
m.p. 185—187 °С. IR, ν/cm–1: 3064, 2986, 2943 (C—H); 1720
(СО2Et); 1703 (C=O); 1603, 1583 (C=C); 1270—1125 (C—F).
Found (%): C, 40.25; H, 2.58; F, 29.01; N, 4.47. С22Н16СuF10N2O6.
Calculated (%): С, 40.16; H, 2.45; F, 28.88; N, 4.26.
{1ꢀ[Nꢀ(3ꢀOxoꢀ3,3,3ꢀtrifluoroꢀ2ꢀethoxycarbonylbutꢀ1ꢀenꢀ
1ꢀyl)aminato]ꢀ2ꢀ[Nꢀ(3ꢀoxoꢀ4,4,5,5,6,6,6ꢀheptafluoroꢀ2ꢀethoxyꢀ
carbonylhexꢀ1ꢀenꢀ1ꢀyl)aminato]benzene}nickel(II) (5i). The yield by
method A was 2.37 g (72%), dark red powder, m.p. 178—180 °С.
IR, ν/cm–1: 2986, 2945 (C—H); 1721 br (СО2Et, С=О); 1602,
1582 (C=C); 1281—1055 (C—F). 1Н NMR, δ: 1.34 (t, 3 Н,
ОСН2СН3, 3J = 7.1 Hz); 1.37 (t, 3 Н, ОСН2СН3, 3J = 7.1 Hz);
4.32 (q, 2 Н, ОСН2СН3, 3J = 7.1 Hz); 4.33 (q, 2 Н, ОСН2СН3,
1,1´ꢀ(1,2ꢀPhenylenebisaminato)bis(3ꢀoxoꢀ4,4,5,5,6,6,6ꢀ
heptafluoroꢀ2ꢀethoxycarbonylhexꢀ1ꢀene)nickel(II) (5d). The
yield by method B was 1.19 g (79%), dark red crystals,
m.p. 212—214 °С. IR, ν/cm–1: 2965, 2945 (C—H); 1727 br
(СО2Et, C=O); 1605, 1583 (C=C); 1225—1122 (C—F).
1Н NMR, δ: 1.34 (t, 6 Н, 2 ОСН2СН3, 3J = 7.2 Hz); 4.31 (q,
2
3
3J = 7.1 Hz); 6.31 (tt, 1 Н, H(CF2)2, JH,F = 53.1 Hz, JH,F
=
= 5.7 Hz); 7.24—7.26 (m, 2 H, C6H4); 7.63—7.67 (m, 2 H,
C6H4); 8.30 (s, 1 H, CH); 8.34 (s, 1 H, CH). 19F NMR, δ: 22.49
(dm, 2 F, HCF2, 2JF,H = 53.1 Hz); 38.13 (m, 2 F, CF2); 42.74 (m,
3
4 Н, 2 ОСН2СН3, J = 7.2 Hz); 7.24 (m, 2 Н, С6Н4); 7.64 (m,
2 Н, С6Н4); 8.30 (s, 2 Н, 2 СН). 19F NMR, δ: 38.10 (m, 4 F,

Fluorinated (O)N2O ligands
Russ.Chem.Bull., Int.Ed., Vol. 59, No. 8, August, 2010
1593
2 F, CF2); 51.43 (m, 2 F, CF2); 81.56 (t, 3 F, CF3, 2J = 9.9 Hz).
Found (%): C, 40.30, H, 2.70; F, 29.85; N, 4.06. С23Н17F11N2NiO6.
Calculated (%): С, 40.32; H, 2.50; F, 30.05; N, 4.09.
{1ꢀ[Nꢀ(3ꢀOxoꢀ4,4,5,5ꢀtetrafluoroꢀ2ꢀethoxycarbonylpentꢀ
1ꢀenꢀ1ꢀyl)aminato]ꢀ2ꢀ[Nꢀ(3ꢀoxoꢀ4,4,5,5,6,6,6ꢀheptafluoroꢀ
2ꢀethoxycarbonylhexꢀ1ꢀenꢀ1ꢀyl)aminato]benzene}copper(II) (5j).
The yield by method B was 2.38 g (69%), dark green powder,
m.p. 195—197 °С. IR, ν/cm–1: 2987, 2945 (C—H); 1722 br (СО2Et,
C=O); 1602, 1584 (C=C); 1277—1193 (C—F). Found (%):
C, 39.62; H, 2.73; F, 29.85; N, 3.85. С23Н17CuF11N2O6. Calculꢀ
ated (%): С, 40.04; H, 2.48; F, 30.19; N, 4.06.
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This work was financially supported by the Presidium
of the Ural Branch of the Russian Academy of Sciences
(Program No. 09ꢀPꢀ3ꢀ1013) and the Russian Foundation
for Basic Research (Project No. 10ꢀ03ꢀ96017).
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Received October 21, 2009;
in revised form April 9, 2010