Design of postmetallocene catalytic systems of arylimine type for olefins polymerization: XIII. Synthesis of tetradentate bis(2-hydroxy-1-naphthaldimine) ligands and their complexes with titanium(IV) dichloride

Article abstract of DOI:10.1134/S1070428010050246

Reactions of 2-hydroxy-1-naphthaldehyde with 1,4-diaminobutane, 1,6-diaminohexane, 4,4′-methylenedianiline and its alkyl- and cycloalkyl-sybstituted derivatives, with 4,4′-sulfonyldianiline, 2,2′- and 4,4′-oxydianiline, 4,4′-(1,4-phenylenebisoxy) dianiline, 4,4′-[propane-2,2-diylbis(1,4-phenylenebisoxy)]dianiline, and p-terphenyl-4,4″-diamine afforded a series of the corresponding diimines that at treating with TiCl₂(OPr-i)₂ formed mono- and binuclear complexes of titanium(IV) dichloride with tetradentate ligands LTiCl₂ and L₂(TiCl₂)₂. Pleiades Publishing, Ltd., 2010.

Full text of DOI:10.1134/S1070428010050246

ISSN 1070-4280, Russian Journal of Organic Chemistry, 2010, Vol. 46, No. 5, pp. 746−752. © Pleiades Publishing, Ltd., 2010.
Original Russian Text © I.I. Oleinik, I.V. Oleinik, S.S. Ivanchev, G.A. Tolstikov, 2010, published in Zhurnal Organicheskoi Khimii, 2010, Vol. 46,
No. 5, pp. 751−757.
Design of Postmetallocene Catalytic Systems
of ArylimineType for Olefins Polymerization: XIII.*
Synthesis of Tetradentate Bis(2-hydroxy-1-naphthaldimine)
Ligands and Their Complexes with Titanium(IV) Dichloride
I. I. Oleinika, I. V. Oleinika, S. S. Ivanchevb, and G. A. Tolstikova
aVorozhtsov Novosibirsk Institute of Organic Chemistry, Siberian Division, Russian Academy of Sciences,
Novosibirsk, 630090, Russia
e-mail: oleynik@nioch.nsc.ru
bSt. Petersburg Division of Boreskov Institute of Catalysis, Siberian Division, Russian Academy of Sciences, Russia
Received April 22, 2009
Abstract— Reactions of 2-hydroxy-1-naphthaldehyde with 1,4-diaminobutane, 1,6-diaminohexane, 4,4'-
methylenedianiline and its alkyl- and cycloalkyl-sybstituted derivatives, with 4,4'-sulfonyldianiline, 2,2'- and 4,4'-
oxydianiline, 4,4'-(1,4-phenylenebisoxy)dianiline, 4,4'-[propane-2,2-diylbis(1,4-phenylenebisoxy)]dianiline, and
p-terphenyl-4,4''-diamine afforded a series of the corresponding diimines that at treating with TiCl2(OPr-i)2 formed
mono- and binuclear complexes of titanium(IV) dichloride with tetradentate ligands LTiCl2 and L2(TiCl2)2.
DOI: 10.1134/S1070428010050246
Desingning new highly effective catalytic systems
remains an urgent task for the need in new polymers is
still great and the opportunity for the control of their struc-
ture and properties depends primarily on the development
of catalysts with specific structure [2]. In the preceding
paper [1] we substantiated the prospects in the preparation
of new catalysts for olefins polymerization through the
structure modification of α-diimine, diiminopyridine, and
bis(salicylaldimine) complexes consisting in the binding
the imine substituents by versatile bridges by using primary
alkyl- or aryldiamines in the synthesis of ligands of the
modified complexes.
ature [3] (chain transfer and β-hydride transfer, transfer
of the ligand to the aluminum cocatalyst [4], 1,2-“migra-
tion” insertion of the alkyl ligand into the C=N bond [5],
and “bimolecular deactivation” [6]). It is expectable that
since the ligands are of polydentate character the modifi-
ed catalysts should be more stable against the thermal
deactivation for in this event the dissociation becomes
stepwise and the reverse process is intramolecular. The
latter fact is especially important for the olefin polymeriz-
ation under homogeneous conditions is carried out at very
low catalyst concentration (10–4–10–8 mol l−1).
Depending on the bridge structure in the tetradentate
bis(phenoxyimine) ligands and on the synthesis conditions
in complexing with halides of the IV group transition
metals two types of complexes can be obtained, mono-
nuclear LMCl2 or binuclear L2(MCl2)2. Our interest in
polynuclear complexes [7], in particular, in binuclear
phenoxyimine ones [8, 9], is due to the hope that alongside
the properties inherent to the mononuclear complexes
they would exhibit specific catalytic behavior depending
on the bridge character as it has been found in
homobinuclear metallocenes. It is presumable that the
The theoretical basis of this approach to the refining
of the structure of the postmetallocene complexes aiming
at increasing the catalytic activity and the temperature
range of their efficient operation is the concept that to
the ligand surrounding the processes are sensitive leading
to the decrease in the catalytic activity, to the loss of the
“living” character of the polymerization and to the
formation of low-molecular polymers at elevated temper-
* For Communication XII, see [1].
746

DESIGN OF POSTMETALLOCENE CATALYTIC SYSTEMS...: XIII.
747
made it possible to obtain with high efficiency even at
70°C linear polyethylene of high and superhigh molecular
weight possessing an elevated melting point.
binuclear complexes apart from the dissociative stability
due to the polidentate character of ligands would be more
stable against the bimolecular deactivation since the larger
steric loading of the molecule should more efficiently
prevent the mutual contacts of the active centers.
The examples cited above show that the now existing
data on the synthesis and catalytic properties of binuclear
complexes with tetradentate phenoxyimine ligands are
scanty. In order to describe the structure of these
complexes required for the operation of the “active
centers cooperation” effect it is necessary to investigate
a set of complexes with versatile tetradentate ligands.
The use in the polymerization of binuclear complexes
opens an opportunity to obtain quite new polymer materials
that are not produced in the presence of mononuclear
analogs because of the “active centers cooperation” [10]
observed only in the olefins polymerization on the binuclear
metallocenes and resulting in the formation of high-
molecular polymer with a wide molecular-weight
distribution, with improved morphology, in the shift of the
maximum of catalytic activity to higher temperature, in
higher branching in ethylene homopolymerization and in
larger fraction of α-olefin in the copolymerization [11].
The catalytic activity of complex A and its mono-
nuclear analog in ethylene and propylene polymerization
was compared in [12]. The activity of the binuclear
complex was considerably lower than that of the mono-
nuclear, and the former practically instantly deactivated
at 90°C. It was concluded from the characteristics of
polymers obtained that the mechanism of the chain
propagation and chain transfer in the course of the
polymerization was materially identical, and the main
process limiting the chain propagation was the bimolecular
reaction of the active centers with the growing polymer
chain. These data showed the absence of the “active
centers cooperation”. Binuclear complex B of the
monophenoxyimine type is considerably more active that
the corresponding mononuclear analog in the ethylene
homopolymerization and provides larger amount of
1-hexene units in the copolymerization [13]. These results
were ascribed to the effect of “active centers coopera-
tion”. It was shown in [8] that binuclear complexes C
In this work in the frame of the systematic investiga-
tion of the influence on the catalytic activity of metallo-
complexes of their structural modification [1, 8, 9, 14,
15] we describe the preparation of tetradentate bis(2-
hydroxy-1-naphthaldimine) ligands containing various
diamine spacers, and their complexes with titanium(IV)
dichloride aiming at making them available for testing as
catalysts of alkenes polymerization. The 2-hydroxy-1-
naphthaldehyde (I) was selected as the carbonyl
component since in patent [16] complexes with bidentate
ligands had been described based on vicinal isomers of
hydroxynaphthaldehydes.
The synthesis of tetradentate ligands is underlain by
the reaction of the vicinal hydroxyaldehyde with primary
diamines formerly performed by an example of substituted
salicylaldehydes [8, 9, 12]. We extended this procedure
to the preparation of new bis(2-hydroxy-1-naphthal-
dimine) ligands III and optimized the conditions of their
synthesis.
The reaction of hydroxynaphthaldehyde I with 1,4-
diaminobutane (IIa) and 1,6-diaminohexane (IIb) in
methanol at room temperature required 30 min and no
catalyst providing in a quantitative yield the corresponding
diimines IIIa and IIIb. The reaction of diamines IIc–
IIh proceeded at boiling in methanol in the presence of
F
F
F
F
F
F
F
R2
R2
N
N
N
N
O
O
O
O
O
O
O
O
R1
R1
F
O
O
Cl2Ti
TiCl2
Cl2Ti
Cl
Cl Cl
Cl
N
TiCl2
F
Zr
Cl
Zr
Cl
N
O
O
R1
R1
F F
F
F
N
N
R2
R2
N
N
F
F F
B
C
A
RUSSIAN JOURNAL OF ORGANIC CHEMISTRY Vol. 46 No. 5 2010

OLEINIK et al.
748
H
X
H
H
O
O
O
N
N
O
LTiCl2
2
IVa, IVb, IVh
3
TiCl2(OPr-i)2
CH3OH
NH2
NH2
+
X
4
8
L2(TiCl2)2
IVc_IVg, IVi_IVl
7
5
6
H2L
IIIa_IIIl
I
IIa_IIl
Me
(d),
Me
(e),
(f),
X = (CH2)4 (a), (CH2)6 (b),
(c),
Me
Me
Me
Me
Me
Me
Me
O2
S
Me
O
O
O
(j),
(g),
(i),
(k),
(h),
(l).
O
O
O
a strong absorption band at 1636 and 1629 cm–1 respec-
tively, whereas in the other Schiff bases the ν(N=CH)
frequency is considerably lower (1622–1625 cm–1). In
the mass spectra of synthesized ligands a strong peak of
the molecular ion was observed.
catalytic quantity of formic acid and completed within
0.5–7 h (yields 94–99%). The condensation of hydroxy-
naphthaldehyde I at both amino groups of diamines IIi–
IIl occurred at boiling the initial compounds in a mixture
of methanol and dichloromethane, 1:1, in the presence of
catalytic quantity of formic acid and afforded diimines
IIIi–IIIl in 94–98% yield.
The phenoxyimine complexes of titanium(IV)
dichloride are usually prepared by reaction of the
deprotonated form of the ligand with titanium tetrachloride
or its adduct with tetrahydrofuran [18]. Although this
procedure provides the complexes in good yields it
possesses obvious disadvantages for the ligand is
deprotonated by the reaction with butyllithium or with
alkali metal hydride. We regard as more convenient
a newly developed one-stage method of the synthesis of
titanium(IV) dichloride complexes [12, 19, 20] underlain
by the capability of the alkoxydihalides of IV group
elements to deprotonate the ligands. We chose this one-
stage method since it lacks the above mentioned
drawbacks for the preparation of mono- and binuclear
complexes of titanium(IV) dichloride with versatile
combination of substituents [8, 9, 15].
The structure of obtained bis(naphthaldimines) IIIa–
IIIl was established from analytic and spectral data. 1H
NMR spectra suggest that the Schiff bases we obtained
are individual Ε-isomers. The singlets of groups N=CH
in the 1H NMR spectra of bisimines appear in the region
8.51–9.64 ppm. In the spectrum of sulfonyl derivative
IIIg the signal of the N=CH group is strongly shifted
downfield (10.82 ppm). The signals of OH groups of
ligands IIIa–IIIi, IIIk give rise to broadened singlets in
the region 12.50–15.80 ppm (this downfield shift indicates
the presence of an intramolecular hydrogen bond between
the hydrogen of the OH group and the nitrogen atom of
the imine moiety). In the 1H NMR spectra of bisimines
IIIj and IIIl taken in DMSO-d6 since they were sparingly
soluble in CDCl3 the signal of hydroxy group was lacking.
The assignment of the proton signals of the naphthalene
skeleton was based on the known assignment of signals
in the spectrum of 2-hydroxy-1-naphthaldehyde [17]. The
spectra of diimines IIIa and IIIb prepared from
diaminoalkanes contain the multiplets of CH2 groups at
1.42–1.98 ppm and triplets of NCH2 groups at 3.74 and
3.66 ppm, and in the spectra of diimines IIIc–IIIf obtained
from methylenedianilines alongside the signals of aromatic
protons the singlets belonging to CH2 groups are observed
at 3.82–4.03 ppm. In the IR spectra of bisimines IIIa
and IIIb with methylene spacers the stretching vibrations
of the C=N bond from the imine moiety give rise to
At treatment of bisimines IIIa–IIIl with an equimolar
amount of TiCl2(OPr-i)2 in toluene solution at room
temperature titanium complexes IVa–IVl were obtained
in high yield. The complexes can be of the mono- or
binuclear structure. The choice between the possible
structures LTiCl2 and L2(TiCl2)2 would be easy from the
molecular weight of compounds. Regretfully, we failed
to determine the molecular weight of complexes IV due
to their extremely low solubility. Still, considering the
available published data on the structure of the titanium
and zirconium dichlorides with tetradentate bis(salicylald-
imine) ligands we may assume that ligands IIIa, IIIb,
IIIh form mononuclear complexes LTiCl2, whereas
RUSSIAN JOURNAL OF ORGANIC CHEMISTRY Vol. 46 No. 5 2010

DESIGN OF POSTMETALLOCENE CATALYTIC SYSTEMS...: XIII.
749
ligands IIIc–IIIg, IIIi–IIIl afford binuclear complexes
L2(TiCl2)2.As shown in [5, 12, 16, 20, 21] when the imine
nitrogen atoms of bisimine ligands are capable due to
the mobility and flexibility of the spacer to occupy the
contiguous vertexes of an octahedron these ligands form
mononuclear complexes LTiCl2, and when the rigidity of
the spacer impedes this location of the imine nitrogen
atoms the binuclear complexes L2(TiCl2)2 are formed.
The assumption on difference in the structures of
complexes IVa, IVb, IVh and those of IVc–IVg, IVi–
IVl is in agreement with the difference in the structure
of titanium dichloride complexes with the ligands obtained
from salicylaldehydes with bulky substituents and
diamines IIa–IIl [1, 8, 9] whose molecular weight has
been determined. The molecular weight of analogs of
complexes IVa, IVb, IVh corresponded to the formula
LTiCl2, of analogs of complexes IVc–IVg, IVi–IVl, to
the structure L2(TiCl2)2.
Diimines IIIa and IIIb. Amixture of 0.172 g (1 mmol)
of 2-hydroxy-1-naphthaldehyde, 0.5 mmol of the cor-
responding diamine IIa or IIb, and 10 ml of methanol
was stirred at room temperature for 30 min till the
disappearance of the initial compounds (TLC monitoring).
The separated precipitate was filtered off and washed
with 3 ml of methanol.
1,1'-[Tetramethylenebis(iminomethyl)]bis(2-
naphthol) (IIIa). Yield 97%, mp 227–229°C. IR
1
spectrum, ν, cm–1: 1636 (N=CH). H NMR spectrum
(CDCl3+DMSO-d6), δ, ppm: 1.75–1.98 m (4H, CH2),
3.74 t (4H, NCH2, J 7.5 Hz), 6.82 d (2H, H3, J 8.5 Hz),
7.19 t (2H, H6, J 8 Hz), 7.40 t (2H, H6, J 8 Hz), 7.58 d
(2H, H5, J 8 Hz), 7.66 d (1H, H4, J 8.5 Hz), 7.93 d (1H,
H8, J 8 Hz), 8.51 s (2H, CH=N), 13.85 br.s (2H, OH).
Found [M]+ 396.18407. C26H24N2O2. Calculated
M 396.18377.
1,1'-[Hexamethylenebis(iminomethyl)]bis(2-
The composition of titanium dichloride complexes IVa–
IVl is confirmed by elemental analysis and IR spectra.
In the IR spectra of complexes IVa–IVl absorption
bands appear in the region 447–478 (Ti–N) and 542–
567cm–1 (Ti–O). The complex formation results in
significant decrease in the ν(N=CH) frequency in the
spectra of complexes IVa and IVb (by 10–18 cm–1),
whereas in the complexes IVc–IVl these changes not
exceed 1–4 cm–1. Due to low solubility of these
complexes and their instability in CDCl3 we failed to
naphthol) (IIIb). Yield 95%, mp 173–174°C (175°C
1
[25]). IR spectrum, ν, cm–1: 1629 (N=CH). H NMR
spectrum (DMSO-d6), δ, ppm: 1.40–1.57 m (4H, CH2),
1.61–1.82 m (4H, CH2), 3.66 t (4H, NCH2, J 7.5 Hz),
6.73 d (2H, H3, J 8.5 Hz), 7.14 t (2H, H6, J 8 Hz), 7.38 t
(2H, H7, J 8 Hz), 7.56 d (2H, H5, J 8 Hz), 7.65 d (1H, H4,
J 8.5 Hz), 8.00 d (1H, H8, J 8 Hz), 9.04 s (2H, CH=N),
14.25 br.s (2H, OH). Found [M]+ 424.21464.
C28H28N2O2. Calculated M 424.21506.
Diimines IIIc–IIIh. A mixture of 0.172 g (1 mmol)
of 2-hydroxy-1-naphthaldehyde, 0.5 mmol of an
appropriate diamine IIc–IIh, 10 ml of methanol, and 5 mg
of anhydrous formic acid was boiled for 0.5–7 h till the
disappearance of the initial compounds (TLC monitoring).
On cooling the reaction mixture the separated precipitate
was filtered off and washed with 3 ml of methanol.
1
register their H NMR spectra.
EXPERIMENTAL
1H NMR spectra were registered on a spectrometer
Bruker AC-200 at operating frequency 200.13 MHz. IR
spectra were recorded on a spectrophotometer Vector
22 from samples pelletized with KBr. The monitoring of
reactions progress and checking of the purity of com-
pounds synthesized was carried out by TLC on Silufol
UV-254 plates, eluent chloroform. The flash-chromato-
graphy [22] was performed with the use of silica gel 5–
40 μ, eluent chloroform–hexane, 1:1. The empirical
formulas of compounds obtained were calculated from
the high resolution mass spectra taken of a Finnigan MAT
8200 instrument. The melting points were determined
by heating compounds between glass plates at a rate
1 deg/min.
1,1'-{Methylenebis[(1,4-phenylene)imino-
methyl]}bis(2-naphthol) (IIIc). Yield 96%, mp 248–
250°C (247–248°C [26]). IR spectrum, ν, cm–1: 1624
(N=CH). 1H NMR spectrum (DMSO-d6), δ, ppm: 4.03 s
(2H, CH2), 6.97 d (4H, H3',5', J 7.8 Hz), 7.30 d (2H, H3,
J8.5 Hz), 7.38 t (2H, H6, J 8 Hz), 7.53 t (2H, H7,
J 8 Hz), 7.58 d (2H, H5, J 8 Hz), 7.76 d (2H, H4, J 8.5 Hz),
7.89 d (2H, H8, J 8 Hz), 8.45 d (4H, H2',6', J 7.8 Hz), 9.60
s (2H, CH=N), 15.80 br.s (2H, OH). Found [M]+
506.20023. C35H26N2O2. Calculated M 506.19942.
1,1'-{Methylenebis[(3,5-dimethyl-1,4-phenyl-
ene)iminomethyl]}bis(2-naphthol) (IIId). Yield 95%,
mp 213–214°C. IR spectrum, ν, cm–1: 1624 (N=CH).
1H NMR spectrum (CDCl3), δ, ppm: 2.26 s (12H, CH3),
2-Hydroxy-1-naphthaldehyde was obtained by
procedure [23], methylenedianilines IId–IIf, by method
[1], 2,2'- and 4,4'-oxydianilines, by method [24].
RUSSIAN JOURNAL OF ORGANIC CHEMISTRY Vol. 46 No. 5 2010

OLEINIK et al.
750
3.82 s (2H, CH2), 6.91 s (4H, H3',5'), 7.12 d (2H, H3,
J 8.5 Hz), 7.25 t (2H, H6, J 8 Hz), 7.40 t (2H, H7,
J 8 Hz), 7.68 d (2H, H5, J 8 Hz), 7.78 d (2H, H4, J 8.5 Hz),
7.96 d (2H, H8, J 8 Hz), 9.13 s (2H, CH=N), 14.85 br.s
(2H, OH). Found [M]+ 562.26200. C39H34N2O2.
Calculat-ed M 562.26201.
boiled for 0.5–7 h till the disappearance of the initial
compounds (TLC monitoring). The solvents were distilled
off on a rotary evaporator in a vacuum of a water-jet
pump at the bath temperature 45°C, the residue of
compounds IIIi, IIIk, IIIl was subjected to flash-
chromatography. From the first bright yellow fraction the
solvent was evaporated, the residue was ground with 5
ml of methanol, the precipitate was filtered off. When
isolating diimine IIIj the residue after distilling off the
solvents was recrystallized from a mixture DMF–
methanol, 1:1.
1,1'-{Methylenebis[(3-methyl-5-cyclopentyl-1,4-
phenylene)iminomethyl]}bis(2-naphthol) (IIIe).
Yield 99%, mp 99–100°C. IR spectrum, ν, cm–1: 1624
1
(N=CH). H NMR spectrum (CDCl3), δ, ppm: 1.51–
2.08 m (16H, CH2), 2.24 s (6H, Me), 2.99–3.22 m (2H,
CH), 3.86 s (2H, CH2); 6.84 s, 7.00 C (4H, H3',5'); 7.12 d
(2H, H3, J 8.5 Hz), 7.23 t (2H, H6, J 8 Hz), 7.38 t (2H,
H7, J 8 Hz), 7.67 d (2H, H5, J 8 Hz), 7.77 d (2H, H4,
J 8.5 Hz), 7.96 d (2H, H8, J 8 Hz), 9.12 s (2H, CH=N),
14.75 br.s (2H, OH). Found [M]+ 562.26200.
C39H34N2O2. Calculated M 562.26201.
1,1'-{Oxybis[(1,4-phenylene)iminomethyl]}-
bis(2-naphthol) (IIIi). Yield 95%, mp 176–177°C. IR
1
spectrum, ν, cm–1: 1622 (N=CH). H NMR spectrum
(CDCl3), δ, ppm: 7.05–7.43 m (12Harom), 7.54 t (2H, H7,
J 8 Hz), 7.76 d (2H, H5, J 8 Hz), 7.86 d (2H, H4, J 8 Hz),
8.15 d (2H, H8, J 7.8 Hz), 9.39 s (2H, CH=N), 15.15 br.s
(2H, OH). Found [M]+ 508.17799. C34H24N2O3.
Calculated M 508.17868.
1,1'-{Methylenebis[(3-methyl-5-cyclohexyl-1,4-
phenylene)iminomethyl]}bis(2-naphthol) (IIIf). Yield
99%, mp 113–114°C. IR spectrum, ν, cm–1: 1624
1,1'-{(1,4-Phenylenedioxy)bis[(1,4-phenylene)-
iminomethyl]}bis(2-naphthol) (IIIj). Yield 94%,
mp 245–246°C. IR spectrum, ν, cm–1: 1622 (N=CH).
1H NMR spectrum (DMSO-d6), δ, ppm: 7.01–7.19 m
(10Harom), 7.36 t (2H, H6, J 8 Hz), 7.55 t (2H, H7,
J 8 Hz), 7.59–7.70 m (4Harom), 7.80 d (2H, H5, J 8 Hz),
7.95 d (2H, H4, J 8.5 Hz), 8.46 d (2H, H8, J 8 Hz), 9.64 s
(2H, CH=N). Found [M]+ 600.20490. C40H28N2O4.
Calculated M 600.20489.
1
(N=CH). H NMR spectrum (CDCl3), δ, ppm: 1.19–
1.53 m (12H, CH2), 1.59–1.98 m (8H, CH2), 2.26 s (6H,
Me), 2.55–2.85 m (2H, CH), 3.86 s (2H, CH2); 6.84 s,
6.97 s (4H, H3',5'); 7.14 d (2H, H3, J 8.5 Hz), 7.23 t (2H,
H6, J 8 Hz), 7.39 t (2H, H7, J 8 Hz), 7.68 d (2H, H5,
J 8 Hz), 7.79 d (2H, H4, J 8.5 Hz), 7.96 d (2H, H8, J 8 Hz),
9.14 s (2H, CH=N), 14.80 br.s (2H, OH). Found
[M]+ 698.38734. C49H50N2O2. Calculated M 698.38721.
1,1'-{Sulfonylbis[(1,4-phenylene)imino-
methyl]}bis(2-naphthol) (IIIg). Yield 94%, mp 267–
269°C (265°C [27]). IR spectrum, ν, cm–1: 1624 (N=CH).
1H NMR spectrum (CDCl3 + DMSO-d6), δ, ppm: 6.59 d
(4H, H3',5', J 7.8 Hz), 7.13 d (2H, H3, J 8.5 Hz), 7.41 t
(2H, H6, J 8 Hz), 7.58 t (2H, H7, J 8 Hz), 7.80 d (2H, H5,
J 8 Hz), 7.88 d (2H, H4, J 8.5 Hz), 8.02 d (2H, H8,
J 8 Hz), 8.69 d (4H, H2',6', J 7.8 Hz), 10.82 s (2H, CH=N),
12.50 br.s (2H, OH). Found [M]+ 556.14498.
C34H24N2O4S. Calculated M 556.14567.
1,1'-{(Propane-2,2-diyl)bis[(1,4-phenylene)-
oxy(1,4-phenylene)iminomethyl]}bis(2-naphthol)
(IIIk). Yield 95%, mp 152–154°C. IR spectrum, ν,
cm–1: 1623 (N=CH). 1H NMR spectrum (CDCl3), δ, ppm:
1.70 C (6H, Me), 6.98–7.41 m (20Harom), 7.55 t (2H, H7,
J 8 Hz), 7.75 d (2H, H5, J 8 Hz), 7.83 d (2H, H4, J 8 Hz),
8.13 d (2H, H8, J 8 Hz), 9.37 s (2H, CH=N), 15.05 br.s
(2H, OH). Found [M]+ 718.28256. C49H38N2O4.
Calculated M 718.28314.
1,1'-[(4,4''-p-Terphenylene)bis(iminomethyl)]-
bis(2-naphthol) (IIIl). Yield 98%, mp 344–345°C (345–
347°C [26]). IR spectrum, ν, cm–1: 1625 (N=CH).
1,1'-{Oxybis[(1,2-phenylene)iminomethyl]}-
bis(2-naphthol) (IIIh). Yield 95%, mp 222–224°C. IR
1
spectrum, ν, cm–1: 1623 (N=CH). H NMR spectrum
1H NMR spectrum (DMSO-d6), δ, ppm: 6.98 d (4Harom
,
(CDCl3), δ, ppm: 6.85–7.31 m (8Harom), 7.35–7.82 m
(6Harom), 7.89–8.06 m (4Harom), 8.34 d (2H, H8, J 8 Hz),
9.32 s (2H, CH=N), 15.35 br.s (2H, OH). Found [M]+
508.17900. C34H24N2O3. Calculated M 508.17868.
J 8 Hz), 7.09–7.41 m (16Harom), 7.55 t (2H, H7, J 8 Hz),
7.75 d (2H, H5, J 8 Hz), 7.83 d (2H, H4, J 8 Hz), 8.13 d
(2H, H8, J 7.8 Hz), 9.70 s (2H, CH=N). Found [M]+
568.21450. C40H28N2O2. Calculated M 568.21506.
Diimines IIIi–IIIl. Amixture of 0.172 g (1 mmol) of
2-hydroxy-1-naphthaldehyde, 0.5 mmol of an appropriate
diamine IIi–IIl, 10 ml of methanola, 10 ml of anhydrous
dichloromethane, and 5 mg of anhydrous formic acid was
Titanium(IV) dichloride complexes IVa–IVl.
A mixture of 1 mmol of ligand IIIa–IIIl, 40 ml of
anhydrous dichloromethane, and 1 mmol of TiCl2(OPr-i)2
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DESIGN OF POSTMETALLOCENE CATALYTIC SYSTEMS...: XIII.
751
spectrum, ν, cm–1: 1622 (C=N), 560 (Ti–O), 460 (Ti–N).
Found, %: C 60.38; H 3.41; Cl 10.29; N 4.28.
C68H44Cl4N4O8S2Ti2. Calculated, %: C 60.64; H 3.29;
Cl 10.53; N 4.16.
as a solution (0.350 mmol/g) in anhydrous toluene was
stirred under an argon atmosphere for 24 h. The solvents
were distilled off in a vacuum of a water-jet pump, the
residue was maintained in a vacuum of an oil; pump for
1 h at 100°C.
{1,1'-Oxybis[(1,2-phenylene)iminomethyl]bis-(2-
naphthyloxy)}titanium(IV) dichloride (IVh). Dark
brown powder. Yield 92%. IR spectrum, ν, cm–1: 1620
(C=N), 559 (Ti–O), 464 (Ti–N). Found, %: C 65.40;
H 3.60; Cl 11.18; N 4.47. C34H22Cl2N2O3Ti. Calculated,
%: C 65.30; H 3.55; Cl 11.34; N 4.48.
[1,1'-Tetramethylenebis(iminomethyl)bis(2-
naphthyloxy)]titanium(IV) dichloride (IVa). Dark
orange powder. Yield 97%. IR spectrum, ν, cm–1: 1618
(C=N), 542 (Ti–O), 447 (Ti–N). Found, %: C 60.49;
H 4.43; Cl 13.65; N 5.58. C26H22Cl2N2O4Ti. Calculated,
%: C 60.84; H 4.32; Cl 13.82; N 5.46.
Bis{1,1'-oxybis[(1,4-phenylene)iminomethyl]-
bis(2-naphthyloxy)}bis[titanium(IV) dichloride]
(IVi). Brown powder. Yield 99%. IR spectrum, ν, cm–1:
1621 (C=N), 550 (Ti–O), 460 (Ti–N). Found, %: C 65.18;
H 3.68; Cl 11.15; N 4.64. C68H44Cl4N4O6Ti2. Calculated,
%: C 65.30; H 3.55; Cl 11.34; N 4.48.
[1,1'-Hexamethylenebis(iminomethyl)bis(2-
naphthyloxy)]titanium(IV) dichloride (IVb). Brown
powder. Yield 99%. IR spectrum, ν, cm–1: 1619 (C=N),
550 (Ti–O), 460 (Ti–N). Found, %: C 61.90; H 4.95; Cl
13.16; N 5.27. C28H26Cl2N2O4Ti. Calculated, %: C 62.13;
H 4.84; Cl 13.10; N 5.18.
Bis{1,1'-(1,4-phenylenedioxy)bis[(1,4-phenyl-
ene)-iminomethyl]bis(2-naphthyloxy)}bis-
[titanium(IV) dichloride] (IVj). Dark brown powder.
Yield 98%. IR spectrum, ν, cm–1: 1621 (C=N), 550 (Ti–
O), 461 (Ti–N). Found, %: C 66.78; H 3.84; Cl 9.70;
N 4.02. C80H52Cl4N4O8Ti2. Calculated, %: C 66.97;
H 3.65; Cl 9.88; N 3.90.
Bis{1,1'-methylenebis[(1,4-phenylene)-
iminomethyl]bis(2-naphthyloxy)}bis[titanium(IV)
dichloride] (IVc). Red-brown powder. Yield 94%. IR
spectrum, ν, cm–1: 1623 (C=N), 550 (Ti–O), 478 (Ti–N).
Found, %: C 67.09; H 4.01; Cl 11.46; N 4.46.
C70H48Cl4N4O4Ti2. Calculated, %: C 67.44; H 3.88;
Cl 11.37; N 4.49.
Bis{1,1'-(propane-2,2-diyl)bis[(1,4-phenylene)-
oxy(1,4-phenylene)iminomethyl]bis(2-naph-
thyloxy)}bis[titanium(IV) dichloride] (IVk). Orange-
brown powder. Yield 99%. IR spectrum, ν, cm–1: 1622
(C=N), 567 (Ti–O), 460 (Ti–N). Found, %: C 70.46;
H 4.51; Cl 8.62; N 3.49. C98H72Cl4N4O8Ti2. Calculated,
%: C 70.43; H 4.34; Cl 8.49; N 3.35.
Bis{1,1'-methylenebis[(3,5-dimethyl-1,4-
phenylene)iminomethyl]bis(2-naphthyloxy)}-
bis[titanium(IV) dichloride] (IVd). Dark brown
powder. Yield 99%. IR spectrum, ν, cm–1: 1621 (C=N),
556 (Ti–O), 470 (Ti–N). Found, %: C 68.78; H 4.89;
Cl 10.15; N 4.25. C78H64Cl4N4O4Ti2. Calculated, %: C
68.94; H 4.75; Cl 10.44; N 4.12.
Bis{[1,1'-(4,4'’-p-terphenylene)bis(imino-
methyl)]-bis(2-naphthyloxy)}bis-[titanium(IV)
dichloride] (IVl). Dark brown powder. Yield 99%. IR
spectrum, , cm–1: 1624 (C=N), 551 (Ti–O), 470 (Ti–N).
Found, %: C 69.78; H 3.97; Cl 10.15; N 4.23.
C80H52Cl4N4O4Ti2. Calculated, %: C 70.09; H 3.82;
Cl 10.34; N 4.09.
Bis{1,1'-methylenebis[(3-methyl-5-cyclopentyl-
1,4-phenylene)iminomethyl]bis(2-naphthyloxy)}-
bis[titanium(IV) dichloride] (IVe). Dark brown
powder. Yield 95%. IR spectrum, ν, cm–1: 1620 (C=N),
555 (Ti–O), 465 (Ti–N). Found, %: C 71.67; H 5.79;
Cl 8.86; N 3.78. C94H88Cl4N4O4Ti2. Calculated, %:
C 71.67; H 5.63; Cl 9.00; N 3.56.
REFERENCES
Bis{1,1'-methylenebis[(3-methyl-5-cyclohexyl-
1,4-phenylene)iminomethyl]bis(2-naphthyloxy)}bis-
[titanium(IV) dichloride] (IVf). Dark brown powder.
Yield 92%. IR spectrum, ν, cm–1: 1621 (C=N), 559 (Ti–
O), 469 (Ti–N). Found, %: C 71.98; H 5.98; Cl 8.49; N
3.59. C98H96Cl4N4O4Ti2. Calculated, %: C 72.15; H 5.93;
Cl 8.69; N 3.43.
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