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Two novel nickel(II) complexes with Schiff base derived

from tripod amine and acetylacetone or salicylaldehyde

František Březina, Martin Biler and Richard Pastorek

Department of Inorganic and Physical Chemistry, Palacký University, Křížkovského 10,

77 147 Olomouc, Czech Republic
Received May 31. 1998

Novel complexes of the type [Ni(TAA-sal)(H2O)]X (TAA-sal = Schiff base derived
from tris(2-aminoethyl)amine - TAA and salicylaldehyde - sal, X = Cl, NO3) or
[Ni(TAA-acac). (H2O)]BPh4 (TAA-acac= Schiff base derived from TAA and
acetylacetone - acac) have been prepared and studied by elemental analyses, IR and
VIS spectra, magnetic measurements and by means of thermal analyses. Physico-
chemical studies account for the deformed octahedral coordination mode.

Key Words: Nickel(II)- complex-Schiff base- tripod amine

A number of hexaimino cryptands have been prepared from aromatic aldehydes
and tripod amines1. The cryptands containing transition metal ions are expected to
show catalytic activity, which is one of the major goals in supramolecular chemistry.
Some macrocyclic complexes are known to be prepared from acetylacetone and
polyamines. In analogy with these known reactions, Sato et al.2 intended to prepare
a new cryptand by condensation of acetylacetone with tris(2-aminoethyl)amine. Al-
though every attempt did not afford the targent cryptand, two kinds of complexes have
been prepared for various metal ions: one containing two tridentate ligands which
have ketoimine moieties at all primary amino groups of TAA, and the other has
a pentadentate ligand having a ketoimine moiety at one of the three amino groups of
TAA. The Sr2+, Ca2+, Mg2+ and Mn2+ give the former type complexes and Cu2+, Co3+
and Zn2+ give the latter. The crystal structures of all the complexes have been charac-
terized by X-ray analyses. The aim of this work was to study the influence of nickel(II)
on composition of such type of complexes.

Materials and methods
Tris(2-aminoethyl)amine (Fluka), salicylaldehyde, acetylacetone (Reachim) and
the other chemicals (Lachema) were used without further modification. The C, H, N
analyses were performed on an EA 1108 CHN analyser of Fisions instruments. IR
absorption spectra were recorded on a Specord M 80 (Carl Zeiss, Jena) using the nujol
technique, electronic spectra were carried out on a Specord M 40 (Carl Zeiss, Jena).
Magnetic susceptibilities were measured by the Faraday method on a laboratory
designed devies usin CoHg(NCS)4 as callibrant. The corrections for diamagnetism
were performed according to3. Thermoanalytical study was recorded on the
derivatograph Q 1500 (MOM Budapest) in the air atmosphere with sample mass of
150–200 mg and temperature gradient 2,5o C/min. The powder diffractograms were
recorded on the X-ray difractometer XRD-7 (Seifert) and the molar conductivities
were measured on Conductivity Meter OK 102/1 (Radelkis, Budapest) at 25o in 5.10-4M
Preparation of [Ni(TAA-acac)(H2O)]BPh4 (1)
To a stirred solution of Ni(ClO4)2.6H2O (0,36g, 1 mmol) in methanol (5 ml) was
added acetylacetone (0,11 ml, 1 mmol) and after 5 min. tris(2-aminoethyl)amine
(0,16 ml, 1 mmol) and triethylamine (0,28 ml, 2 mmol). The pale brown solution was
stirred at room temperature owernight. NaBPh4 (0,34g, 1 mmol) in methanol (10 ml)
was added to this solution and the precipitate deposited after evaporation of a part of
solvent was collected and washed with ethanol and ether.
Found: C, 67,3; H, 7,4; N, 8,7; Ni, 9,4.
Calcd. for NiC35H45N4O2: C, 67,4; H, 7,6; N, 9,0; Ni, 9,4%
Preparation of [Ni(TAA-sal)(H2O)]Cl (2)
To a stirred solution of NiCl2.6H2O (0,36g, 1,5 mmol) in methanol (10 ml) was
added salicylaldehyde (0,16 ml, 1,5 mmol) and after 5 min. tris(2-aminoethyl)amine
(0,28 ml, 1,75 mmol). and triethylamine (0,22 ml, 1,6 mmol). The reaction mixture was
stirred at room temperature owernight and then was left to stand for several days.
After the solution was evaporated nearly to dryness, the pulverized substance was
obtained by stirring in methylcyanide, then it was washed with ethanol and ether.
Found: C, 43,1; H, 6,5; N, 15,1; Ni, 15,9.
Calc. for NiC13H23N4O2Cl: C, 43,1; H, 6,6; N, 15,5; Ni, 16,2%.
Preparation of [Ni(TAA-sal)(H2O)]NO3 (3)
This compound was prepared in a similar way from Ni(NO3)2.6H2O (0,44g, 1,5 mmol)
in methanol (10 ml).
Found: C, 40,4; H, 6,3; N, 17,9; Ni, 14,3.
Calc. for NiC13H23N5O5: C, 40,2; H, 6,0; N, 18,1; Ni, 15,1%.

Results and discussion

On the basis of elemental analyses, the complexes were formulated as Ni(SB)(H2O)X,
where SB = Schiff base and X = Cl, NO3, BPh4. The effective magnetic moments of all
prepared complexes are typical for octahedral Ni(II) complexes and their values are
3,38 BM for (1), 3,09 BM for (2) and 3,22 BM for (3) at 298 K.

The electronic spectra show (Table 1) three distinct bands at ca 10.000 cm-1(3A2g<—3T2g) ,
18.000 cm-1, (3A2g <— 3T1g(F)) and at ca 27.000 cm-1 (3A2g<—3T1g(P)) which are
characteristic for octahedral Ni(II) coordination.

Table 1. Electronic spectral data for the Ni(II) complexes

Complex Band maxima (cm-1)

1 10 600, 12 300 18000 CT

2 11 600, 12 500 18 000 26 800
3 11 600, 12 500 18 000 26 800

The IR spectra of all complexes show characteristic strong band corresponding to

the vibration of C-N at ca 1590 cm-1. The sharp bands at 3280 resp. 3288 cm-1 are
attributed4 to the N-H stretching vibration, the band at 1444 cm-1 is assignated to the
CH2-bending vibration and NH2-twisting vibrations appear at ca 1030 cm-1. The
maxima of middle or strong intensity at 1180 cm-1 or 1196 cm-1 respectively, may be
attributed to NH-wagging vibrations. The band at 828 cm-1 belong to5 anion NO3-. The
frequencies corresponding to acetylacetone vibrations6 are given in Table 2.

Table 2. IR spectra (cm-1) of the prepared compounds

Ni(sal-TAA)Cl Ni(Sal-TAA)(NO3) Ni(acac-TAA)BPh4

3280s 3288s
1652s 1650s
1596s 1592m 1592s
1444s 1444s 1444s
1335s 1336m
1290s 1294m 1290m
1180s 1180m 1196m
1034m 1036m 1025s
914m 916m 924m

The ionic character of NO3 group was confirmed by measurement of the molar
conductivity. The value of 90,85 S.cm2.mol-1obtained for Ni(TAA-sal)(H2O)(NO3) in
5.10 M-4 solution in methanol is typical7 for 1:1 electrolyte. Analogical, the value of
87,7 S.cm2.mol-1 for Ni(TAA-sal)(H2O)Cl is characteristic for 1:1 electrolyte.

The thermal analysis of Ni(TAA-sal)(H2O)NO3 shows that the compound starts its
decomposition at 110oC losing its water molecule in an endotherming proces (weight
loss: exp. 6,3, th. 4,7%). The anhydrous salt is relatively stable from 165 up to 220 oC,
above this temperature the thermal decomposition continued in one step. A constant
mass is achieved at 380oC, at which temperature the weight of residue was in accord-
ance with this calculated for NiO (NiO was identified by X-ray powder diffraction
pattern). The thermal decomposition of all three compounds is quite similar with the
start at 106oC for chloride (anhydrous salt is stable from 165 up to 225oC), and at
130oC for tetraphenylboronate, respective.
Consequently, based on the composition of these complexes and on the results of
physico-chemical methods, we can concluded that these compounds are octahedral
nickel(II) complexes with Schiff bases obtained by template reaction from (1:1)
tris(aminoethyl)amine and salicylaldehyde or acetylacetone.

1. Guerrieo, P., Tamburini, S., Vigato, P. A.: Coord. Chem. Rev. 139, 17 (1995).
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3. Boudreaux, E. A., Mulay, L.N.: Theory and Application of Molecular Paramagnetism, Wiley, N. York
4. Buckingham, D. A., Jones. D.: Inorg. Chem. 4, 1387 (1965).
5. Hart, F. A., Laming, F. P.: J. Inorg. Nucl. Chem. 27, 1605 (1965).
6. Gmelins Handbuch der Anorganischen Chemie, Nickel, Teil C, Lieferung 2, p. 514, Verlag Chemie
GMBH, Weinheim (1969).
7. Geary, W. J.: Coord. Chem. Rev. 7, 81 (1971).