ACTA UNIVERSITATIS PALACKIANAE OLOMUCENSIS

FACULTAS RERUM NATURALIUM 1998 CHEMICA 37

Mixed ligand nickel complexes involving derivatives

of tetrahydroisoquinoline and phenethylamine

Pavel Kopel,1 Roman Štarha2 and Zdeněk Šindelář1

1
Department of Inorganic and Physical Chemistry, Palacký University, Křížkovského 10,
771 47 Olomouc, Czech Republic; e-mail: kopel@risc.upol.cz, sindelar@risc.upol.cz
2
Department of Chemistry, University of Ostrava, Bráfova 7, 701 03, Ostrava, Czech
Republic; e-mail: starha@prf1.osu.cz
Received May 31, 1998

Abstract
Nickel(II) complexes based on combination of N-N ligands with 6,7-dimethoxy-
1,2,3,4-tetrahydroisoquinoline (6,7-THIQ) or 3,4-dimethoxyphenethylamine (3,4-PHA)
of composition Ni(phen)(6,7-THIQ)Cl2.3H2O, Ni(bpy)(6,7-THIQ)Cl2.2H2O, Ni(en)(6,7-
THIQ)Cl2.2H2O, Ni(nphen)(6,7-THIQ)Cl2.3H2O, Ni(phen)(3,4-PHA)2Cl2.H2O and
Ni(bpy)(3,4-PHA)2Cl2.H2O, where phen = 1,10-phenanthroline, bpy = 2,2’ -bipyridine,
en = ethylenediamine and nphen = 5-nitro-1,10-phenanthroline, have been prepared
and characterized by elemental analyses, conductivity and magnetochemical measure-
ments, IR and UV-VIS spectroscopies. From the obtained data we suggest deformed
octahedral arrangement about nickel center with one chloride coordinated to nickel
and the other one is situated out of coordination sphere.

Key words: Nickel(II), 6,7-dimethoxy-1,2,3,4-tetrahydroisoquinoline, 3,4-dimethoxy-

phenethylamine, complex

Introduction
Many cactuses contain tetrahydroisoquinolines together with derivatives of
phenethylamines. Phenethylamine is a precursor for formation of tetrahydroisoquinoline
alkaloids. Among cactuses containing many alkaloids belong Lophophora williamsii.
This cactus is well known, primarily because of its amount of the halucinogenic
alkaloid mescaline 1. These types of alkaloids are the subject of research because of
their potential use in medicine in treatment of many kinds of diseases and it is highly
important to know how they can be bonded in live organisms.

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 Phenethylamine and its derivatives were used for preparation of Schiff bases and
these were used for preparation of complexes. Complexes NiL2, CuL2 and CoL3, where
HL = Schiff base derived from acetylacetone or benzoylacetone and phenethylamine,
were synthesized and characterized by Abdul Samath et al 2. Tetrahedral geometry for
Cu(II) and Ni(II) and the meridional octahedral geometry for Co(III) are suggested.
Preparation of square-planar bis(N-salicylidenephenethylamine)nickel(II) complex
and kinetics of ligand substitution by N,N’-bis(salicylidene)ethylenediamine in ac-
etone is reported in 3. Kinetics and mechanism of substitution in trans-
dichlorobis(ethylenediamine)cobalt(III) chloride by organic amines including
phenylethylamine in MeOH-DMF solution was studied by Paulraj et al4.
Phenethylamine, mescaline and N-methylphenethylamine were employed as ligands
for copper(II) complexes in 5,6.
These complexes were prepared as models which might correspond to the com-
plexes formed with hallucinogenic drugs in vivo. Phenethylamine was also used for
preparation of dithiocarbamate 7. The authors used a direct reaction of amine and CS2,
followed by the reaction with metal chloride or acetate to obtain Cu(II), Ni(II) and
Pd(II) complexes. These dithiocarbamates show optical activity.

Experimental
Chemicals and solvents were purchased from Aldrich and Lachema except for the
methoxy derivatives of tetrahydroisoquinoline and phenethylamine. These were pre-
pared according to literature 8,9.
C, H, N elemental analyses were performed on an EA 1108 instrument (Fisons
Instruments). IR spectra were recorded on a Specord M 80 (Carl Zeiss, Jena) spectro-
photometer in Nujol mulls. Diffusion-reflection spectra were obtained on a Specord
M 40. The magnetic susceptibilities were measured at 296 K using the Faraday method
on a magnetic device designed by Z. Šindelář. Hg[Co(SCN)4] was used as a calibrant.
The correction for diamagnetism was calculated using Pascal’s constants. Conductivi-
ties were measured on a conductivity meter OK - 102/1 (Radelkis, Hungary).

General preparation of Ni(N-N)(6,7-THIQ)Cl2.nH2O

N-N ligand (0.5 mmol) was added to a solution of NiCl2.6H2O (0.5 mmol) in water-
ethanol (1:1). The solution was boiled and after its cooling 6,7-THIQ (0.5 mmol) in
5 ml of ethanol was added. After standing for two weeks the resulting glassy product or
thick solution was treated with acetone and diethylether to get hygroscopic powder.
The product was stored in desiccator over KOH.

Preparation of Ni(phen)(3,4-PHA)2Cl2.H2O and Ni(bpy)(3,4-PHA)2Cl2.H2O

Phen or bpy (0.55 mmol) in 10 ml of ethanol was added to a solution of NiCl2.6H2O
(0.5 mmol) in water (10 ml). The solution was then boiled over a few minutes and after
cooling 3,4-PHA (1.1 mmol) in 5 ml of ethanol was added. After a week the glassy
product was treated with small amounts of ethanol and finally with diethylether. The
obtained powders were stored in dessicator over KOH.

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Results and discussion
Composition of complexes and results of physico-chemical measurements are listed
in Table 1. The vibrations found in IR spectra and their intensities are given in Table 2.

Table 1. Analytical data, molar conductivity, diffuse – reflectance spectra, color and magnetic moments
_____________________________________________________________________________________________________________________

Compound Found(Calcd.) % meff lM nmax color

C H N Cl (B.M.) (S.cm2.mol-1) x 103 (cm-1)
______________________________________________________________________________________________________________________

Ni(phen)(6,7-THIQ)Cl2.3H2O 49.5 5.2 7.3 12.2 3.26 77 16.0, 26.0 green

(49.8) (4.5) (7.6) (12.8) 29.0

Ni(bpy)(6,7-THIQ)Cl2.2H2O 48.9 5.2 8.2 12.7 3.35 70 26.0, 29.0 green

(49.2) (4.9) (8.2) (13.8) 32.0

Ni(en)(6,7-THIQ)Cl2.2H2O 37.0 6.5 10.5 16.2 3.53 70 16.0, 25.5 green

(37.5) (6.0) (10.1) (17.0) 29.0, 32.5

Ni(nphen)(6,7-THIQ)Cl2.3H2O 46.3 4.5 9.2 11.6 3.47 66 16.0, 26.0 brown

(46.0) (4.4) (9.3) (11.8) 29.0, 31.5

Ni(phen)(3,4-PHA)2Cl2.H2O 55.8 6.1 7.3 8.7 2.91 66 16.5, 26.0 yellow-

(55.7) (5.8) (8.1) (10.3) 29.0 brown

Ni(bpy)(3,4-PHA)2Cl2.H2O 54.7 6.4 7.6 9.8 2.66 48 15.5, 25.0 yellow-

(54.1) (6.1) (8.4) (10.6) brown
________________________________________________________________________________________________________________________

Table 2. Infrared spectra of the complexes

_____________________________________________________________________________________________________________________

Compound
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Ni(phen)(6,7-THIQ)Cl2.3H2O 1720(w), 1624(w), 1604(m), 1518(vs), 1444(s), 1426(s), 1378(m), 1264(m),

1226(m), 1122(m), 1018(w), 850(s), 784(w), 726(vs), 644(w), 422(w)
Ni(bpy)(6,7-THIQ)Cl2.2H2O 1628(w), 1598(s), 1562(m), 1510(vs), 1432(s), 1368(s), 1312(m), 1260(m),
1226(m), 1120(m), 1058(w), 1018(m), 768(vs), 736(vs), 652(w), 632(w),
416(m)
Ni(en)(6,7-THIQ)Cl2.2H2O 1592(w), 1510(vs), 1416(s), 1328(m), 1260(m), 1220(m), 1120(m),
1016(m), 864(w), 668(m), 610(w), 504(m), 430(w)
Ni(nphen)(6,7-THIQ)Cl2.3H2O 1650(m), 1600(w), 1510(vs), 1414(vs), 1328(s), 1224(sh), 1120(m),
1016(m), 904(w), 836(m), 814(w), 750(w), 690(w), 640(w), 420(m)
Ni(phen)(3,4-PHA)2Cl2.H2O 1624(w), 1588(m), 1510(w), 1438(vs), 1372(vs), 1262(m), 1230(w),
1142(m), 1020(m), 846(m), 764(w), 724(vs), 638(w), 422(w)
Ni(bpy)(3,4-PHA)2Cl2.H2O 1596(m), 1510(s), 1438(vs), 1262(m), 1232(m), 1142(m), 1020(m), 854(w),
808(w), 764(s), 724(vs), 632(w), 416(w)
________________________________________________________________________________________________________________________

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 The bands corresponding to the symmetric and antisymmetric stretching of the
amino-group and those corresponding to the imino-groups of free ligands are mainly
shifted to lower energies on coordination. The aromatic carbon-nitrogen stretch
vibration appears between 1335–1250 cm-1 and can be found in the spectra of all the
complexes. The peaks near 1615 cm-1, in the spectra of Ni(phen)(3,4-PHA)2Cl2.H2O
and Ni(bpy)(3,4-PHA)2Cl2.H2O, can be attributed to the ring band which also overlaps
with NH2 deformation band. Antisymmetric vibration of NO2 group in Ni(nphen)(6,7-
THIQ)Cl2.3H2O lies probably at 1650 cm-1. Symmetric vibration of NO2 group which
should occur in 1390 - 1280 cm-1 region can not be assorted, since in the spectra of all
complexes the peaks in the region are nearly identical 10,11. In general, we can not
expect to obtain much information from IR spectra as the complexes contain similar
ligands and do not differ in, for example, content of any other characteristic group.
Diffuse – reflectance spectra of the all complexes are very similar to each other. If
we assume the complexes are deformed octahedral then one set of d-d bands observed
at 15500–16500 cm-1 can be attributed to [3A2g ® 3T1g(F)] transition, the second one at
25000–26000 cm-1 can belong to [3A2g ® 3T1g(P)] transition. The d-d bands of third
transition [3A2g ® 3T2g] were not observed within the studied range. The bands at
29000 cm-1 and near 32000 cm-1 can be assigned to CT or p - p* transition 12.
The magnetic moments of the Ni(II) complexes (see Table 1) vary in the range of
3.26 - 3.53 B.M. for complexes involving 6,7-dimethoxy-1,2,3,4-tetrahydroisoquinoline.
The spin only value of magnetic moment for a d8 ion is 2.83 B.M. and higher values are
due to orbital contribution to the magnetic moment. The calculated values lie within
the range or somewhat higher then those found for octahedral Ni(II) complexes. The
explanation might be as follows: a) the complexes are deformed octahedral and we can
not exclude the presence of paramagnetic impurities, b) complexes are penta-coordi-
nated with probably trigonal bipyramidal stereochemistry due to bulkiness of the
ligand. 3,4-dimethoxyphenethylamine complexes have the calculated magnetic mo-
ments equal to 2.66 and 2.91 B.M., respectively. The values are typical of octahedrally
coordinated Ni(II) and lower value can be caused by hygroscopic properties of the
complex 13,14.
From conductivity measurements, performed in dimethylformamide, it follows that
the complexes behave as uni-univalent electrolytes 15. Somewhat lower conductivity
value measured for Ni(bpy)(3,4-PHA)2Cl2.H2O was probably caused by incomplete
solubility of the sample in DMF. We can conclude from the measurement, that one
chloride anion is bound to nickel center and the second one is situated out of
coordination sphere.
On the base of physico-chemical measurements we propose deformed octahedral
stereochemistry for the complexes, although the number five coordination, in the case
of tetrahydroquinoline complexes, can not be completely ruled out. Hypothetic mo-
lecular structures of two complexes are depicted in Figures 1. and 2. All our attempts
to prepare monocrystals suitable for X-ray analyses unfortunately failed. Therefore
the structure could not have been confirmed by this direct method.

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Figure 1. The proposed molecular structure of [Ni(phen)(6,7-THIQ)(H2O)2Cl]+

Figure 2. The proposed molecular structure of [Ni(bpy)(3,4-PHA)2(H2O)Cl]+

15
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