Studies on nickel(II) and palladium(II) complexes with some tetraazamacrocycles containing tellurium

Article abstract of DOI:10.2298/JSC101211200R

The synthesis of 10-membered and 12-membered tellurium-containing tetraazamacrocyclic complexes of divalent nickel and palladium by template condensation of diaryltellurium dichlorides, (aryl = p-hydroxyphenyl, 4-hydroxy-3-methyl-phenyl, p-methoxyphenyl)

Full text of DOI:10.2298/JSC101211200R

J. Serb. Chem. Soc. 76 (0) 1–14 (2011)
UDC
JSCS–4958
Original scientific paper
Studies on nickel (II) and palladium (II) complexes with some
tetraazamacrocycles containing tellurium
NITU RATHEE and KRISHAN KUMAR VERMA*
Department of Chemistry, Maharshi Dayanand University, Rohtak – 124001, Haryana, India
(
Received 11 December 2010, revised 13 July 2011)
Abstract: The synthesis of 10-membered and 12-membered tellurium
containing tetraazamacrocyclic complexes of divalent nickel and palladium by
template condensation of diaryltellurium dichlorides, (aryl = p-hydroxyphenyl,
3
1
-methyl-4-hydroxyphenyl, p-methoxyphenyl) with 1,2-diaminoethane and
,3-diaminopropane in the presence of metal dichloride is reported. The
resulting complexes have been subjected to elemental analyses, magnetic
measurements, electronic absorption, infra-red, and proton magnetic resonance
spectral studies. The formation of proposed macrocyclic skeletons and their
donor sites have been identified on the basis of spectral studies. Distorted
octahedral structure for the nickel complexes in the solid state and square-
planar structure for the palladium complexes have been suggested.
Keywords: tetraazamacrocycles; diaryltellurium dichlorides; template
condensation; ethylenediamine; 1,3-diaminopropane.
INTRODUCTION
The coordination chemistry of organotellurium ligands containing hard
donor atoms such as nitrogen and oxygen along with soft tellurium is interesting
as such ligand framework can provide ‘insight’ into competitive coordination
1
,2
behavior between the hard and soft donors towards a metal center. Such
molecular systems may be important in transition metal catalyzed asymmetric
3
,4
5-7
synthesis, and as single source precursors in MOCVD processes. Also,
macrocycle complexes are significant as they have been found to act as possible
8
-12
models for biochemically important proteins and enzymes.
Some recent publications
containing macrocycles. Srivastava et al reported the route of synthesis of metal
1
3-15
exhibit the development of tellurium
1
6
complexes with tellurium containing macrocycles. In continuation of our earlier
17,18
work,
we herein report the synthesis and characterization of divalent nickel
*
Corresponding author. E-mail: vermakk123@rediffmail.com
doi: 10.2298/JSC101211200R
1

2
RATHEE and VERMA
and palladium complexes with six novel tellurium tetraazamacrocycles (Te
system).
2
N
4
RESULTS AND DISCUSSION
The formation of diaryltellurium(IV) dichlorides by the reactions of TeCl
4
19
20
21
with phenol, o-cresol and anisole involves two step reactions. In first step,
there is an electrophilic substitution of the phenyl ring by a trichlorotellurium
moiety at a position para to the hydroxyl or the methoxy groups. This can be
represented by the following equation :
R-H + TeCl
R = p-hydroxy, p-methoxy or 3-methyl-4-hydroxyphenyl ).
These aryltellurium trichlorides, further react with phenol/o-cresol or anisole
4
→ RTeCl
3
+ HCl
(1)
(
to give the diaryltellurium(IV) dichlorides as per equation below:
RTeCl + R-H → R TeCl + HCl
(2)
3
2
2
These diaryltellurium dichlorides when refluxed with 1, 2-diaminoethane or
, 3-diaminopropane in presence of NiCl /PdCl in 2: 2:1 molar ratios yield the
0-membered and 12-membered tetraazamacrocyclic complexes respectively, as
1
1
2
2
shown in Scheme - 1.
These complexes are colored, crystalline solids, fairly stable in dry air, and
are soluble only in polar donor organic solvents.
Infra-red spectra
The important IR bands and their assignments are reported in Table I. The
spectra are quite complex and an attempt has thus been made to draw the
conclusions by comparing the spectra of metal complexes with those of
corresponding constituent diarytellurium dichlorides and diaminoalkanes.
The metal complexes under study did not show bands characteristics of free
2
NH group, instead the entire complexes exhibit a single sharp absorption band at
-
1
around 3180-3250 cm (sometimes mixed with O-H) attributed to ν
N−H
vibrations. The assignment of this sharp band is based on the fact that
macrocyclic ligands which have coordinated secondary amino group, have
1
8,22-24
-1
22
bands
in the vicinity of 3200 cm . This contention finds support from
-
1
appearance of bands of medium to strong intensity at 1627-1655 cm and 809-
27 cm assigned as N-H deformation coupled with N-H out of the plane
bending vibrations. Bands at 1156-1185 cm may be reasonably assigned to C-N
stretching vibration.
-
1
8
-
1
1
8,25,26
18,22,25,26
The above observation strongly suggests
that
proposed macrocyclic framework is formed. The formation of tellurium
containing macrocyclic ring is supported by appearance of new weak intensity
-
1
18,27
bands around 420-410 cm due to Te-N.
Evidence for the formation of
proposed macrocycles and coordination through N atoms is further supported by
-
1
new medium to weak intensity bands around 480-450 cm assignable to Ni-N

TELLURIUM CONTAINING TETRAAZAMACROCYCLIC METAL COMPLEXES
3
28
stretching. The M-Cl and Pd-N vibrations could not be ascertained due to non-
availability of the far-infrared data.
Proton magnetic resonance spectra
The proton chemical shifts for metal complexes with 10-membered and 12-
membered tetraazamacrocycles which are soluble in DMSO-d
Tables II and III, respectively.
6
are presented in
The phenyl protons in metal complexes resonate at slightly upfield side
1
9,20,29
(
6.89-7.88 δ ppm) as compared to parent diaryltellurium dichlorides
due to
an increase in electron density at the tellurium atom as a result of replacement of
(
a)
(b)
(a)
3
0
2
Cl by 2 N atoms. Ethylenediamine, H N− (CH ) − NH shows two sets
2
2
2
2
of four equivalent protons each at (a) = 1.19 δ ppm and (b) = 2.74 δ ppm .Metal
complexes do not show any signal attributable to free – NH , instead a broad
2
singlet at around 1.74-2.04 δ ppm, which may be assigned to coordinated
31
secondary amino group is observed. This confirms the formation of proposed
1
0-membered macrocycle skeleton. The deshielding of –NH– protons further
suggests the donation of electron density to the metal-ions. The methylene
protons in these metal complexes resonate at 2.17-2.50 δ ppm, as a multiplet as
1
8,24,26
reported
for other tetraazamacrocyles derived from ethylenediamine.
32
1
,3-Diaminopropane,
NH
2
-CH
2
-CH
2
-CH
2
-NH
2
,
exhibits
protons
resonances at 1.15 (4H), 2.76 (4H) and 1.59 (2H) δ ppm due to amino,
methylene (adjacent to N) and middle methylene groups, respectively. The metal
complexes do not show any signal due to free amino group. Instead, a broad
3
1
singlet at 1.78-1.91 δ ppm assignable to coordinated secondary amino group
confirms the formation of 12-membered tellurium containing
tetraazamacrocycles skeleton. The middle methylene protons and those adjacent
to N-atoms resonate at 2.01 -2.50 and 2.86 -3.33 δ ppm, respectively. This
behavior of complexes under study is quite similar to those of other
18,24,33
tetraazamacrocycles
derived from 1, 3-diaminopropane.
Further, the independence of aryl proton chemical shifts on the nature of
metal- ions precludes the possibility of Te-M bond. The proton magnetic
resonance studies on these Ni(II) and Pd(II) complexes support the tetra dentate
nature of these ligands through four N-atoms as predicted by infrared studies.
Electronic absorption spectra and magnetic studies
The electronic absorption and magnetic moment data for the complexes are
presented in Table IV.
The electronic spectral data of all the six Ni(II) complexes exhibit three spin
3
3
3
3
allowed transitions from A → T , T (F), and T (P) which appear at 9850-
2
g
-1
2g
1g
1g
-
1
-1
1
0700 cm , 13600-15052 cm and 24096-28668 cm , respectively. This spectral
pattern corresponds to a octahedral/distorted octahedral geometry
16,34
Also, the

4
RATHEE and VERMA
3
6,37
ratio of ν
2
/ ν
1
̴
1.4 is an indicative
of an octahedral stereochemistry for all
these Ni(II) complexes. The third spin allowed d-d transitions appears as broad
shoulder to the CT bands and extends up to 450 nm as reported for other
tetraazamacrocyclic complexes of Ni(II). The magnetic moment values in present
3
8
Ni(II) complexes (2.90 - 3.44 μ ) also suggest an octahedral stereochemistry for
B
39,40
these complexes and rules out the possibility of square planer geometry.
Pd(II) complexes under study display two bands at 20829-24752 cm and 26900-
8800 cm which may be assigned to A1g → A2g, and A1g → B1g. These
transitions in Pd (II) complexes establish square planer coordination around
The
-
1
-
1
1
1
1
1
2
3
4,41
palladium.
This is further supported by their diamagnetic nature.
On the basis of above studies, nickel appears to be hexa coordinated
especially in the solid state, presumably in a distorted octahedral fashion
involving four N atoms of tetraazamacrocycles and two chlorine atoms, whereas
palladium is tetra coordinated in a square- planar arrangement involving four N
atoms of the macrocyclic ring. However, the proton magnetic resonance spectral
4
2
pattern of nickel complexes also indicates the presence of diamagnetic square-
planar configuration. Probably in solution, dissociation of chloride anions takes
place and nickel (II) complexes form equilibrium of octahedral (paramagnetic)
and square-planar (diamagnetic) species.
EXPERIMENTAL
All preparations were carried out under an atmosphere of dry N and the solvents were
2
dried and purified by the standard methods before use.
Preparation of diaryltellurium dichlorides
The bis(p-hydroxyphenyl), bis(3-methyl-4hydroxyphenyl), and bis(p-methoxyphenyl)
tellurium dichlorides were prepared by the rections of tellurium tetrachloride with phenol,
19-21
o-cresol, and anisole, respectively.
Synthesis of metal complexes with tellurium containing 10-membered and 12-membered
tetraazamacrocycles
The complexes were prepared by template condensation of diaryltellurium dichlorides
with diaminoalkanes in presence of metal dichlorides in 2: 2: 1 molar ratio. A general
procedure is given below.
A saturated methanolic solution of 4.0 mmol of diaryltellurium dichloride [1.538 g,
1
.650 g, 1.650 g for bis(p-hydroxyphenyl), bis(3-methyl-4hydroxyphenyl) and bis(p-
methoxyphenyl) tellurium dichlorides, respectively] was added to ethylenediamine ( 0.240 g,
.0 mmol ) or 1,3-diaminopropane ( 0.296 g, 4.0 mmol ) in about 10 mL dry methanol with
4
constant stirring. An immediate change in color was observed along with a little turbidity. The
contents were stirred and refluxed for about 3 h. This was followed by addition of a solution
of 2.0 mmol of metal dichloride ( 0.575 g, 0.355 g for NiCl .6H O and PdCl , respectively )
2 2 2
in about 10 mL methanol. This resulted in a distinct change in color along with slight
precipitation of a solid product. The solution was then refluxed for about 6 h and then cooled.
A small amount of colored solid thus separated was filtered and the filtrate was concentrated
to about one third of its original volume and kept in a freeze overnight to get the second crop

TELLURIUM CONTAINING TETRAAZAMACROCYCLIC METAL COMPLEXES
5
of the crystalline product. This was filtered and washed with benzene and dried in a vacuum
desiccator over P
4
10
O .
The purity of these compounds was checked by T.L.C using silica gel – G. The
analytical data and physical properties of the complexes are presented in Table V.
Analytical methods and physical measurements
Carbon, hydrogen, and nitrogen analyses were obtained micro analytically from
Sophisticated Analytical Instrumentation Facility, Panjab University, Chandigarh. The
4
3
tellurium and chlorine contents were determined volumetrically
and palladium
4
3
gravimetrically. Nickel was estimated Atomic Absorption Spectrophotometerically. IR
spectra were recorded in the region 4000-400 cm at SAIF, Panjab University, Chandigarh on
a Perkin Elmer Model 2000 FTIR Spectrometer using the KBr pellets technique. H NMR
-1
1
spectra were recorded at Kurukshetra University, Kurukshetra on BRUKER XWIN – NMR
AVANCE 300 operating at 300.13 MHz in DMSO – d using tetramethylsilane as an internal
6
reference. The magnetic susceptibility data were obtained from National Physical Laboratory,
New Delhi on a Gouy’s balance (Model Johnson Matthey Alfa Products) using glycerin as a
caliberant. The electronic spectra were recorded in dimethylsulphoxide on a Thermo
Spectronic UV-1 UV-VISIBLE Spectrophotometer (Electron Corporation, India).
CONCLUSIONS
Nickel (II) and palladium (II) complexes have been prepared by
condensation of diaryltellurium dichlorides with diaminoalkanes in the presence
of metal chlorides. These metal complexes have been characterized using
elemental analyses, magnetic measurements, electronic absorption, infra-red and
proton magnetic resonance spectral techniques. A distorted octahedral structure
for the Ni (II) complexes in the solid state and a square- planer structure for the
Pd (II) complexes have been assigned on the basis of these studies. The Ni (II)
complexes in solution probably form equilibrium of octahedral and square-planar
species.
Acknowledgments. The authors are thankful to Maharshi Dayanand University, Rohtak,
India for providing the necessary facilities.
И З В О Д
ИСПИТИВАЊЕ КОМПЛЕКСА НИКЛА(II) И ПАЛАДИЈУМА(II) СА НЕКИМ
ТЕРААЗАМАКРОЦИКЛИЧНИМ ЛИГАНДИМА КОЈИ САДРЖЕ ТЕЛУР
NITU RATHEE и KRISHAN KUMAR VERMA
Department of Chemistry, Maharshi Dayanand University, Rohtak – 124001, Haryana, India
Темплаттном кондензационом реакцијом полазећи од диарилтелур-дихлорида (арил =
p-парахидроксифенил, 3-метил-4-хидроксифенил, p-метоксифенил) и 1,2-диаминоетана и
1
,3-диаминопропана
у
присуству одговарајућег хлорида метала (Ni(II)
и
Pd(II))
синтетизовани су комплекси никла(II) и паладијума(II) са десеточланим и дванаесточланим
тетраазамакроцикличним лигандима који садрже телур. Синтетисани комплекси су
окарактерисани на основу резултата елементалне микроанализе, магнетних мерења, UV–Vis,
1
IR и H-NMR спектара. Грађење макроцикличног скелета са одговарајућим донорским
атомима је праћено на основу спектроскопских мерења. На основу ових резултата је нађено

6
RATHEE and VERMA
да комплекси никла(II) имају дисторговану окатедарску, док комплекси паладијума(II) имају
квадратно-планарну геометрију.
(
Примљено 11. децембра 2010, ревидирано 13. јула 2011)
REFERENCES
1
2
3
.
.
.
P. G. Jones, M. Carman, R. D. Arellano, J. Chem. Soc. Dalton Trans. (1996) 2713
C. O. Kienitz, C. Thone, P. G. Jones, Inorg. Chem. 35 (1996) 3990
Y. Nishibayashi, K. Segawa, J. D. Singh, S. I. Fukuzawa, K. Ohe, S. Uemura,
Organometallics 15 (1996) 370
4
.
Y. Nishibayashi, J. D. Singh, Y. Arikawa, S. Uemura, M. Hidai, J. Organometal. Chem.
5
31 (1997) 13
5
6
7
.
.
.
Y. Chang, T. Emge, J. G. Brennan, Inorg. Chem. 35 (1996) 7339
M. L. Steigerwald, C. R. Sprinkle, J. Am. Chem. Soc. 109 (1987) 7200
W. Hirpo, S. Dhingra, A. C. Sutorik, M. G. Kanatzidis, J. Am. Chem. Soc. 115 (1993)
1
597
8
9
1
.
.
R. R. Gagne, J. L. Allison, R. S. Gall, C. A. Koval, J. Am. Chem. Soc. 99 (1977) 7170
J. W. L. Martin, J. H. Johnson, N. F. Curtis, J. Chem. Soc. Dalton Trans. (1978) 68
nd
0. M. N.Hughes, Inorganic Chemistry of Biological Processes, 2 ed., Wiley, New York,
1
981
1
1. L. Casella, M. Gullotii, L. D. Gioia, M. Monzani, F. Chillemi, J. Chem. Soc. Dalton
Trans. (1991) 2945
1
1
1
1
1
1
1
1
2
2. S. R. James, D. W. Margerum, Inorg. Chem. 19 (1980) 2784
3. W. Levason, S. D. Orchard, G. Reid, Coord. Chem. Rev. 225 (2002) 159
4. A. K. Singh, S. Sharma, Coord. Chem. Rev. 209 (2000) 49
5. A. Panda, Coord. Chem. Rev. 253 (2009) 1947
6. S. Srivastava, A. Kalam, J. Indian Chem. Soc. 83 (2006) 563
7. Nitu, K. K. Verma, J. Chem. Pharm. Res. 2(4) (2010) 793
8. Nitu, K. K. Verma, Int. J. Chem. Sci., 9(1) (2011) 229
9. B. L. Khandelwal, K. Kumar, F. J. Berry, Inorg. Chim. Acta 47 (1981) 135
0. B. L. Khandelwal, K. Kumar, K. Raina, Synth. React. Inorg. Met.-Org. Chem. 11 (1981)
6
5
2
2
2
2
2
1. J. Bergman, Tetrahedron 28 (1972) 3323
2. V. B. Rana, P. Singh, D. P. Singh, M. P. Teotia, Polyhedron 1 (1982) 377
3. D. A. House, N. F. Curtis, J. Am. Chem. Soc. 86 (1964) 1331
4. M. Shakir, S. P. Varkey, P. S. Hameed, Polyhedron 13 (1994) 1355
5. A. K. Panda, A. Panda, S. Sutar, P. Mishra, S. Pradhan, S. Ghos, S. Pany, J. Indian
Chem. Soc. 86 (2009) 908
2
2
2
6. S. Srivastava, A. Kalam, Synth. React. Inorg. Met. – Org. Chem. 34 (2004) 1529
7. Y. D. Kulkarni, S. Srivastava, Indian J. Chem. 24A (1985) 429
8. K. Nakamoto, Infrared and Raman Spectra of Inorganic and Coordination Compounds,
th
Part-B 5 ed., John Wiley and Sons, New York, 1997, p. 15
2
3
9. K. Raina, B. L. Khandelwal, Indian J. Chem. 14A (1976) 63
0. Academic Press Hand Book Series – Hand Book of Proton NMR Spectra and Data,
Edited by Asani Research Centre Vol. 1, p. 47
3
1. S. C. Menon, H. B. Singh, R. P. Patel, S. K. Kulshreshtha, J. Chem. Soc., Dalton Trans.
(
1996) 1203

TELLURIUM CONTAINING TETRAAZAMACROCYCLIC METAL COMPLEXES
7
3
3
3
3
2. K. Kawakami, M. Miya – Uchi, T. Tanaka, J. Inorg. Nucl. Chem. 33 (1971) 3773
3. M. G. B. Drew, F. S. Esho, S. M. Nelson, J. Chem. Soc. Dalton Trans. (1983) 1653
4. A. B. P. Lever, Inorganic Electronic Spectroscopy Elsevier, Amsterdam, 1968
5. T. M. Dunn, in Modern Coordination Chemistry, J. Lewis and R. G. Wilkins (Eds.),
Interscience, New York, 1960, p. 230
3
3
3
3
4
4
4
4
6. K. Abe, K. Matsufuji, M. Ohba, H. Okawa, Inorg. Chem. 41 (2002) 4461
7. M. J. M
Campbell, R. Grzeskowiak, J. Chem. Soc. A (1967) 396
8. S. Chandra, K. Gupta, S. Sharma, Synth. React. Inorg. Met. - Org. Chem. 31 (2000) 1205
9. M. L. Dianu, A. Kriza, N. Stanica, A. M. Musuc, J. Serb. Chem. Soc. 75 (2010) 1515
0. Y. Baran, L. Yilmaz, Trans. Met. Chem. 26 (2001) 36
1. S. Chandra, S. Verma, P. Meera, J. Indian Chem. Soc. 85 (2008) 896
2. A. Dei, Inorg. Chem. 18 (1979) 891
3. A. I. Vogel, A Text Book of Quantitative Inorganic Analysis Including Elementary
rd
Instrumental Analysis, 3 ed., Longman, London, 1975, pp. 266, 324, 511.

8
RATHEE and VERMA
TABLES CAPTIONS
-
1
TABLE I. . Important IR data (cm ) for metal complexes
1
TABLE II. H NMR data (δ ppm) for 10-membered macrocyclic metal
complexes in DMSO–d
6
1
TABLE III. H NMR data (δ ppm) for 12-membered macrocyclic metal
complexes in DMSO –d6
TABLE IV. Electronic absorption spectra and magnetic moment data for
metal complexes
TABLE V. Physical characteristics and elemental analysis of metal
complexes
-1
TABLE I. Important IR data (cm ) for metal complexes
N-H out of
plane bending
825 s
812 s
819 vs
827 s
Complex
νN−H
3180 m
3191 m
3210 m
3250 m
N-H def.
νC−N
1185 m
1176 m
1176 vs
1173 s
1
[
[
[
[
NiL Cl
2
2
2
]
]
]
1630 m
1640 m
1649 m
1635 m
2
NiL Cl
3
NiL Cl
4
NiL Cl ]
2
5
1630
[
NiL Cl ]
3250 m
813 s
1178 m
2
m
6
[
[
[
[
[
[
[
NiL Cl ]
3215 m
3210 m
3180 m
3230 m
3190 s
1645 m
1640 m
1635 m
1650 m
1630 m
1627 m
1655 m
822 s
824 vs
809 vs
816 s
825 m
809 s
822 s
1176 vs
1172 s
1173 m
1176 s
2
1
PdL ]Cl
2
2
PdL ]Cl
2
2
2
2
2
3
PdL ]Cl
4
PdL ]Cl
1156 vs
5
PdL ]Cl
3210 m
3210 m
1172 m
6
PdL ]Cl
1177 vs
*
mixed with moisture band, s = strong, m = medium, vs = very strong.

TELLURIUM CONTAINING TETRAAZAMACROCYCLIC METAL COMPLEXES
9
1
TABLE II. H NMR data (δ ppm) for 10-membered macrocyclic metal
complexes in DMSO – d
6
2
–CH –
Complex
–NH–
–OCH
3
Phenyl
–OH
d
6
.93 (J = 8.7 Hz,
s
1
1.45 (4H)
m
8H)
b
[
[
[
NiL Cl
2
]
2.17 (8H)
_
d
9.85 (4H)
7
8
6
.83 (J = 8.7 Hz,
H)
.91 (J = 8.7 Hz,
d
1
s
m
8H)
b
PdL ]Cl
2
1.40 (4H) 2.50 (8H) _
d
8.35 (4H)
7
.74 (J = 8.7 Hz,
8
7
H)
d
.11 (J = 8.4 Hz
3
s
m
s
,8H)
PdL ]Cl
1.75 (4H) 2.50 (8H) 3.78 (12H)
d
_
2
7
.87 (J = 8.4 Hz,
8
H)
s = singlet, d = doublet, m = multiplet, b = broad
1
TABLE III. H NMR data (δ ppm) for 12-membered macrocyclic metal
complexes in DMSO – d
6
–
CH
2
–
*
3
–
CH
2
–
− CH
Complex –NH–
s
(adjacent to
N)
–OCH
3
Phenyl
–OH
(
middle)
d
6.89 (J = 8.7
1
.89
m
b
m
2.86 (8H)
_
_
Hz,8H)
8.63
4
[
NiL Cl
2
] (4H)
2.27 (4H)
d
7
.77 (J = 8.7 (4H)
Hz,8H)
d
6
.92 (J = 8.7
s
m
b
4
1.91
(
2.50
m
_
_
_
Hz,8H)
8.14
[
PdL ]Cl
2
2.88 (8H)
d
4H)
(4H)*
7.74 (J = 8.7 (4H)
Hz,8H)
d
6
.92 (J = 8.4
s
s
Hz,4H)
b
1.91
(
m
m
2.49
(12H)
s
d
8.10
5
[
NiL Cl
2
]
2.06 (4H) 2.90 (8H)
7.34 , 7.64
4H)
(4H)
(
J = 8.4
Hz,8H)
d
6
.89 (J = 8.7
s
s
6
1.78
(
m
m
3.72
Hz,8H)
7.88 (J = 8.7
[
NiL Cl ]
2.01 (4H) 3.33 (8H)
_
d
_
2
4H)
(12H)
Hz,8H)
*
May be mixed with solvent peak, s = singlet, d = doublet, m = multiplet, b = broad.

1
0
RATHEE and VERMA
TABLE IV. Electronic absorption spectra and magnetic moment data for
metal complexes
-
1
Observed
Magnetic
Moment
Absorption, cm
Nickel(II)
Complex
3
3
3
3
3
3
μB
[
A → T
]
[
A → T (F)
]
[
A → T (P)
]
2
g
2g
2g
1g
2g
1g
1
9994
14500
14040
13600
14525
15052
13855
29740
24096
25700
28668
27689
26550
1
3.44
[
[
[
[
[
[
NiL Cl
2
]
2
9850
NiL Cl ]
2.99
3.19
3.10
3.00
2.90
2
3
10100
10700
10428
9941
1
NiL Cl
2
]
4
NiL Cl ]
2
5
NiL Cl ]
2
6
NiL Cl
2
]
Palladium(II)
Complex
1
1
A
1g → A2g
A
1g → B1g
24500∗
21700
24752∗
22026
20829
21100
27737
28490
26815
27600
28800
26900
1
[
[
[
[
[
PdL ]Cl
2
2
2
Diamagnetic
Diamagnetic
Diamagnetic
Diamagnetic
Diamagnetic
Diamagnetic
2
PdL ]Cl
3
PdL ]Cl
4
PdL ]Cl2
5
PdL ]Cl
2
2
6
[
PdL ]Cl
∗
1
1
A
1g → E
g

TELLURIUM CONTAINING TETRAAZAMACROCYCLIC METAL COMPLEXES
11
TABLE V. Physical characteristics and elemental analysis of metal complexes
Elemental analyses found (calculated) %
mp,
Empirical formula
Yield
(%)
Complex
Color ºC
dec.)
(
Formula weight)
C
H
N
Cl
Te
M
(
1
C
28
H
32Cl
2
2
2
2
2
2
2
2
2
2
2
2
N
4
N
4
N
4
N
4
N
4
N
4
N
4
N
4
N
4
N
4
N
4
N
4
O
4
O
4
O
4
O
4
O
4
O
4
O
4
O
4
O
4
O
4
O
4
O
4
Te
Te
Te
Te
Te
Te
Te
Te
Te
Te
Te
Te
2
2
2
2
2
2
2
2
2
2
2
2
Ni
38.15 3.37 6.11 8.15 28.81 6.45
(38.51)(3.69)(6.41)(8.12) (29.22) (6.51)
[
[
[
[
[
[
[
[
[
[
[
[
NiL Cl
2
]
Pink 85-88 70
(
873.4)
2
C
32
H40Cl
Ni Red 145-
brown 147
Ni Light 157-
brown 160
Ni Light 150-
orange 152
Ni Red 135-
brown 138
Ni Light 177-
green 180
Pd Dark 155-
brown 158
Pd
Pd
Pd
40.95 3.87 6.11 7.61 26.71
6.18
NiL Cl ]
81
68
70
78
69
55
68
50
75
66
2
(
929.5)
(41.35)(4.34)(6.03)(7.63) (27.46)(6.31)
41.30 4.44 6.26 7.59 26.97 6.06
(41.35)(4.34)(6.03)(7.63) (27.46)(6.31)
39.52 3.89 5.99 7.85 28.22 6.45
(39.97)(4.03)(6.22)(7.87) (28.31)(6.51)
42.26 4.33 5.37 7.43 26.10 6.04
(42.65)(4.63)(5.85)(7.41) (26.65)(6.13)
42.37 4.41 5.68 7.27 27.19 5.88
(42.65)(4.63)(5.85)(7.41) (26.65)(6.13)
36.12 3.21 5.78 7.65 27.70 11.18
(36.51)(3.50)(6.08)(7.70) (27.71)(11.55)
39.03 3.93 5.24 7.38 26.40 10.62
(39.33)(4.13)(5.73)(7.26) (26.12)(10.89)
39.16 3.98 5.44 7.14 25.94 10.66
(39.33)(4.13)(5.73)(7.26) (26.12)(10.89)
37.67 3.53 5.46 7.47 26.09 10.83
(37.96)(3.82)(5.90)(7.41) (26.27)(11.21)
40.22 4.11 5.17 7.09 24.90 10.21
(40.62)(4.41)(5.57)(7.05) (25.39)(10.59)
40.46 4.23 5.29 6.97 25.11 10.25
(40.62)(4.41)(5.57)(7.05) (25.39)(10.59)
3
C
32
H40Cl
NiL Cl
2
]
(
929.5)
4
C
30
H36Cl
NiL Cl ]
2
(
901.4)
5
C
34
H44Cl
NiL Cl ]
2
(
957.5)
6
C
34
H44Cl
NiL Cl
2
]
(
957.5)
1
C
28
H32Cl
PdL ]Cl
2
2
2
2
2
2
(
921.1)
2
C
32
H40Cl
210-
212
118-
120
168-
170
PdL ]Cl
Orange
Orange
Brown
(
977.2)
3
C
32
H40Cl
PdL ]Cl
(
977.2)
4
C
30
H36Cl
PdL ]Cl
(
949.2)
5
C
34
H44Cl
Pd Dark 222-
orange 225
Pd
PdL ]Cl
(
1005.3)
6
C H44Cl
34
PdL ]Cl
Orange 87-90 53
(
1005.3)

1
2
RATHEE and VERMA
SCHEME CAPTION
Scheme 1. Formation of Ni(II) and Pd(II) Complexes
(
CH2)n
2
R TeCl +
2 H N
NH2 + NiCl / PdCl2
2
2
2
2
(
CH2)
n
H
N
H
N
Cl
R
R
R
Te
Ni
Cl
Te
R
N
H
N
H
(
CH2)
n
(
CH2)
n
H
N
H
N
R
R
Te
Te
Cl
2
Pd
R
R
N
H
N
H
(
2
CH )
n
1
L ;
R = p-hydroxyphenyl, n = 2
R = 3-methyl-4-hydroxyphenyl, n = 2
R = p-methoxyphenyl, n = 2
R = p-hydroxyphenyl, n = 3
R = 3-methyl-4-hydroxyphenyl, n = 3
R = p-methoxyphenyl, n = 3
2
L ;
3
L ;
4
L ;
5
L ;
6
L ;
Scheme 1.

Copyright of Journal of the Serbian Chemical Society is the property of National Library of Serbia and its
content may not be copied or emailed to multiple sites or posted to a listserv without the copyright holder's
express written permission. However, users may print, download, or email articles for individual use.