Thermal characterization of new complexes of Zn(II) and Cd(II) with some bipyridine isomers and propionates

Article abstract of DOI:10.1007/s10973-008-9204-y

New mixed ligand complexes of the following stoichiometric formulae: M(2-bpy)₂(RCOO)₂?nH₂O, M(4-bpy)(RCOO) ₂?H₂O and M(2,4'-bpy)₂(RCOO) ₂?H₂O (where M(II)=Zn, Cd; 2-bpy=2,2'-bipyridine, 4-bpy=4,4'-bipyridine, 2,4'-bpy=2,4'-bipyridine; R=C₂H₅; n=2 or 4) were prepared in pure solid-state. These complexes were characterized by chemical and elemental analysis, IR and conductivity studies. Thermal behaviour of compounds was studied by means of DTA, DTG, TG techniques under static conditions in air. The final products of pyrolysis of Cd(II) and Zn(II) compounds were metal oxides MO. A coupled TG/MS system was used to analyse of principal volatile products of thermal decomposition or fragmentation of Zn(4-bpy)(RCOO)2?H2O under dynamic air and argon atmosphere. The principal species correspond to: C⁺, CH⁺, CH₃ ⁺, C₂H₂⁺, HCN⁺, C ₂H₅⁺ or CHO⁺, CH₂O ⁺ or NO⁺, CO₂⁺, ¹³C ¹⁶O₂⁺ and ¹²C¹⁶O ¹⁸O⁺ and others; additionally CO⁺ in argon atmosphere.

Full text of DOI:10.1007/s10973-008-9204-y

Journal of Thermal Analysis and Calorimetry, Vol. 93 (2008) 3, 789–794
THERMAL CHARACTERIZATION OF NEW COMPLEXES OF Zn(II)
AND Cd(II) WITH SOME BIPYRIDINE ISOMERS AND PROPIONATES
*
D. Czakis-Sulikowska , J. RadwaÕska-Doczekalska, M. Markiewicz and M. Pietrzak
Institute of General and Ecological Chemistry, Technical University of ˜ódü, Poland
New mixed ligand complexes of the following stoichiometric formulae: M(2-bpy)
M(2,4’-bpy) (RCOO) ·H O (where M(II)=Zn, Cd; 2-bpy=2,2’-bipyridine, 4-bpy=4,4’-bipyridine, 2,4’-bpy=2,4’-bipyridine;
R=C ; n=2 or 4) were prepared in pure solid-state. These complexes were characterized by chemical and elemental analysis, IR
2 2 2 2 2
(RCOO) ·nH O, M(4-bpy)(RCOO) ·H O and
2
2
2
2
H
5
and conductivity studies.
Thermal behaviour of compounds was studied by means of DTA, DTG, TG techniques under static conditions in air. The final
products of pyrolysis of Cd(II) and Zn(II) compounds were metal oxides MO. A coupled TG/MS system was used to analyse of
2 2
principal volatile products of thermal decomposition or fragmentation of Zn(4-bpy)(RCOO) ·H O under dynamic air and argon
+
+
+
3
+
2
+
+
5
+
2
2 2
atmosphere. The principal species correspond to: C , CH , CH , C H , HCN , C H or CHO , CH O or NO , CO , C O and
+
+
+
13 16
+
2
2
1
2
16 18
+
C O O and others; additionally CO in argon atmosphere.
+
Keywords: bipyridine–propionato complexes, IR spectra, TG-MS data, thermal decomposition, transition metal complexes
Introduction
crystallography [13]. Thermal decomposition of
cis[Co(2-bpy)(C COO) ]NO (where 2-bpy=
H
2
5
2
3
Transition metal complexes with carboxylates are a
2,2’-bipyridine) was carried out [14]. Thus, also
investigations of coordination compounds of Zn(II)
and Cd(II) with N-donors and propionates are of
significant interest. In our previous report we
described the preparation and characterization of
4,4’-bipyridine–propionato complexes of Mn(II),
Co(II), Ni(II) and Cu(II) [15]. This paper includes the
results of the synthesis, molar conductivity and thermal
properties of mixed ligand complexes of Zn(II) and
Cd(II) with bipyridine isomers (2-bpy, 4-bpy and
2,4’-bpy) and propionates in the solid state.
subject
MaÓecka et al. [1] described the synthesis and thermal
behaviour of some cadmium(II) carboxylates [1, 2, 4].
The thermal decomposition of Zn(C COO) ·H
was also studied [6].
of
considerable
interest
[1–6].
H
O
2
2
5
2
The work presented here is a continuation of our
earlier investigations on transition metal complexes with
bipyridine and carboxylates. Mixed ligand complexes of
Zn(II) containing N-donor ligands and COO groups
are especially attractive due to their important role in
biological systems [7–9]. For example: Zn(C
H COO)
2 5 2
(
imidazole) was applied as a model compound in the
2
studies of active metal ion sites of metalloenzymes
10]. On the other hand cadmium(II) complexes are
inhibitors of different biological processes [7].
The crystal structure of [Cd(CH CH COO) phen]
CH CH COOH (where phen=1,10-phenanthroline)
Experimental
[
Materials
·
2
3
2
2
Water solutions of zinc(II) and cadmium(II) propionates
were obtained by adding 40 mL 3 M propionic acid to
freshly precipitated metal carbonates in ca equimolar
ratio. Other chemicals used in this work were the same
as those described in [15–17] and from POCh-Gliwice.
2
3
2
was determined [11]. The compound was charac-
terized by thermal behaviour and other physical
properties. Mikurija et al. reported the preparation
and X-ray researches of the chain structures
of [Cu
(4-bpy)(C H COO) ]
2 2 5 4 n
Synthesis of the complexes and analysis
and [Cu (4-bpy)(C H COO)(OCH ) (CH OH) ] 2n·
2 2 5 3 2 n
3 2
CH
3
OH (where 4-bpy=4,4’-bipyridine) [12]. Also the
Preparation of mixed metal(II) bipyridine-propionato
complexes: zinc(II) and cadmium(II) compounds with
bipyridyne and propionates was prepared as result of
the reaction of metal(II) propionates with bpy (where
complex of Cu(II) with 2,4’-bipyridine (2,4’-bpy) and
propionates was synthesized, characterized by thermal
analysis, IR and electronic spectroscopy and X-ray
*
Author for correspondence: dczakis@p.lodz.pl
1
388–6150/$20.00
Akadémiai Kiadó, Budapest, Hungary
Springer, Dordrecht, The Netherlands
©
2008 Akadémiai Kiadó, Budapest

CZAKIS-SULIKOWSKA et al.
bpy=2-bpy, 4-bpy or 2,4’-bpy) in ca 75% v/v ethanol
for 2-bpy or 4-bpy and in water solution for 2,4’-bpy.
A solution of 12.0 mmol of 2-bpy or 4-bpy in 23.3 mL
of 96% v/v ethanol was added to 6.7 mL M(C COO)
M(II)=Zn, Cd) water solutions (6.0 mmol). 2,4’-bpy
8.0 mmol) dissolved in 14.8 mL water (containing
.2 mL 96% v/v ethanol) was mixed with 4.0 mmol of
M(C COO) (M(II)=Zn, Cd) in 15.0 mL of water.
from Balcers); platinum crucible, sample 8.36 mg;
an ion source temperature of ca 150°C (70 eV
electron impact ionisation). All thermal investi-
gations were carried out in the range of temperature
H
2
5
2
–
20–1000°C, at a heating rate, 10°C min . The m/z
1
(
1
12
14
values are given based on H, C, N and
16
(
O
1
(additionally C and O in the case of CO
3
18
0
). Molar
2
H
conductivities (L ) of the studied complexes were
2
5
2
M
–
3
–1
The obtained products were washed with 40% v/v
ethanol (or water for 2,4’-bpy complexes) and then
with ethanol and diethyl ether mixture (1:1). All
compounds were dried in open air and analysed. The
equation for synthesis of complexes is:
measured [16] using 1.0·10 mol L solutions in
MeOH, DMF and DMS. The apparatus and other
experimental conditions were described in previous
papers [16, 17].
M(C
2
H
5
COO)
2
+n bpy+m solvent«
Results and discussion
«
M(C H COO) (bpy) ·m solvent¯
2
5
2
n
(
where n=1 or 2).
The new small-crystalline compounds with empirical
formulae Zn(2-bpy)
Cd(2-bpy) (RCOO)
Zn(4-bpy)(RCOO) ·H
Cd(4-bpy)(RCOO) ·H
Zn(2,4’-bpy) (RCOO) ·H O (V) and
2
(RCOO)
·4H O (II),
O (III),
O (IV),
2 2
·2H O (I),
The contents of metal(II) in obtained complexes and
solutions of zinc(II) or cadmium(II) propionates were
determined complexometrically; C, H and N by
2
2
2
2
2
2
2
elemental analysis with V
The assumed composition was confirmed by analysis
maximal deviations 0.05–0.5%).
2 5
O as an oxidizing agent.
2
2
2
Cd(2,4’-bpy) (RCOO) ·H O (VI) (where R=C H )
2 2 2 2 5
(
were isolated. The observed molar conductivities values
in MeOH, DMF and DMSO are given in Table 1. Low
2
Physical measurements
1
–1
values of molar conductivity L
all the obtained compounds in DMSO solutions (LM
in the range 1.1–2.4) and complex (III) in DMF
M
(W cm mol ) for
Thermal decomposition was investigated on Q-500
derivatograph using Al O as a standard. The samples
2 3
(
L =1.6) point out that complexes are non-electrolytes
M
of 100 mg were heated in ceramic crucible in static air
atmosphere. A coupled TG/MS system was used to analyse
principal volatile products of thermal decomposition
or fragmentation for a complex of Zn(II) with 4-bpy
and propionates. Dynamic measurements were carried
in these solutions. The molar conductivity data of all
the complexes in MeOH (L
in the range 25.1–65.1)
M
and compounds (I), (II) and (IV)–(VI) in DMF (LM
in the range 17.7–50.6) probably show behaviour
intermediate between those of non-electrolytes and
3
–1
out in air or argon atmosphere (at flow rate of 1 L h ).
Data were recorded with commercial software
Derivatograph TG/DTA-SETYS-16/18, coupled to a
Mass-Spectrometer QMS-422 model Thermo Star
1
:1 electrolytes. They dissociate in a limited degree in
the solutions used [18].
(
–
1
2
–1
–3
–1
Table 1 Analytical data, molar conductivity L
M
(W cm mol ) in MeOH, DMF and DMSO c=1·10 mol L at 25°C, (R=C
2 5
H )
Analysis: found (calculated)/%
L
M
No.
I
Complex
M
C
N
H
MeOH
65.1
DMF
35.1
DMSO
1.8
Zn(2-bpy) (RCOO) ·2H O
2 2 2
11.94
55.98
10.25
5.32
(
(
(
(
(
(
11.67)
(55.77)
(10.01)
(5.40)
II
Cd(2-bpy) (RCOO) ·4H O
2 2 2
16.49
48.89
8.11
5.25
49.4
30.5
25.4
29.7
25.1
39.5
1.6
2.4
1.2
2.3
1.1
2.3
17.48)
(48.57)
(8.71)
(5.33)
III
IV
V
Zn(4-bpy)(RCOO)2·
H O
2
17.22
50.05
7.16
5.00
16.85)
(49.82)
(7.26)
(5.23)
Cd(4-bpy)(RCOO) ·H O
2 2
25.74
44.63
6.27
4.59
17.7
50.6
37.8
25.97)
(44.41)
(6.47)
(4.66)
Zn(2,4’-bpy) (RCOO) ·H O
2 2 2
12.24
58.01
10.31
5.15
12.06)
(57.63)
(10.34)
(5.21)
VI
Cd(2,4’-bpy) (RCOO) ·H O
2 2 2
19.09
53.46
9.43
4.70
19.08)
(53.03)
(9.51)
(4.79)
790
J. Therm. Anal. Cal., 93, 2008

THERMAL CHARACTERIZATION OF NEW COMPLEXES OF Zn(II) AND Cd(II)
–
Table 2 Principal IR bands [cm ] for complexes, bipyridine isomers and COO group of propionates
1
n
(CC,CN,CCi.r.)
n
(CC,CN)
Ring
Complex
n
as(OCO)
n
s(OCO)
DnOCO
(A
1
)
(B
1
)
breathing
2
-bpy [19]
I Zn(2-bpy)
II Cd(2-bpy)
-bpy [20]
1579
1598.0
1590.0
1588
1553
1562.2
1563.2
1530
993
1020.0
1010.6
988
2
(RCOO)
2
·2H
2
O
1578.0
1580.0
1444.6
1436.9
133.4
143.1
2
(RCOO)
2
·4H
2
O
4
III Zn(4-bpy)(RCOO)
2
2
·H
·H
2
2
O
O
1605.6
1542.0
1004.8
a)
1560.0
1566.1
1440.0
*
120.0
–
IV Cd(4-bpy)(RCOO)
1602.7
1535.2
1006.8
a)
2
,4’-bpy (4-sub) [20]
1595
1405
990 sh
V Zn(2,4’-bpy)
2
(RCOO)
2
·H
2
O
1610.5
1415.7
1019
a)
1585.4
*
1436.9
1440.0
1416
148.5
–
VI Cd(2,4’-bpy)
2
(RCOO)
2
·H
2
O
1609.5
–
1416.6
–
1011.6
a)
RCOONa [26]
–
1558
142
R=C
2
H
5
3
, DnOCO=nas(OCO)–ns(OCO), a) – partly superimposed on the CH wagging vibration of propionate groups, * – nature of the
M-propionate bond does not interpreted
IR spectra
data [23–25] prove the coordination through the least
hindered 4’N atom of 2,4’-bpy.
Water vibrations
The presence of water in all complexes is shown by
the apperance of a broad band in the stretching vibrations
Propionates vibrations
–
region (3400–3300 cm ) followed by a shoulder at
1
For all the investigated compounds the most
fundamental vibrations for carboxylates groups
asymmetric (nas(OCO)) and symmetric (ns(OCO)) stretching
modes were observed (Table 2). The spectrum of
ionic sodium propionate shows nas(OCO) and ns(OCO)
–
1
ca 1630 cm assignable to water deformation frequencies.
2
-bpy, 4-bpy and 2,4’-bpy vibrations
–
1
bands at 1558 and 1416 cm , respectively [26]. The
bands of nas(OCO) and ns(OCO) in the IR spectra of (II)
and (V) complexes shift to higher vibrations
relatively to those in ionic salt. The separations values
Dn=nas(OCO)–ns(OCO) for (II) and (V) are almost the same
in comparison with the corresponding value for
NaRCOO. Due to the spectroscopic criteria and
literature data [27–32] the carboxylate groups in these
complexes are probably of bidentate bridging ligands.
In the case of (I) and (III) values Dn decrease to about
The most significant IR bands of these bipyridine
isomers and their complexes together with possible
assigments described in [19, 20] are given in Table 2.
The characteristic bands attributed to the ring
stretching vibrations n(CC,CN,CCir ) , (A1 symmetry)
n(CN,CC) (B
symmetry) and ring ‘breathing’ modes are
1
shifted to higher frequencies in comparison with
unbonded ligands. However, the ring ‘breathing’
vibration is partially obscured by the wagging
vibration of the CH
changes provide evidence for coordination of
N-donors to Zn(II) and Cd(II) [21–23]. The strong
3
group of propionates. These
–1
1
33.4 and 120.0 cm , respectively, indicating of
bidentate chelate coordination of propionate groups in
these compounds. The superposition of bands due to
s(OCO) and 4-bpy (for Cd(4-bpy)(RCOO) ·H O) as
well as and 2,4’-bpy (for
Cd(2,4’-bpy) (RCOO) ·H O) respectively are ob-
–
1
band appears at 753 cm (associated with gC–H out of
the plane deformation mode for free 2-Bpy) shifts by
n
2
2
–
ca 15 cm towards higher frequencies, also weak
1
nas(OCO)
–
1
satellite of this band (at 735 cm ) gains intensity and
is strongly split away from parent peak. Thus, it can
be concluded that (I) and (II) are 2,2’-bipyridine
chelates [21, 22]. Upon the coordination with Zn(II)
and Cd(II) the IR spectrum of unbonded 2,4’-bpy
2
2
2
served. Thus, the interpretation of the coordination
mode of Cd–propionates is difficult to discuss.
Thermal properties of compounds
changes in the region of the vibrations n(CC,CN,CCir )
n(CN,CC) and ring ‘breathing’ 4-substituted pyridine
4-sub). These observations and literature
,
The thermoanalytical data are presented in Table 3.
The results of thermal, chemical and X-ray analyses
(
J. Therm. Anal. Cal., 93, 2008
791

CZAKIS-SULIKOWSKA et al.
Table 3 Thermal decomposition of complexes in air (R=C
2
H
5
, sample mass 100 mg)
Mass loss/%
Ranges of
Intermediate and final
solid products
No.
Complex
DTA peak/°C
decomp./°C
found
calc.
3.22
I
Zn(2-bpy)
2
(RCOO)
2
·2H
2
O
60–120
75 endo
3.0
Zn(2-bpy)
2 2 2
(RCOO) ·H O
a)
1
20–265
120 endo sh
38.5
38.08
Zn(2-bpy)0.75(RCOO)
2
210 exo br
2
3
65–375
75–480
320 endo sh
385, 440 exo
75 endo
42.0
2.0
ZnO with organic residue
pure ZnO
44.16
2.80
II
Cd(2-bpy)
2
(RCOO)
2
·4H
2
O
60–130
2.5
Cd(2-bpy)
2 2 2
(RCOO) ·3H O
a)
1
30–220
20–380
80–520
200 endo sh
315 endo, 360 exo
440 exo sh
110 endo
20.0
56.5
2.5
20.05
Cd(2-bpy)1.5(RCOO)
2
2
3
CdO with organic residue
pure CdO
57.17
4.65
III Zn(4-bpy)(RCOO)
2
·H
2
O
65–120
50–250
4.5
Zn(4-bpy)(RCOO)
Zn(4-bpy)0.75(RCOO)
2
2
a)
1
250 endo
11.0
61.0
3.0
10.12
2
3
50–370
70–495
295 endo
ZnO with organic residue
pure ZnO
400 exo
64.11
4.16
IV Cd(4-bpy)(RCOO)
2
·H
2
O
110–150
145 endo
4.0
Cd(4-bpy)(RCOO)
2
2
10–350
300, 320 endo,
63.0
CdO with organic residue
310 exo
3
50–515
360 exo
60 endo
3.0
3.0
66.17
3.32
pure CdO
V
Zn(2,4’-bpy) (RCOO) ·H O
2 2 2
60–160
2 2
Zn(2,4’-bpy) (RCOO)
1
60–350
240 exo br, 300
endo br
80.0
ZnO with organic residue
3
50–490
385, 480 exo
105 endo
2.0
3.0
81.92
3.06
pure ZnO
VI Cd(2,4’-bpy) (RCOO) ·H O
2 2 2
80–110
2 2
Cd(2,4’-bpy) (RCOO)
1
50–360
60–500
160, 310 endo
450 exo sh
73.5
2.5
CdO with organic residue
pure CdO
3
75.14
a
by projecting minimum of DTA curve on TG curve; br – broad; sh – shoulder
Fig. 2 X-ray diffraction pattern of decomposition of complex
Cd(4-bpy)(C COO) ·H O heated up 550°C
2
H
5
2
2
Fig. 1 Thermoanalytical curves of
dehydration takes place. The dehydration occurs in one
endothermic step for (III)–(VI); in two endothermic
steps for (I) and (II). In the case of (I), (II)
and (V) compounds, decomposition of organic li-
gands occurs immediately after dehydration. The
final stage of dehydration for (I) and (II) complexes is
connected with partial elimination of 2-bpy. Thermal
decompositions of anhydrous complexes (III), (IV)
and (VI) begin at 150, 210 and 150°C, respectively.
For the obtained complexes the deamination overlaps
a – Zn(2-bpy)(C
b – Zn(4-bpy)(C
c – Cd(2,4’-bpy)
2
H
5
COO)
COO)
(C COO)
0°C min , mass sample 100 mg
2
·2H
·H O;
·H
2
O;
2
H
5
2
2
2
2
H
5
2
2
O in air, heating rate
–
1
1
make it possible to postulate the decomposition products
of solid complexes. The thermal profiles (TG, DTA
and DTG) of some complexes are given in Fig. 1.
The complexes (I)–(III) and (V)–(VI) are stable up to
about 60–80°C, whereas (IV) to 110°C, where
792
J. Therm. Anal. Cal., 93, 2008

THERMAL CHARACTERIZATION OF NEW COMPLEXES OF Zn(II) AND Cd(II)
1
given for H, C, N and O (additionally C and O
12
14
16
13
18
+
in the case of CO ). MS data for the complex detected
2
several profiles of ion current. The first peaks of ion
+
+
current for H
10°C in air and 125°C in argon. They correspond to
the elimination of crystalline water (the first step of
mass loss is observed in TG curve) (Fig. 3). The peaks
O and OH (m/z=18 and 17) appeared at
2
1
+
of ions H O and OH appear also at ca 300°C (in air)
+
2
and 320°C (in argon) as a consequence of oxidation of
organic ligands. Major maxima of signals are observed
in the temperature range 300–330 and 310–370°C in
air and argon, respectively. The MS peaks of ions with
+
m/z=12, 13, 15, 26, 27, 29, 30, 44, 45, 46 (C , CH ,
+
+
3
+
+
+
5
+
CH , C H , HCN , C H or CHO , CH
+
O or NO ,
+
2
13 16
2
2
12 16 18
2
+
+
+
CO , C O and C O O ) were monitored. Addi-
2
2
+
tionally, in argon the elimination of molecular ion CO
+
is observed. The peaks of CO or N (m/z=28) appear
+
2
at 320°C (strong) and 630°C (small). The maxima of
ion signals coincide with the sudden mass loss
occurring on TG curve (Fig. 1b). In gaseous products
+
+
the molecular ionCO and additionally CO (in argon)
2
formed by total pyrolysis of organic ligands dominate.
Figure 3 shows some profiles of ion current detected in
mass spectrometer for Zn(4-bpy)(RCOO) ·H O in air
2 2
(Fig. 3a) and in argon (Fig. 3b).
Conclusions
Fig. 3 Ion current detected by the MS for complex
Zn(4-bpy)(C COO) ·H O; a – in air, mass sample
.62 mg; m/z=1-18; 2-26; 3-27; 4-30; 5-44 with
In this paper new mixed-ligand complexes:
Zn(2-bpy) (RCOO) ·2H O, Cd(2-bpy) (RCOO) ·4H O,
M(4-bpy)(RCOO) ·H O and M(2,4’-bpy) (RCOO) ·H O
2
H
5
2
2
2
2
2
2
2
2
7
sensitivity of: E-09, E-11, E-12, E–11, E–10 A,
respectively; b – in argon; mass sample 8.36 mg;
m/z=1-18; 2-27; 3-28; 4-30; 5-44 with sensitivity of:
E-09, E-12, E-10, E–12, E–12 A, respectively; heating
2
2
2
2
2
(M(II)=Zn, Cd) were prepared and studied. Previously
we described complexes of empirical formulae
M(4-bpy)(RCOO) ·2H O, where M(II)=Mn, Co and
Ni [15]. As it was shown in IR data presented above,
bipyridine and propionates coordinated to metal(II)
ions. The compounds M(2-bpy) (RCOO) ·nH O are
2
2
–
1
rate 10°C min
the process of full decomposition of propionates. The
products of this stage of pyrolysis are suitable metal
oxides with ca 2% organic residue. The separate steps
of bpy elimination are not clearly observed. Accord-
ing to the DTG curves, bpy is lost stepwise only for
2
2
2
cis-bis 2,2’-bipyridine chelates [21, 22]. 2,4’-Bpy
coordinates via the least hindered nitrogen atom N(4’)
in complexes (V) and (VI). All the complexes are
small crystalline solids and air stable. The thermal
decomposition of the hydrated complexes begins with
the release of water. During heating complexes (III)–(VI)
lose water molecules in one stage. Anhydrous mixed
ligand complex of Cd(II) with 4-bpy and propionates
(
I)–(III) complexes. Final solid products of the
thermal decomposition of (I)–(VI) complexes are
pure ZnO or CdO. They were identified on the basis
of powder diffractograms [33] and analysis of TG
curves. Figure 2 shows as an example the diffraction
is most stable. The decomposition of Cd(4-bpy)(RCOO)
2
pattern of Cd(4-bpy)(RCOO)
·H O heated up to
2 2
begins above 210°C. The complexes (I) and (II) lose
water in two stages. Thermoanalytical data of bipyri-
dino–propionate complexes of Zn(II) and Cd(II) indi-
cate that several decomposition processes of these
compounds are very weakly separated. Previously we
described similar observations for some d-metal
bipyridino-lactate or propionate complexes [15, 34].
Thermal decomposition of obtained complexes in air is
multistage and yields pure ZnO and CdO as final products.
5
50°C. The DTA curves exhibit several exothermic
peaks, which are associated with oxidation of organic
fragments (Table 3).
Mass spectrometer was used for the characteriza-
tion of principal volatile products evaluated during
thermal decomposition and fragmentation processes
only for the Zn(4-bpy)(RCOO) ·H O complex in the
2 2
dynamic air or argon atmosphere. The m/z values are
J. Therm. Anal. Cal., 93, 2008
793

CZAKIS-SULIKOWSKA et al.
Generally, the MS detected during pyrolysis of
complexes of type M(4-bpy)(C COO) ·nH O (where
15 D. Czakis-Sulikowska, J. RadwaÕska-Doczekalska,
A. Czylkowska and J. GoÓuchowska, J. Therm. Anal. Cal.,
8 (2004) 501.
H
2
5
2
2
7
M(II)=Mn, Co, Ni [15] and Zn) are very similar.
The maxima of ion current are associated with the
decrease in mass sample observed on TG curve. The ion
1
6 D. Czakis-Sulikowska, A. Czylkowska and
A. Malinowska, J. Therm. Anal. Cal., 79 (2005) 1635.
7 D. Czakis-Sulikowska, A. Malinowska and K. Kafarska,
Pol. J. Chem., 80 (2006) 1945.
1
+
currents corresponding to C , CH , CH , C H ,
+
+
+
3
2
13 16
2
+
+
+
+
+
+
HCN , C H or CHO , CH O or NO , CO , C O2
2
and C O O (m/z=12, 13, 15, 26, 27, 29, 30, 44, 45
+
2
2
16 18
5
2
18 W. I. Geary, Coord. Chem. Rev., 7 (1971) 81 and
references therein.
1
+
and 46, respectively) were detected.
19 J. S. Strukl and J. L. Walter, Spectrochim. Acta,
27 A, (1971) 223.
2
2
2
0 C. K. Pearce, D. W. Grosse and W. Hessel, Chem. Eng.
Data, 15 (1970) 567.
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