Vol.3, No.7, 535-541 (2011) Natural Science
http://dx.doi.org/10.4236/ns.2011.37075
Copyright © 2011 SciRes. OPEN ACCESS
Thermochemical parameters of
1,2,3,4-tetrahydroquinoline adducts of some divalent
transition metal bromides
Pedro Oliver Dunstan*
Instituto de Química, Universidade Estadual de Campinas, Campinas, Brazil; *Corresponding Author: dunstan@iqm.unicamp.br
Received 14 May, 2011; revised 30 May 2011; accepted 4 June 2011.
ABSTRACT
The adducts [MBr2(L)n], where M = Fe, Co, Ni, Cu
or Zn; L = 1,2,3,4-tetrahydroquinoline (THQ); n =
0.75, 1 or 2 have been obtained from the inter-
action in hot solution of THQ with the metal(II)
bromides. The compounds were characterized
by melting points, elemental analysis, thermal
analysis and IR spectroscopy. From calorimetric
studies in solution, the standard enthalpies of
formation of them and several other thermo-
chemical parameters were determined. The mean
standard enthalpies of the metal(II)-nitrogen
bonds have been estimated.
Keywords: Transition Metal Complexes;
Thermochemistry; Coordinated Bonds Energies;
Dissolution Enthalpies; Calorimetry
1. INTRODUCTION
Quinoline and quinoline derivatives are known to
form complexes with transition metal(II) halides [1-23].
Thermochemical parameters related to the transition
metal(II)-nitrogen coordinated bonds formed in these
compounds are not found in the literature. In a recent
article [23] it was determined the values for several
thermochemical parameters of adducts of some transi-
tion metal(II) bromides with quinoline. Following with
the purpose of filling the lack of information on the en-
ergy evolved in the formation of these compounds, in the
present article, it is reported the calorimetric determina-
tion of the energy involved in the formation of the coor-
dinated metal(II)-nitrogen bonds, as well as, the values
of several thermochemical parameters for the com-
pounds formed between some metal(II) bromides with
tetrahidroquinoline. The knowledge of these energy val-
ues is very important for understanding the coordinated
metal(II)-nitrogen bonds formed. The thermodynamic
properties of the compounds eventually could be used in
determining their applications in catalysis and in the
chromatographic separation of the metallic ions.
2. EXPERIMENTAL
1,2,3,4-Tetrahidroquinoline (98%, Aldrich was puri-
fied by distillation through an efficient column and
stored over Linde 4Å molecular sieves. All the anhy-
drous metal(II) bromides used in the preparation of the
adducts were of reagent grade (99%+). Solvents used in
the synthesis of the compounds and in calorimetric mea-
surements were purified by distillation and stored over
Linde 4Å molecular sieves.
2.1. Adducts Synthesis
The adducts were prepared by the interaction of metal
(II) bromides and ligand in solution. It was used hot etha-
nol or hot methanol. It was used a molar ratio salt/ligand
of 1/4 or 1/2. Following, the solvent was evaporated by
using vacuum. The solid obtain was re-crystallized,
washed with three portions of petroleum ether and dried
in vacuum. A typical procedure is given below.
CoBr2-THQ
To a solution of 1.0 g of CoBr2 (4.57 mmol) in 50 mL
of hot ethanol, 2.3 mL (18.29 mmol) of tetrahidroquino-
line was added slowly and dropwise under stirring. After
filtering and evaporation of the solvent, a green solid
was obtained. This was re-crystallized from chlorophor-
me. The product was dried for several hours in vacuum
and stored in a desiccator over calcium chloride.
2.2. Analytical and Physical Measurements
Carbon, hydrogen and nitrogen were determined by
micro analytical procedures [24]. Halide analysis was
made by gravimetry using standard N/10 AgNO3 aque-
ous solution, after the adducts were dissolved in water
P. O. Dunstan / Natural Science 3 (2011) 535-541
Copyright © 2011 SciRes. OPEN ACCESS
536
[25]. Metal contents were determined by complexomet-
ric titration with 0.01 M EDTA solution of aqueous solu-
tion of the adducts [26]. The capillary melting points of
them were determined with a UNIMELT equipment
from Thomas Hover. Spectra were obtained with sam-
ples in KBr matrix for the solid adducts. For tetrahidro-
quinoline, a film of the ligand sandwiched between KBr
plates was used. A Perkin-Elmer 1600 series FT-IR
spectrophotometer in the 4000 - 400 cm–1 region was
used. TG/DTG and DSC measurements were obtained in
argon atmosphere in a Du Pont 951 TG analyzer with the
sample varying in mass from 5,58 to 19,94 mg
(TG/DTG) and from 2,44 to 9,09 mg (DSC) and a heat-
ing rate of 10 K·min–1 in the 298 - 678 K (DSC) and
298-1248 (TG/DTG) temperature ranges. TG calibration
for temperature was made with metallic aluminum as a
standard (mp = 660.37oC) and the equipment carried out
the calibration for mass automatically. The DSC calibra-
tion was made with metallic indium as a standard (mp =
165.73oC, slH = 28.4 J·g–1). Spectra in the 350 - 2000
nm region were obtained with a UV-Vis-NIR Varian-
Cary 5G spectrophotometer with a standard reflectance
attachment for obtaining the spectra of the solid adducts.
All the solution calorimetric measurements were carried
out in an LKB 8700-1 calorimeter as described before
[27]. The solution calorimetric measurements were per-
formed by dissolving samples of 2.7 - 85.3 mg of the
adducts or metal(II) bromides in 100 mL of 1.2 M
aqueous HCl and the ligand in this last solution main-
taining a molar relation salt/ligand equal to the stoichio-
metry of the adduct. The accuracy of the calorimeter was
checked by determining the heat of dissolution of tris
[(hydroxymethyl)amino] methane in 0.1 mol·dm–3 HCl.
The result (–29.78 0.03 kJ·mol–1) is in agreement with
the value recommended by IUPAC (–29.763 0.003
kJ·mol–1) [28].
3. RESULTS AND DISCUSSION
3.1. Characterization of the Compounds
All the adducts were solids. The yields range from
22% to 60%. The capillary melting points and analytical
data are summarized in Table 1.
3.1.1 Infrared Studies
The more important IR bands of the compounds are
reported in Table 2. The spectra show shift of several
bands after coordination with respect to the free ligand.
Shifts to lower frequencies of the N-H stretching modes
of the coordinated tetrahidroquinoline are observed. This
is indicative of coordination to the metallic(II) ion
through the nitrogen atom [13,29].
3.1.2. Thermal Studies
The themogravimetry of the compounds shows the
Table 1. Melting points, yields, appearance and analytical data of the adducts.
% Calculated (found)
Compound Yield % mp
oC % C % H % N % Br % Metal
[FeBr2(THQ)0.75] 34 108-11 25.69(25.39) 2.64(2.71) 3.32(3.30) 50.65(50.75) 17.70(17.73)
[CoBr2(THQ)2] 32 235-38 44.56(44.76) 4.57(4.47) 5.77(5.73) 32.94(32.90) 12.15(12.04)
[NiBr2(THQ)1.5] 89 368-71 38.76(38.98) 3.98(4.22) 5.02(4.97) 38.20(38.15) 14.03(13.99)
[CuBr2(THQ)2] 5 95-98 44.15(43.85) 4.53(4.30) 5.72(5.62) 32.63(32.81) 12.97(13.01)
[ZnBr2(THQ)2] 60 48-51 51.91(51.80) 5.32(5.23) 6.73(6.55) 25.58(25.69) 10.46(10.50)
[ZnBr2(THQ)3] 22 pastry 43.98(43.70) 4.51(4.33) 5.70(5.57) 32.51(32.56) 13.30(13.34)
Table 2. Main IR spectral data (cm–1) of the compounds.
Band assignments
Compound
(N-H)
(C-C)
(N-H) Ring
(C-C)
THQ 3406s 1606s 1584m 1033m 747s
[FeBr2(THQ)0.75] 3386s, b 1558m no 995m 753s
[CoBr2(THQ)2] 3396m, b 1581m 1581m 957m 740s
[NiBr2(THQ)1.5] 3406m, 3054m 1557m 1606m 996m 752s
[CuBr2(THQ)2] 3443s, 2923m 1594m 1594m 805m 779m
ZnBr2(THQ)2] 3410s, 3224m 1535m 1588m 967m 749s
[ZnBr2(THQ)3] 3408s, 3146m 1586m 1586m 1002m 750s
P. O. Dunstan / Natural Science 3 (2011) 535-541
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537
loss of part of the ligand in 2 - 4 steps of mass loss,
alone or together with the loss of part of the bromine or
with part of bromine and part of the metal content in the
last step of mass loss. Bromine is lost in the last step or
in the two final steps of mass loss, alone or together with
the mass loss of part of the metal content. A residue is
left that is part of the metal content. The DSC curves are
consistent with the TG data. They present endothermic
peaks due to the elimination of part of the ligand or part
of bromine, alone or together with the elimination of part
of the metal content. They present exothermic peaks due
to the decomposition of the ligand or intermediate com-
pounds. Table 3 presents the thermoanalytical data of
the adducts.
3.1.3 Electronic Spectra
The ligand field parameters for the cobalt adduct have
been calculated according to Lever [30]. Considering the
number and position of the bands [31,32] and according
with the magnitude of the crystal field parameters as
compared with that of Bolster [33], it is concluded that
two nitrogen atoms from two ligand molecules and by
two bromides ions pseudo-tetrahedrally surround Co(II)
ion. The ligand field parameters for the Ni(II) adduct
were calculated according to Reedijk et al. [34] and
Lever [30]. According to the number and position of the
observed bands and considering the magnitude of the
crystal field parameters as compared with that of Bolster
[33], it is concluded that the Ni(II) ion is pseudo-tetra-
hedrally surrounded by two nitrogen atoms from two
ligand molecules and two bromides ions, one of which is
bridging to other Ni(II) ion in a dimeric structure. This
last ion is surrounded by one nitrogen atom from one
ligand molecule and three bromine ions, one of which is
the mentioned bridge with the first nickel ion. For the
Cu(II) adduct, the electronic spectra showed a rather
broad asymmetrical band with maxima at 10528 cm–1.
Its intensity and position correspond with those observe
for pseudo-octahedral compounds [33], with the Cu(II)
ion being surrounded by two nitrogen atoms from two
ligand molecules and by four bromide ions in a bridge
structure. The ligand parameters for the adduct of Fe(II)
were calculated according to Bolster [33]. It is con-
cluded that one unit is formed by Fe(II) ion
pseudo-octahedrally surrounded by one nitrogen atom
from one ligand molecule and five bromide ions in a
polymeric structure bridging with other units of Fe(II)
ion surrounded by six bromide ions. Table 4 contains the
band maxima assignments and calculated ligand field
parameters for the adducts.
Table 3. Thermal analysis of the compounds.
Mass loss (%)
Compound Apparent
mp K Calcd. Obs.
TG temperature
range K Species lost DSC peak
temperature H
(kJ·mol–1)
[FeBr2(THQ)0.75] 381-4 7.60 7.70 356 - 394 -0.18L 394 61.63
24.05 24.82 394 - 562 -0.57L 507 1.59
17.73 17.71 914 - 938 -0.70Br
25.33 25.73 938 - 1086 -Br
24.04 1248 residue
[CoBr2(THQ)2] 508-11 27.45 27.22 477 - 546 -L 342 2.73
27.45 23.47 546 - 565 -L 516 27.44
34.13 38.68 565 - 957 -2Br-0.1Co 530 6.48
10.63 1248 residue
[NiBr2(THQ)1.5] 368-71 16.72 16.39 369 - 409 -0.7L 387 71.16
36.79 37.24 409 - 494 -1.3L-0.3Br 441 –75.95
32.47 32.64 846-959 -1.7Br 490 90.66
13.73 1248 residue
[CuBr2(THQ)2] 428-31 6.80 6.40 365 - 399 -0.25L 372 –19.40
14.96 15.09 399 - 508 -0.55L 399 –1.22
8.16 8.47 508 - 646 -0.30L 439 –28.63
61.00 60.80 646 - 1056 -0.90L-2Br-0.3Cu 499 1.59
9.24 1248 residue
[ZnBr2(THQ)2] 321-4 35.22 35.48 228-544 -1.3L 357 31.15
54.13 54.31 544-742 -0.7L-2Br-0.2Zn 284 –5.08
8.65 8.28 742-1069 -0.65Zn 496 –3.24
1.93 1248 residue
[ZnBr2(THQ)3 pastry 42.64 44.20 392 - 526 -2L 320 27.22
34.11 36.16 526 - 732 -L-Br 448 –28.86
12.79 10.25 813 - 831 -Br
6.28 5.11 831 - /1020 -0.60Zn
4.28 1248 residue
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538
Table 4. Band maxima and calculated ligand field parameters for the compounds.
Band maxima (×103 cm–1)
Compound d-d Intraligand + charge transfer
[FeBr2(THQ)0.75] 10.60 21.17
2
3 Dq (cm–1) B(cm–1) Dq/B
(B/B0)[33]
[CoBr2(THQ)2] 7.36 15.28 431 648 0.665 0.667 20.63 32.65
[NiBr2(THQ)1.5] 8.38 14.28 243 1272 0.191 1.235 21.77
[CuBr2(THQ)2] 10.53 23.78 34.83
3.1.4. Calorimetric Measurements
The standard enthalpies of dissolution of metal(II)
bromides, tetrahidroquinoline and adducts were obtained
as previously reported [27]. The standard enthalpies of
dissolution were obtained according to the standard en-
thalpies of the following reactions in solution:

1
2s
MBrcalorimetric solventsolution A,
H
 (1)

2
1
n THQsolution Asolution B,
H
  (2)


2S
3
MBrTHQncalorimetric solvent
solution C, H



(3)
4
solutionsolution C, BH
 (4)
The application of Hess’ law to the series of reactions
(1) - (4) gives the standard enthalpies of the acid/base
reactions (rH
) according to the reaction:
 


2r
2s 1ns
MBrn THQMBrTHQ,
H

 

(5)
where r123
H
HHH

 since the final
thermodynamic state of reactions (2) and (3) is the same
and 4H
= 0. Ta b l e 5 gives the values obtained for the
enthalpies of dissolution of MBr2 (1H
), THQ into the
solution of MBr2 (2H
) and of the adducts (3H
). Un-
certainty intervals given in this table are twice the stan-
dard deviation of the mean of 4 - 9 replicate measure-
ments. The thermochemical parameters were calculated
for hypothetical monomeric adducts. From the values
obtained for the standard enthalpies of the acid/base re-
actions (rH
) and by using appropriate thermochemical
cycles [29], the following thermochemical parameters
for the adducts were determined: the standard enthalpies
of formation (fH
), the standard enthalpies of decom-
position (DH
), the standard lattice enthalpies (MH
)
and the standard enthalpies of the Lewis acid/base reac-
tions in the gaseous phase (rH
(g)). These later values
can be used to calculate the standard enthalpies of the
M-N bonds, being equal to
D(M-N) = –rH
(g)/n [35].
Table 6 lists the values of all these thermochemical pa-
rameters. The standard enthalpies of: formation and
Table 5. Enthalpies of dissolution at 298.15 K.
Compound Calorimetric solvent Number of experiments i iH (kJ·mol–1)
FeBr2(s) 1.2 M aq. HCl 5 1 –76.82 ± 1.12
THQ(l) 0.75:1 Febr2-1.2 M aq. HCl 6 2 –21.45 ± 0.60
[FeBr2(THQ)0.75](s) 1.2 M aq. HCl 5 3 –13.04 ± 0.42
CoBr2(s) 1.2 M aq. HCl 5 1 –57.92 ± 0.43
THQ(l) 2:1 CoBr2-1.2 M aq. HCl 6 2 –58.12 ± 1.75
[CoBr2(THQ)2](s) 1.2 M aq. HCl 4 3 –32.72 ± 0.28
NiBr2(s) 1.2 M aq. HCl 4 1 –64.79 ± 1.48
THQ(l) 1.5:1 NiBr2-1.2 M aq. HCl 5 2 –46.64 ± 2.13
[NiBr2(THQ)1.5](s) 1.2 M aq. HCl 5 3 6.32 ± 0.40
CuBr2(s) 1.2 M aq. HCl 8 1 –24.40 ± 1.02
THQ(l) 2:1 CuBr2-1.2 M aq. HCl 5 2 –52.68 ± 0.42
[CuBr2(THQ)2](s) 1.2 M aq. HCl 4 3 –11.56 ± 0.73
ZnBr2(s) Ethanol 9 1 –43.59 ± 0.50
THQ(l) 2:1 ZnBr2-Ethanol 5 2 5.46 ± 0.16
ZnBr2(THQ)2](s) Ethanol 4 3 25.46 ± 1.08
THQ(l) 3:1 ZnBr2-Ethanol 5 2 8.30 ± 0.17
[ZnBr2(THQ)3](s) Ethanol 3 3 35.80 ± 1.60
P. O. Dunstan / Natural Science 3 (2011) 535-541
Copyright © 2011 SciRes. OPEN ACCESS
539
Table 6. Summary of the thermochemical results (KJ·mol–1) for the compounds.
Compound rH
fH
gs,lH
MH
FeBr2(s) –249.8 [36] 204 [37]
CoBr2(s) –220.9 [36] 183 [37]
NiBr2(s) –212.1 [36] 170 [37]
CuBr2(s) –141.8 [36] 182.4 [37]
ZnBr2(s) –328.65 [36] 159.7 [37]
THQ(l) 38.15 59.22
[FeBr2(THQ)0.75](s) –85.27 ± 1.34 –306.5 ± 2.5 132 ± 16 [38] –318 ± 2 113.88 ± 2.41 –186 ± 16 248 ± 21
[CoBr2(THQ)2](s) –83.32 ± 1.82 –227.9 ± 2.9 121 ± 15 [38] –385 ± 3 201.76 ± 2.70 –264 ± 15 132 ± 8
[NiBr2(THQ)1.5](s) –105.11 ± 2.62 –260.0 ± 3.2 115 ± 14 [38] –331 ± 3 162.34 ± 3.02 –217 ± 14 145 ± 9
[CuBr2(THQ)2](s) –65.52 ± 1.32 –131.0 ± 3.1 120.8 ± 14.5 [38]–324.2 ± 2.6–141.82 ± 2.40 –203.4 ± 14.7 101.7 ± 7.4
[ZnBr2(THQ)2](s) –63.59 ± 1.20 –315.94 ± 3.07109.5 ± 13.1[38]–341.7 ± 3.1182.03 ± 2.33 –232.2 ± 13.5 116.1 ± 6.8
[ZnBr2(THQ)3](s) –71.09 ± 1.68 –285.29 ± 3.98109.5 ± 13.1[38]–408.5 ± 4.0248.75 ± 3.43 –299.0 ± 13.7 99.7 ± 4.6
Table 7. Auxiliary data and enthalpy changes of the ionic complex formation process in the gaseous phase (KJ·mol–1).
Compound fH
fIH
Br(g) –219.07 [36]
Fe2+(g) 2751.6 ± 2.3 [39]
Co2+(g) 2841.7 ± 3.4 [39
Ni2+(g) 2930.5 ± 1.5 [39]
Cu2+(g) 3054.5 ± 2.1 [39]
Zn2+(g) 2781.0 ± 0.4 [39]
[FeBr2(THQ)0.75](g) –362 ± 16 –186 ± 16 –2748 ± 16
[CoBr2(THQ)2](g) –107 ± 15 –264 ± 15 –2705 ± 16
[NiBr2(THQ)1.5](g) –113 ± 14 –217 ± 14 –2751 ± 14
[CuBr2(THQ)2](g) 31.9 ± 15.0 203.4 ± 14.7 –2778.9 ± 15.4
[ZnBr2(THQ)2](g) –206.5 ± 13.7 –232.2 ± 13.5 –2741.1 ± 13.9
[ZnBr2(THQ)3](g) –175.9 ± 14.1 –299.0 ± 13.7 –2810.9 ± 14.6
sublimation of THQ as these values are not found in the
literature. They were calculated by a group contribution
method, from the enthalpies values for quinoline [40-42].
The enthalpies for the process of hypothetical monomer
complex formation in the gaseous phase, from metal(II)
ions, bromide ions and THQ molecules can be evalu-
ated:




2
fJ
M2Br n THQ
MBr2THQng,
gg
g
H
 


(6)
where








θ2+
fI ff
gg
θθ
ff
gg
adductΔHM
2ΔHBrn ΔHTHQ
HH


 .
Table 7 lists the values obtained for these enthalpies
values.
4. CONCLUSIONS
The interaction of transition metal(II) bromides with
tetrahidroquinoline produced solid adducts of defined
stoichiometry. The calorimetric study of them deter-
mined the standard enthalpies of formation and several
other thermochemical parameters. The mean standard
enthalpies of metal(II)-nitrogen coordinate bonds have
values from 100 to 248 KJ·mol–1. Comparing with the
values obtained for quinoline adducts of metal(II) bro-
mides of the same stoichiomety [23], it is observed that
the bonds formed by THQ are weaker than the bonds
P. O. Dunstan / Natural Science 3 (2011) 535-541
Copyright © 2011 SciRes. OPEN ACCESS
540
formed by quinoline. This means that the hydrogenation
of the heterocycle of quinoline to get THQ leads to the
weakness of the bond formed by the nitrogen atom with
metal(II) ions. The basicity order of the ligands is: THQ
< quinoline. Based on the rH
values obtained for the
adducts, the acidity order of the salts, for the adducts of
the same stoichiometry can be established: CoBr2 >
CuBr2 > ZnBr2. Using the
D(M-N) values, the order is:
CoBr2 > ZnBr2 > CuBr2.
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