Thermochemical parameters of 1,2,3,4-tetrahydroquinoline adducts of some divalent transition metal bromides

doi:10.4236/ns.2011.37075

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Vol.3, No.7, 535-541 (2011) Natural Science

http://dx.doi.org/10.4236/ns.2011.37075

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: [email protected]

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

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

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

P. O. Dunstan / Natural Science 3 (2011) 535-541

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



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:



MBrcalorimetric solventsolution A,



 (1)



n THQsolution Asolution B,



  (2)



MBrTHQncalorimetric solvent

solution C, H









 (3)

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:

 



2s 1ns

MBrn THQMBrTHQ,





 



(5)

where r123

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

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:





M2Br n THQ

MBr2THQng,





 







(6)

where



θ2+

fI ff

θθ

adductΔHM

2ΔHBrn ΔHTHQ







 .

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

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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