INTERACTIONS OF ANTIMONY(II1) HALIDES WITH

AMIDES AND TETRAMETHYLUREA IN

1,2-DICHLOROETHANE SOLUTION

CLAUDIO AIROLDI*, PEDRO L. 0. VOLPE and JOSEFA M. M. de M. LIRAt

Instituto de Quimica, Universidade Estadual de Campinas, 13100 Campinas, SBo Paulo, Brasil

(Received 11 November 1982; accepted 10 January 1983)

Abstract-The interactions of SbCl,, SbBr, and SbI, with N,N-dimethylformamide (DMF);

N,Ndimethylacetamide (DMA) and tetramethylurea (TMU) have been studied in 1,2dichloroethane
solution. The equilibrium constants and the respective variations of enthalpy for 1: 1 and 1: 2 specieswere
obtained by means of the incremental calorimetric titration technique. From AH; values.,the acidity order
SbCl, > SbBr, > SbI, and the basicity order TMU > DMA > DMF were established. The ionization in
solution such as autocomplex formation and halides displacement are discussed using conductometric
titration values.

The majority of p-block elements in lower valence
states have a lone electron pair which gives rise to an
irrcegmar coordination in tie adbucr 5onned. Ttis
lone pair of electrons in antimony(II1) halides is
wx&tere& ta beepre~attiinauZl_va? s-character, Aue to
th~e’jatiY.na~‘m’%&, m6recrhes~~e~-S”D-X an&es are
97-W. The38 f&g%3 ir%!ieate th& the St-X bend.
involves mainly the metal p-orbitals. The lone pair
leads to a high electron density close to the metal, in
spite of the difference in electronegativities of the
atcoms’m ‘Ihe m&h-hriirhebonh anh ConsepuenYry, 31
shum\b be bjffic& ‘lo accommoda1e a Letis base in
the coordination sphere. For 5 :5 ahon&forma’rjon a
rehybridisation is required to arrange the new ligand
in a trigonal-bipyramidal geometry, where the lone
pair is lying in an equatorial position. Identically, with
two molecules of bases an octahedral geometry is
formed, the lone pair occupying one site of coordi-
nation. X-Ray structure determinations of SbCl, ad-
ducts of aniline’, tetramethylthiourea3 and tri-
phenylarsine4 illustrate this behaviour, where the
strain of the lone pair causes a highly distorted geom-
etry.
The Lewis acid properties of these metal halides are
dir@?& by an in&r8aW in &oorcziRafioRnWzz&?~of
the metal through the formation of a u ligand-metal
bond. In solution this beltaauiaur can he iUstrated by
the interaction of SbCl, with some aliphatic and
aromatic amides.’ Molecular adducts are formed in
1: 1 and 1:2 stoichiometries, these reactions being
folIowed by vibrational spectroscopy. The relative
dcnar ability at the amides coward SK{, as a tied
acid was established by means of carbonyl and
antimony-chloride frequency shifts. Thus, in benzene
the order is DMA > DMF >NMA (NMA=
N,,~~~~~‘carni~~,~Ihi~~l:~~~,ir,cp#~~~~~n~
such as chloroform. In agreement with these results,
*Author to whom correspondence should be addressed.
tPermanent address: Departamento de Qulmica-
CCEN, Universidade Federal da Faraiba, Campus I-
Cidade UniversitPria, 58000 Jo20 Pessoa, Paraiba, Brasil.
in an aprotic solvent the basicity order
TMU)DMA)DMF was recently obtained using a
ca1orime%xictecYmi9ueP
Thermodynamic parameters involving the equi-
Vzkium bezween Sbx,, &ss~~veb in I,.~-&cltla-
r&inane anb a x&us ti3 ‘i_xanhs have &en I&-
stin&tic&$$ &t&W&. AxWng $!%3seligW&-j, tier8
are oxygen donors such as pyridine N-oxide, dimethyl
sulphoxide and triphenylphosphine oxide, which
showed successive formation of 1: 1 and 1: 2 adducts
in tk&nt% hp. where X, ) K_,.M D abrup’r Wmrence
was obseruet%in the enthaYip& d these sips d CDM-
&na%on. The ‘irgan& WJQ an& C,H,ND gave ti,&
stability constants at the first step of wmplexation, in
comparison with the analogous phosphorus and ni-
trogen donors, which presented small enthalpies of
formation. However, three moles of aliphatic amines
reacted quantitatively with metal-halides to produce
very large exothermic enthalpy changes. In this case,
it was suggested that the aliphatic amines are wordi-
nated to the halogen in the adducts rather than to the
metal.
In this paper, SbX3 were calorimetrically titrated
with N,N-dimethylformamide (DMF); N,N-
&n&2~.8~W22k!J.e (D2&BA) a.& t.&?AW~~~kz?~
(TMU) in the assumed inert solvent 1,2dichloro-
ethane. Ram the iaccemeatal ca~ariutetric titration
results, the stability constants and the variation of
enthalpy for the two steps of coordination of these
oxygen donors ligands were calculated.
Materials. All solvents for preparation of metal halides,
for calorimetry and for conductance measurements were
carefully dried, distilled and stored over molecular sieves.
N.Ndimethvlformamide:* N.N-dime~~vlacetamide9 and
tetramethylurea’O were previously distilled and dried over
barium oxide or sodium carbonate. After standing over-
night these solvents were distilled through an efficient
column under reduced pressure, collecting the fractions at
36°C and 30mmHg; 30°C and 6 mmHg and 80°C and
30mmHg for DMF, DMA and TMU, respectively. After
distillation these solvents were stored over molecular sieves.
All the manipulations concerning the metal halides were

1125
1126 C. AIROL .DI et al.

carried out under an atmosphere of dry nitrogen on a Table 1. Titration of 90.0 cm3 of SbCl, solution (1.30 x
vacuum line or in a dry-box. Antimony chloride (Carlo 1O-2 M) with 0.15 M DMF solution
Erba) was purified by sublimation in vacuum, giving a
melting point of 73”C, literature 73°C.” Antimony tri- 3
V/cm
- Qobs'J - Z Q,,,/J
bromide was prepared from the reaction of antimony with
an excess of bromine in carbon disulphide under an atmo-
90.00 0 0
sphere of nitrogen. When the antimony vanished, the sohr-
tion was pumped to dryness and the solid was crystallized 90.25 0.44 0.44
twice in carbon disulphide to give a product of melting point 90.54 0.88 1.32
96°C literature 96”C.‘* Antimony triiodide was prepared by 90.78 0.66 1.98
means of a direct reaction of the metal and iodine in 3.4;
91.29 1.50
benzene. After filtration the product was dried in oacIu) and
91.85 1.29 4.17
recrystallized in toluene, giving a melting point 17O”C,
literature 17O”C.‘* 92.65 2.07 6.84
Calorimetric measurements. All calorimetric experiments 93.45 1.75 8.59
were performed with the solvent 1,2-dichloroethane by 94.45 2.20 10.79
means of a LKB 8700-2 precision calorimetric system. The
95.46 1.86 12.65
titrand solution at (25.00 f O.OS’C) was incrementally ad-
ded to 9O.Ocm’ of the desired solution, already in the 96.67 2.13 14.70
calorimeter vessel and the heat recorded or described 98.17 2.09 16.87
previously.‘3J4 The calorimeter’s performance was checked 100.00 1.76 18.63
using the enthalpy of titration of hydrochloric acid with
tris(hydroxyamino)methane. is The metal halides were ti-
trated twice with each of the three ligands. In a typical
example, an SbCI, solution (1.30 x lo-* moles.l-‘) was
Table 2. Dilution of 90.0 cm3 of DMF solution (0.15 M)
titrated with a DMF solution of 0.15 moles.l-‘. A new
with 1,Zdichloroethane
titration of the same SbCI, solution was carried out with
a DMF solution 1.16 moles. I - ‘. The final volume in each
3
V/CllB QobdJ
case was ca. 100cm3 and the relative number of moles of ' 'obdJ
SbCI, to the number of hgand was 1.3/l and 10/l with
between 15 and 25 points. 90.00 0 0
The net enthalpy for each increment of titrand (Q”) was 90.49 0.46 0.46
calculated after subtracting the heat of dilution. The effect
91.14 0.53 0.99
produced by the ligand solution was determined when its
solution was added to 90.0 cm3 of 1,Zdichloroethane (Qs). 91.91 0.56 1.55
The heat of dilution of the metal halide solution was 92.70 0.56 2.11
calculated after the addition of solvent to the calorimeter 93.63 0.64 2.75
vessel containing 90.0 cm3 of the halide solution (Qc). Thus, 94.04 0.68 3.43
the variation of enthalpy due to the chemical reaction (Q,&
96.02 0.69 4.12
can be obtained by: Qob.= QA- Qr, - Qc. The K,, K,, AH,
and AH2 values are related to the interactions of metal 97.29 0.73 4.85
halides (SbX,) with the hgands (L): 90.74 0.79 5.64
100.00 0.74 ' 6.38
SbX, + L = SbX, . L; K,, AH:

SbX, . L + L = SbX, .2L; K2, AH;

where K, = ISbX, . L\/ISbX,~~L~ and K2 = ISbX, .2Ll/

Table 3. Dilution of 90.0cm3 of SbCl, solution (1.30 x
SbX, . LllL. A previously described procedure of calcu- IO-* M) with 1,2dichloroethane
Iation was 1ollowed to find, K,, K2, AH f and AH; values.
This method consists in adjusting the points of the ti- V/C”, 3 'obsJJ ' 'obstJ
trations of the calculated curve (Q,& to the experimental
one (Q.,,& In this procedure the function 90.00 0 0
U = Z (Qob,- Q&* is minimized by using a least square
90.63 0.28 0.28
programme.‘3~‘4
91.72 0.38 0.66
Conductance measurements. The metal halides were con-
ductometrically titrated at (25.00 + O.OZ’C)with the hgands 93.15 0.36 1.02
in 1,2dichloroethane to high concentration of metal 95.15 0.38 1.40
halide/hgand; i.e. about l/10. In these series of mea- 97.44 0.38 1.78
surements a Metrohm Herisau Konduktoskop E 365 bridge 2.21
100.00 0.43
was used.

RESULTS AND DISCUSSION

The progress of the reaction between the metal
halides SbXj (X = Cl, Br, I) and the ligands L
(L = DMF, DMA, TMU) was studied in
l,Zdichloroethane, which is considered to be a very
poor interacting solvent. The results of a typical
calorimetric titration are listed in Table 1 and the
enthalpies of dilutions QBand Qc are given in Tables
2 and 3, respectively. The plot of the heat obtained
against the volume is presented in Fig. 1. From these
incremental calorimetric titrimetry values the thermo-
dynamic parameters of Table 4 were calculated. In an
attempt to obtain information about the ionic behav-
iour in 1,2dichloroethane, the metal halides were
conductometrically titrated in the same range of con-
centration as that carried out in the calorimetry mea-
surements. The plot of Fig. 2 represents the ionic
character of the metal halides when titrated with
tetramethyhtrea. The curves of distribution of SbBr,,
SbBr, * DMF and SbBr, * 2DMF species in Fig. 3
 Interactions of antimony(II1) halides 1127

Table 4. Stability constants and the corresponding variation of enthalpies for interactions of antimony
halides with the ligands
-1
Acid K~/oD~-~ II - Ali;/kJmol-' K2Jd -AU;/kJ mol-'

SbCl3 1160 f 1 26.8 f 0.1 216 f 1 20.9 t 0.1

460 f 1 36.4 f 0.1 1915 f 1 31.7 f 0.1
79 i 1 58.7 f 0.1 25 f 1 38.0 t 0.1

SbBr3 473 f 1 28.9 f 0.2 4220 f 2 21.1 f 0.2

(900 t 41105 39.4 f 0.2 100 t 2 29.2 t 0.2
800 f 1 42.8 f 0.2 1375 f 2 44.3 t 0.2

SbI3 (320 f 2)103 27.9 f 0.2 (110 t 2)104 17.6 + 0.2

(140 f 2)105 28.6 f 0.2 (170 f 2)104 19.7 t 0.2
(600 f 2)103 33.5 f 0.2 (98 f 2)104 21.2 f 0.2

Fig. 1. Calorimetric titration of 90.0 cm3 of a 1.30 x 10e2 M solution of SbCl, with 0.15 M DMF solution.
The experimental points in curves A, B and C represent the summation of QA’s,Qis and Qc’s, respectively.
The calculated points in curve D represent the summation of the Qw

Fig. 2. Conductometric titration of 90.0cm3 of metal halides with TMU in 1,2dichloroethane:

1.42xl0-2MSbCI,and0.99MTMU,1.31x10-2MSbBr,and0.99MTMU;3.03x10-3MSbI,and
0.28 M TMU.
1128 C. AIROLDI ef al.
3. Distribution curve of SbBr, ’ 2DMF and SbBr, . DMF adducts in the SbBr,-DMF system in
1,Zdichloroethane at 298 K.
were calculated from values of K, and K2 obtained
from the titrations.
The halides SbX, (X = Cl, Br) interact exother-
mically with the amides. However, SbIS produces an
endothermic effect in this process except with DMA in
high concentration. In all cases the dilution leads to
an endothermic effect more pronounced with SbI,, in
spite of its lower concentration, due to its reduced
solubility in the solvent.
Calorimetric measurements between SbX, and
DMA have been previously obtainedi with the fol-
lowing AH? values: - 35.98 (SbCl,), - 30.96 (SbBr,)
and -31.80 (Sb13) kJ mol-‘, which are comparable
with our results. From these values the authors did
not establish any acidity order for these metal halides.
In the mean time, our AHf results (Table 4) demon-
strate that TMU is a more suitable base to
differentiate the acidity properties of the metal ha-
lides, giving the order SbCl, > SbBr, > Sb13, as is also
observed with triphenylphosphine oxide.’ This behav-
iour is associated with the donor number of the
ligands.” Whereas DMF and DMA have the values
26.6 and 27.8, respectively, leading to similar en-
thalpies; TMU with donor number 31, leads to a
different AH,” values.
The enthalpies values listed in Table 4 show an
increase from DMF to TMU, reflecting the increasing
donor number of these ligands. In all cases the basic-
ity order TMU > DMA > DMF can be proposed,
since any metal halide is tixed as acceptor. This
sequence of basicity is clearly seen with SbCl,. On the
other hand, the same sequence was previously estab-
lished for the interaction of this acid with the above
bases by means of the reactions in condensed phase,6
viz. SbCl,(s) + L(e) = SbC& 1L(e, s); AH;:
-27.82 + 0.15; -37.96 + 0.16 and -44.86 If:
0.27 kJmol-’ for DMF, DMA and TMU, re-
spectively.
The metal halides in the concentration range of the
calorimetric titrations give the same specific conduc-
tivity of the net solvent, thus they maintained their
characteristic molecular properties in this medium.
Although the metal halides present some degree of
dissociation during the conductometric titrations with
the ligands, the molar conductivity is much below that
of 1: 1 electrolyte type behaviour.” Figure 2 shows a
conductometric titration of SbXs with TMU. The
conductance results reveal the donor-acceptor com-
plex formation, which depends on the donor proper-
ties of the ligand, the polarizability and the energy of
Sb-X bond. The highest conductance values observed
for SbI, (Fig. 2) fit very well with the most basic ligand
and the characteristics of Sb-I bond.
The stability constant values of K,, for the for-
mation of the adducts of SbC&, increase from TMU
to DMF, which is the inverse order of the donor
ability of the ligands. This enhancement of the equi-
librium constant in that sequence suggests that the
autocomplex should be formed, producing ionic spe-
cies in solution, with a consequent decrease of the
amount of the adduct formed. This fact can be
explained in considering the equations of formation
of adduct and autocomplex:r9
SbCI, + L + SbQ . L;
K, = [SbC&, . L]/[SbCl,][L]
ZSbCl, . L G SbCl,L: + SbCl; ;
K, = [SbCl,L;][SbCI, J/[SbCI, . L]*.
The autocomplex is more easily formed with TMU
due to its highest donor power. In this way the K,
value turns out to be the smallest among these values.
For the second step of complexation TMU and DMF
present K2 <K,, which are normally interpreted by
statistical effects. Thus, K2 values for both ligands
suggest the predominance of SbCI, .2L species in
solution due to the reaction SbCl, . L + L
e SbCI, .2L. However, the highest K2 value for
DMA indicates an ionization in solution with the
 Interactions of antimony(III) halides
displacement of chloride: SbCl, 1DMA + DMA
e [SbC& . ZDMA] + + Cl-. These results corrobo-
rate with that found in the conductance titrations,
where DMA presents a higher conductance in com-
parison with other ligands. This behaviour also
affects the interaction of SbBr, and DMA, where the
K, value suggests the presence of ionic species in
solution due to autocomplex formation:
2SbBr, +DMA P [SbBr22DMA]+ + [SbBr,]-. A de-
crease of this constant is observed with DMF and
TMU; such results indicating the predominance of
the formation of the adduct: SbBr, + L # SbBr, . L.
In examining Kz for this system, higher values are
shown for TMU and DMF. The displacement of
bromide for these bases can be suggested as:
SbBr, . L + L * [SbBr, .2L]+ + Br- . The lowest Ks
value for DMA favours an equilibrium in the course
of adduct formation SbBr, . DMA . + DMA
Z$ SbBr3 ’ 2DMA.
The equilibrium constants involving the ligands
and Sb13 are all large in value (Table 4). The first
species formation suggests that it might have an
auto-association in solution. As previously described
ionized species should prevail in solution, being more
accentuated with DMA. For the second step of
complexation, for all cases, an ionization occurs with
exchange of ligand, with predominance of ionic spe-
cies in solution. This fact is consistent with the
conductometric data which show that Sb13 presents
the highest degree of conductivity among the metal
halides and that DMA more easily displaces the
halides from SbX,. The conductivity order for the
trihalides is SbI, > SbBr, > SbCl, and for the amides
the displacement order of halide is
DMA > TMU > DMF.
Acknowledgements-The authors are indebted to
FINEP for financial support. One of us
1129
(J.M.M.M.L.) gratefully acknowledges a feilowship
from CAPES-PICD.
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