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Empirical Formulae to Molecular Structures of Metal

Complexes by Molar Conductance
a a a
Imran Ali , Waseem A. Wani & Kishwar Saleem
a
Department of Chemistry, Jamia Millia Islamia (Central University) , New Delhi , India
Accepted author version posted online: 22 Apr 2013.Published online: 14 May 2013.

To cite this article: Imran Ali , Waseem A. Wani & Kishwar Saleem (2013) Empirical Formulae to Molecular Structures of Metal
Complexes by Molar Conductance, Synthesis and Reactivity in Inorganic, Metal-Organic, and Nano-Metal Chemistry, 43:9,
1162-1170, DOI: 10.1080/15533174.2012.756898

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 Synthesis and Reactivity in Inorganic, Metal-Organic, and Nano-Metal Chemistry, 43:1162–1170, 2013
Copyright C Taylor & Francis Group, LLC
ISSN: 1553-3174 print / 1553-3182 online
DOI: 10.1080/15533174.2012.756898
Empirical Formulae to Molecular Structures of Metal
Complexes by Molar Conductance
Imran Ali, Waseem A. Wani, and Kishwar Saleem
Department of Chemistry, Jamia Millia Islamia (Central University), New Delhi, India
Molar conductance studies of electrolytic solutions have always
been exciting for chemists. The studies of electrolytic behavior of
metal complex solutions provide brief insights into their nature
Downloaded by [Universita degli Studi di Torino] at 17:09 18 July 2013
and composition. These studies provide a clue of the number of
ions present in a particular solution responsible for the conduction
of electric current and, thereby, quite significant structural infor-
mation can be obtained. Molar conductance data are exploited
to ascertain electrolytic and non-electrolytic nature of metal com-
plexes. Attempts have been made to summarize molar conductance
ranges of metal complexes in various solvents, which might prove
useful to researchers and academia. Besides, molar conductance
data have been applied to predict geometries of metal complexes.
Moreover, efforts have been made to discuss the applications of
conductance data for the estimation of the size of structurally rel-
evant complexes. In addition, molar conductance has been applied
to determine metal-ligand stoichiometry. Finally, the structural
variance of metal complexes in different solvents is discussed in
terms of molar conductance measurements.
Keywords electrolytic and non-electrolytic metal complexes, ge-
ometries, molar conductance, stoichiometry, structural
variance
INTRODUCTION
Conductivity is a physical property having a wide range of
applications in various chemical and biochemical processes.[1,2]
The concept of conductance has diverse applications in assess-
ing solvent purity, ionic strengths of solutions (including func-
tioning as a detector for ion chromatography), dissolution ki-
netics, critical micellar concentrations, enzymatic reactions and
thermodynamic data.[1] The measured values of conductivity
for different solutions are not easy to compare because of their
concentration dependent nature. However, molar conductivity
is a characteristic property of chemical substances independent
of concentration.[3,4] The molar conductivity (m) is given by
Received 14 June 2012; accepted 4 December 2012.
The authors are thankful to University Grants Commissions for
providing BSR fellowship to Waseem A. Wani.
Address correspondence to Imran Ali, Department of Chemistry,
Jamia Millia Islamia (Central University), New Delhi-110025, India.
E-mail: drimran ali@yahoo.com; drimran.chiral@gmail.com
1162
the following equation.
m = k/C [1]
where k and C are specific conductivity and concentration
in mol cm−3, respectively. The unit of molar conductivity is
−1cm2mol−1.
Similar to other physicochemical methods, molar conduc-
tance has been used for structure elucidation of newly synthe-
sized metal complexes.[5–15] The tentative structures of metal
complexes can be established easily with the help of molar con-
ductance data. The structure elucidation of metal complexes
can be fully predicted if the elemental composition (CHNS)
and spectroscopic data is available. First, such types of attempts
were made by Geary in 1971.[16] This review has been a source
of reference for many academicians and researchers for several
years. The time of 42 years has passed and various advance-
ments have been made during this period. The article of Geary
does not fulfill all the requirements of structural chemists in
the present scenario, which needs the advanced version of the
article. Therefore, attempts have been made to write an article
extending the work of Geary. Besides, some new fundamen-
tal concepts have been included in this article for discussing the
applications of molar conductance data for the structure elucida-
tion of newly synthesized metal complexes. The new addition
into this article includes the possibility of estimating the size
of ligands in series of structurally relevant complexes and the
stoichiometry of the complexes in terms of metal-ligand ratio
from their available molar conductance data. Moreover, efforts
have been made to discuss the solution structures of coordina-
tion complexes in solvents of varying polarities and dielectric
constants. This article is useful for researchers, academia, and
students of undergraduate and graduate levels.
EXPERIMENTAL
Structure Determination of Metal Complexes
A thorough search of literature was carried out and we col-
lected molar conductance data for about one thousand metal
complexes. The review article by Geary was also considered.
Based on these data, we developed two tables (Tables 1 and 2),
predicting the electrolytic and non-electrolytic nature of metal
 CONDUCTANCE AND STRUCTURES OF METAL COMPLEXES 1163

TABLE 1 N
Molar conductance ranges for nonelectrolytes and electrolytes
in different solvents
O
Non-electrolyte Electrolyte OH
molar molar Cu
Cl
conductance conductance H2O
range range H2O
H2O
S. No. Solvent (−1cm2mol−1) (−1cm2mol−1)
1 Nitromethane <70 >75 FIG. 1. Octahedral Cu(II) complex.
2 Nitrobenzene <20 >20
3 Acetonitrile <120 >120
4 Acetone <95 >100
5 DMF <60 >65 of a metal complex can be predicted easily. By using these mo-
6 Methanol <80 >80 lar conductance data and the pre-established structure of ligand,
7 Ethanol <30 >35 one can easily predict the geometry (square planar, octahedral,
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8 DMSO <50 >50 tetragonal) of any metal complex.

9 Water <80 >118
complexes and the ratios of their positive (coordination sphere
cations) and negative counterpart charges, respectively.
Definitely, the compilation of molar conductance data in tab-
ular form is a remarkable and innovative achievement for struc-
tural chemists. It is important to note that the empirical formula,
the structure and the nature of coordinating groups should be
known prior to the application of molar conductance data. The
application of molar conductance data starts with the determi-
nation of molar conductivity, which determines electrolytic or
non-electrolytic nature of the metal complexes. It is clear from
Table 1 that one can determine electrolytic or non-electrolytic
nature of metal complexes just by measuring its molar conduc-
tance and comparing with the data of Table 1. Besides, Table 2
shows molar conductance ranges of different solvents for 1:1,
1:2, 1:3, and 1:4 cationic and anionic counterparts of metal com-
plexes. From this table, the number of anions (primary valency)
Metal complexes have different values of molar conduc-
tance; characteristic features of their structures. These values
often vary for same complexes when investigated in differ-
ent solvents. These variations may be due to different polar-
ities and densities of the solvents. These solvent properties
are responsible for causing differential ionization and move-
ment of counter ions of a complex. Moreover, solvent interac-
tions with the ions of the complexes also play a crucial role
in determining the conductance of complexes. For example, a
complex, [Cu(HL)(H2 O)3 ]Cl (Figure 1) in DMF has molar
conductance of 80 −1cm2mol−1,[17] while the same com-
plex in acetonitrile has a molar conductance value of 132
−1cm2mol−1. Both these values indicate 1:1 electrolytic nature
of the complex. The higher molar conductance of this complex in
acetonitrile as compared to DMF may be due to higher polarity
and lower density of acetonitrile as compared to DMF; affect-
ing the ionization of [Cu(HL)(H2 O)3 ]Cl to a greater extent than
DMSO. The lower density of acetonitrile might be helping in the
quicker movement of ions and, thus, contributing to higher molar
conductance.

TABLE 2
The ranges of molar conductances of metal complexes with 1:1, 1:2, 1:3, and 1:4 ratios of cationic and anionic species
Molar conductance (−1cm2mol−1) ranges
S. No. Solvents 1:1 Electrolyte 1:2 Electrolyte 1:3 Electrolyte 1:4 Electrolyte References
[16]
1 Nitromethane 75–95 150–180 220–260 290–330
[16]
2 Nitrobenzene 20–30 50–60 70–82 90–100
3 Acetonitrile 120–160 220–300 340–420 >500 [16]

4 Acetone 100–140 160–200 270–330 >360 [16]

5 DMF 65–90 130–170 200–240 >300 [16,24]

6 Methanol 80–122 160–220 290–350 >450 [16,25]

7 Ethanol 35–45 70–90 120–140 >160 [16]

[16,26,27]
8 DMSO 50–90 110–195 200–240 —
[28,29]
9 Water 118–131 145–273 408–435 540–560
 1164 I. ALI ET AL.

TABLE 3
Molar conductance values and geometry of complexes
S. No. Complex m Solvent Nature of the organic ligand Geometry References
[30]
1 [Ni(C12 H9 SNOBr)2 ] 3.41 DMSO Mono-negative and bidentate Square-planar
[18]
2 [CuC20 H42 N6 O2 ]Cl2 152.5 Water Neutral tetradentate macrocycle Square-planar
[18]
3 [NiC20 H42 N6 O2 ]Cl2 148.7 Water Neutral tetradentate macrocycle Square-planar
[18]
4 [CoC20 H42 N6 O2 ]Cl2 192.0 Water Neutral tetradentate macrocycle Square-planar
[31]
5 [Cu(C6 H7 N3 OS)2 ]Cl2 136 DMF Neutral bidentate Schiff base Square-planar
[32]
6 [Cu(C7 H9 N3 O2 )2 ]Cl2 154 DMF Neutral bidentate Schiff base Square-planar
[32]
7 [Cu(C7 H9 N3 OS)2 ]Cl2 152 DMF Neutral bidentate Schiff base Square-planar
[32]
8 [Pt(C15 H10 N3 S)2 ]C3 H6 O·2H2 O 23.5 DMF Di-negative and bidentate Square-planar
[33]
9 [CoC22 H18 N6 O8 ](NO3 )2 120 DMSO Neutral tetradentate Schiff base Square-planar
[33]
10 [NiC22 H18 N6 O8 ](NO3 )2 113 DMSO Neutral tetradentate Schiff base Square-planar
[33]
11 [CuC22 H18 N6 O8 ](NO3 )2 117 DMSO Neutral tetradentate Schiff base Square-planar
[33]
12 [ZnC22 H18 N6 O8 ](NO3 )2 114 DMSO Neutral tetradentate Schiff base Square-planar
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[19]
13 [CoC30 H26 N2 O4 ]Cl2 185 DMSO Neutral hexadentate macrocycle Octahedral
[19]
14 [Mn(C30 H26 N2 O4 ](NO3 )2 175 DMSO Neutral hexadentate macrocycle Octahedral
[8]
15 [Mn(C15 H15 NO)2 Cl2] 18 DMF Neutral bidentate Schiff base Octahedral
[8]
16 [Ni(C15 H15 NO)2 Cl2] 18 DMF Neutral bidentate Schiff base Octahedral
[8]
17 [Co(C15 H15 NO)2 Cl2] 18 DMF Neutral bidentate Schiff base Octahedral
[34]
18 [Co(C12 H10 N3 O3 S)2 ] 23.8 DMSO Uni-negative and tridentate Octahedral
[34]
19 [Co(C13 H12 N3 O3 S)2 ] 17.25 DMSO Uni-negative and tridentate Octahedral
[34]
20 [Ni(C12 H10 N3 O3 S)2 ] 22.88 DMSO Uni-negative and tridentate Octahedral
[21]
21 [Cr(C16 H12 N4 )Cl2 ]Cl 88.5 DMF Neutral tetradentate macrocycle Octahedral
[21]
22 [Cr(C16 H12 N4 )Cl2 ]Cl 95.0 DMF Neutral tetradentate macrocycle Octahedral
[21]
23 [Cr(C22 H24 N4 )Cl2 ]Cl 81.0 DMF Neutral tetradentate macrocycle Octahedral
[21]
24 [Ni(C16 H12 N4 )Cl2 ] 8.5 DMF Neutral tetradentate macrocycle Octahedral
[21]
25 [Ni(C16 H12 N4 )Cl2 ] 8.2 DMF Neutral tetradentate macrocycle Octahedral
[21]
26 [Ni(C22 H24 N4 )] Cl2 7.4 DMF Neutral tetradentate macrocycle Octahedral
[35]
27 [Co(C28 H23 N4 OF)2 Cl2 ] 19.22 DMF Neutral bidentate Schiff base Octahedral
[35]
28 [Ni(C28 H23 N4 OF)2 Cl2 ] 22.25 DMF Neutral bidentate Schiff base Octahedral
[35]
29 [Cu(C28 H23 N4 OF)2 Cl2 ] 23.67 DMF Neutral bidentate Schiff base Octahedral
[35]
30 [Mn(C28 H23 N4 OF)2 Cl2 ] 23.4 DMF Neutral bidentate Schiff base Octahedral
[36]
31 [Co(C12 H20 N8 S2 )Cl2 ] 17 DMSO Neutral tetradentate macrocycle Octahedral
[36]
32 [Co(C12 H20 N8 S2 )(NO3 )2 ] 12 DMSO Neutral tetradentate macrocycle Octahedral
[36]
33 [Co(C12 H20 N8 S2 )(OCOCH3 )2 ] 11 DMSO Neutral tetradentate macrocycle Octahedral
[36]
34 [Ni(C12 H20 N8 S2)Cl2 ] 16 DMSO Neutral tetradentate macrocycle Octahedral
[36]
35 [Ni(C12 H20 N8 S2 )(NO3 )2 ] 15 DMSO Neutral tetradentate macrocycle Octahedral
[36]
36 [Ni(C12 H20 N8 S2 )(OCOCH3 )2 ] 12 DMSO Neutral tetradentate macrocycle Octahedral
[36]
37 [Zn(C12 H20 N8 S2 )(OCOCH3 )2 ] 12 DMSO Neutral tetradentate macrocycle Octahedral
[37]
38 [MnC22 H20 N12 O2 S2 ]Cl2 82.70 DMSO Neutral tridentate ligand Octahedral
[37]
39 [FeC22 H20 N12 O2 S2 ]Cl3 225.8 DMSO Neutral tridentate ligand Octahedral
[37]
40 [CoC22 H20 N12 O2 S2] ]Cl2 91.90 DMSO Neutral tridentate ligand Octahedral
[37]
41 [NiC22 H20 N12 O2 S2 ]Cl2 108.6 DMSO Neutral tridentate ligand Octahedral
[37]
42 [ZnC22 H20 N12 O2 S2 ]Cl2 107.6 DMSO Neutral tridentate ligand Octahedral
[20]
43 [Cu(C10 H12 N4 S4 O4 ) Cl2 ] 12 DMSO Neutral tetradentate macrocycle Tetragonal
[8]
44 [Cu(C15 H15 NO)2 Cl2] 17 DMF Neutral bidentate Schiff base Tetragonal
[34]
45 [Cu(C13 H12 N3 O3 S)2 ] 21.11 DMSO Uni-negative and tridentate Tetragonal
[36]
46 [Cu(C12 H20 N8 S2 )Cl2 ] 17 DMSO Neutral tetradentate macrocycle Tetragonal
[36]
47 [Cu(C12 H20 N8 S2 )(NO3 )2 ] 12 DMSO Neutral tetradentate macrocycle Tetragonal
[36]
48 [Cu(C12 H20 N8 S2 )(OCOCH3 )2 ] 12 DMSO Neutral tetradentate macrocycle Tetragonal
[37]
49 [CuC22 H20 N12 O2 S2 ]Cl2 79.20 DMSO Neutral tridentate ligand Tetragonal
[38]
50 [CuC22 H24 N4 O6 ] 17.9 DMSO Di-negative hexadentate ligand Tetragonal
 CONDUCTANCE AND STRUCTURES OF METAL COMPLEXES
OH
HO N N
N Cu N
N N
Cl2
FIG. 2. Square-planar copper(II) macrocyclic complex.
Attempts have been made to discuss the structures of some
complexes by using molar conductance data, which are given in
Table 3. Let us discuss the most commonly observed geometries
(square planar, octahedral and tetragonal) in metal complexes.
First example is of copper complex with CuC20 H42 N6 O2 Cl2 as
Downloaded by [Universita degli Studi di Torino] at 17:09 18 July 2013
empirical formula. In this empirical formula, the structure of the
main ligand has already been established as neutral tetradentate
macrocyle by elemental analyses and spectroscopic data. Its
molar conductance in water is 152.5 (−1cm2mol−1), which in-
dicates that the complex is electrolytic in nature with 1:2 ratio
of coordinating sphere cation and anion (Table 2). This is pos-
sible only if two chloride ions exist outside the coordination
sphere. Therefore, the molecular formula of this complex can
be written as [CuC20 H42 N6 O2 ]Cl2 . It is known that ligand is
tetradentate and the only possibility is of square-planar geome-
try. This geometry has also been verified by experimental data
(Figure 2).[18]
Further, let us take one more example of another complex
(i.e., CoC30 H26 N2 O4 Cl2 ) with neutral hexadentate macrocycle
as ligand. The molar conductance of this complex in DMSO
is 185.0 −1cm2mol−1. According to Tables 1 and 2, it is
electrolytic in nature with 1:2 coordination sphere cation and
anion ratio. Therefore, the molecular formula is written as
[CoC30 H26 N2 O4 ]Cl2 . Applying the knowledge of coordination
chemistry, the complex is octahedral in nature as shown in
Figure 3.[19] Similarly, the ligand of CuC10 H12 N4 S4 O4 Cl2 com-
plex is a neutral tetradentate macrocycle. Its molar conductance
in DMSO is 12.0 −1cm2mol−1; indicating the non-electrolytic
nature of the complex (Tables 1 and 2). Therefore, two chloride
anions should be inside the coordination sphere, giving rise to
John Teller Distortion
[CuC10H12N4S4O4Cl2]
(Octahedral)
Theoritical structure
FIG. 4.
1165
O N O
Co
O O Cl2
N
FIG. 3. Octahedral cobalt(II) complex.
[CuC10 H12 N4 S4 O4 Cl2 ] as the molecular formula of this com-
plex. Now, applying the knowledge of coordination chemistry,
the complex is octahedral but in nature it exists as tetragonal
(Figure 4) due to the John Teller effect.[20] Efforts have been
made to correlate the structures of various metal complexes
with their molar conductance values and are summarized in Ta-
ble 3. These data may be used to elucidate the structures of other
newly synthesized complexes in future.
Relative Size of Ligands
It is a well-known fact that electrolytic conductance is di-
rectly proportional to the mobility of the constituent ions (ionic
mobility) of the electrolyte. Ionic mobility measures the speed
with which ions in an electrolyte move under the influence of
an external electric field. A metal complex in a given solvent
dissociates into two parts viz. a large coordination part and
the counter ions (primary valency satisfiers). Large sized ions
are expected to move slower than the small sized ions. Molar
conductance data gives us an insight into estimating the rela-
tive size of ligands in series of structurally relevant complexes.
For example, the molar conductance of nickel(II) complexes
(Figure 5) of 12-, 14-, and 16-membered macrocycles, is in the
order; 12-membered > 14-membered > 16-membered. This or-
der can be explained on the basis of the fact that an increase in
ligand size of the complexes tends to decrease their molar con-
ductance values. However, little difference exists between the
molar conductance of fourteen and 12 membered complexes due
to their near similar sizes. In this way the molar conductance
O O
NH S HN
S Cl Cu Cl S
NH HN
S
O O
(Tetragonal)
Actual structure
Tetragonal copper(II) complex.
 1166 I. ALI ET AL.

H H H H TABLE 4
Cl Molar conductance values of complexes 1, 2, and 3 in water,
Cl
N N N N methanol, acetonitrile and nitromethane
Ni Ni
Molar Conductance (−1cm2mol−1)
N N N N
Cl Complex Water Methanol Acetonitrile Nitromethane
Cl
H H H H
Twelve membered nickel complex Fourteen membered nickel complex 1 270 124 74 29
2 254 100 107 55
FIG. 5. Nickel complexes of structural isomeric 12- and 14-membered macro- 3 200 136 130 92
cycles.

data provides the structural clue for structurally related provides a clue for determining their metal-ligand stoichiome-
complexes.[21] tries. For example, a neutral organic ligand (L) with three po-
tential donor atoms (e.g., S, O, or N) while reacting with a metal
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ion such as copper(II) (M) can be assumed to form two main

Metal to Ligand Stoichiometry
The molar conductance values also provide useful informa-
tion for metal to ligand stoichiometry. It has been observed that
metal complexes with 1:2 metal-ligand stoichiometries have
lower molar conductance values as compared to the analo-
gous complexes with 1:1 metal-ligand stoichiometry. A keen
observation of the molar conductance data of the complexes
types of complexes viz. [ML2 ]X2 (1:2; metal-ligand complex)
and [MLX]X (1:1; metal-ligand complex); where X is a unineg-
ative counter ion. The molar conductance of the first and second
complex will correspond to 1:2 and 1:1 electrolytic nature. This
is due to the fact that the first complex will dissociate into
ML+2 −
2 and 2 Cl ions while second complex will dissociate into
+1 −
ML and Cl ions, respectively. Therefore, which complex is

NH

N
Co Cl PF6
N
NH

Methanol

NH NH
NH NH

N N
N Acetonitrile Co Cl Co Cl
N
Co H2 O
Co Cl PF6 Water PF6 Cl PF
PF6 N 6
N N
N NH
NH NH
NH
Solid sate
b' b"

Nitromethane

NH

N
Co Cl
PF6
N
NH

FIG. 6. (a) Structures of complex 3 in solid state, water, methanol, acetonitrile, and nitromethane. (Continued)
 CONDUCTANCE AND STRUCTURES OF METAL COMPLEXES 1167

CH3
N
MeOH
N
Co
Cl Cl
N
N
CH3

Methanol

CH3 CH3 CH3

N N N
Acn Cl OH2
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N Acetonitrile N N
Co Co Water Co
Cl Cl Cl OH2 Cl2
N N N
N N N
CH3 CH3 CH3
Solid sate

Nitromethane
CH3
N
Cl
N
Co
Cl
N
N
CH3

FIG. 6. (b) Structures of complex 1 in solid state, water, methanol, acetonitrile, and nitromethane. (Continued)

practically formed will be decided by the molar conductance
data. In this way, molar conductance data may be exploited to
establish metal-ligand stoichiometry.
Structural Variations of Complexes in Different Solvents
It is well known that the structures of metal complexes vary
in different solvents. The structural variance of a complex in
different solvents is of prime importance in physical, chemi-
cal, and biological processes. The molar conductance data also
provides some clue for determining the structures of metal com-
plexes in different solvents. Solvent molecules themselves act as
coordinating ligands and, therefore, coordinate to metal ions in
a complex by the displacement of counterions. These displace-
ment reactions quite significantly change the molar conductance
ranges of complexes. Analysis of all such changes provides
the information about the structures of complexes in solution
phase. Hubin and coworkers studied the solution structures of
cobalt(II) and copper(II) complexes of a series of topologically
constrained and cross-bridged tetraazamacrocycles.[22,23] Hubin
et al. determined the molar conductances of Co(II) complexes
of topologically constrained tetraazamacrocycles in water, ace-
tonitrile, methanol and nitromethane (Table 4). The results pre-
sented in this table support the fact that the solution ionization
(displacement of chloride by solvent) of these complexes is con-
sistent with the dielectric constant and coordinating ability of
the solvent.
Two of the three complexes (1 and 2; Figure 6) in water
have molar conductance values in the range of 1:2 electrolytes
natures, indicating the replacement of two chlorido ligands
by two water molecules. Surprisingly, the conductance of the
 1168 I. ALI ET AL.

CH3
N
MeOH
N
Co
Cl Cl
N
2 N
CH3

Methanol

CH3 CH3
N CH3
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N
N
Acn Cl
N N OH2
Acetonitrile Co Water N
Co Co
Cl Cl Cl Cl2
N OH2
N N
N N N
CH3 CH3 CH3
Solid sate

Nitromethane

CH 3
N
Cl
N
Co
Cl
N
N
CH 3

FIG. 6. (c) Structures of complex 2 in solid state, water, methanol, acetonitrile, and nitromethane. (Continued)

five-coordinate complex 3 is between 1:1 and 2:1 electrolytes.
This suggests that the single chlorido ligand is only partially
displaced in water. Therefore, complex 3 exists in equilibrium
with the structures b and b as shown in Figure 6. How-
ever, in methanol, the first chlorido ligand is fully replaced
by solvent molecules and all the three complexes exceeded typ-
ical 1:1 electrolyte behavior. Contrarily, there is no effect of
methanol on the second chloride. Moreover, in acetonitrile all
the three complexes have conductance values slightly less than
1:1 electrolytes. This implies that one molecule of the solvent
has partially displaced one chlorido ligand from the coordina-
tion spheres of both the six-coordinate complexes. Furthermore,
there is no chlorido displacement in the five- coordinate complex
3. Finally, in nitromethane, a solvent with low dielectric con-
stant and non-coordinating ability, the six-coordinate complexes
behave as non-electrolytes, revealing that the chlorido ligands
remain in bound form. The structure of the complex in solution is
six-coordinate pseudo-octahedral as in the solid state. However,
five-coordinate complex 3 in nitromethane has a molar conduc-
tance consistent with a 1:1 electrolyte. This indicates the pres-
ence of the unbound PF6 anion, without singly bound chlorido
ligand dissociation. The solution structures of complexes 1 and
2 in nitromethane, acetonitrile, methanol, and water are given in
Figure 6. This type of information is very important for deter-
mining the fate of the complexes in biological and environmental
matrices.
 CONDUCTANCE AND STRUCTURES OF METAL COMPLEXES
CONCLUSION
The molar conductance data is very important information
for the structure elucidation of metal complexes. The data of
electrolytic and non-electrolytic natures and the ratio of coordi-
nating cationic sphere and anions (in case of electrolytic metal
complexes) can be applied to empirical formulae of metal com-
plexes for predicting their three dimensional structures. More-
over, ligand sizes of structurally relevant complexes, the amount
of ligand forming part of a complex and the solution structures
of metal complexes can be easily established from their molar
conductance data. Briefly, this approach is highly useful for de-
termining the structures of newly synthesized metal complexes
without involving sophisticated paraphernalia.
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