Coordination complex

Complexes or coordination compounds are molecules that posess a metal center

that is bound to ligands (atoms, ions, or molecules that donate electrons to the
metal). These complexes can be neutral or charged. When the complex is charged,
it is stabilized by neighboring counter-ions.

Introduction

Coordination chemistry emerged from the work of Alfred Werner, a Swiss chemist
who examined different compounds composed of cobalt (III) chloride and
ammonia. Upon the addition of hydrochloric acid, Werner observed that ammonia
could not be completely removed. He then proposed that the ammonia must be
bound more tightly to the central cobalt ion. However, when aqueous silver nitrate
was added, one of the products formed was solid silver chloride. The amount of
silver chloride formed was related to the number of ammonia molecules bound to
the cobalt (III) chloride. For example, when silver nitrate was added to
CoCl3·6NH3, all three chlorides were converted to silver chloride. However, when
silver nitrate was added to CoCl3·5NH3, only 2 of the 3 chlorides formed silver
chloride. When CoCl3·4NH3 was treated with silver nitrate, one of the three
chlorides precipitated as silver chloride[1].

Properties of Coordination Complexes

Some methods of verifying the presence of complex ions include studying its
chemical behavior. This can be achieved by observing the compounds' color,
solubility, absorption spectrum, magnetic properties, etc. The properties of
complex compounds are separate from the properties of the individual atoms. By
forming coordination compounds, the properties of both the metal and the ligand
are altered.
Metal-ligand bonds are typically thought of Lewis acid-base interactions. The
metal atom acts as an electron pair acceptor (Lewis acid), while the ligands act as
electron pair donors (Lewis base). The nature of the bond between metal and
ligand is stronger than intermolecular forces because they form directional bonds
between the metal ion and the ligand, but are weaker than covalent bonds and ionic
bonds[2].

Common Ligands

Monodentate ligands donate one pair of electrons to the central metal atoms. An
example of these ligands are the haldide ions (F-, Cl-, Br-, I-). Polydentate ligands,
also called chelates or chelating agents, donate more than one pair of electrons to
the metal atom forming a stronger bond and a more stable complex. A common
chelating agent is ethylenediamine (en), which, as the name suggests, contains two
ammines or :NH2 sites which can bind to two sites on the central metal. An
example of a tridentate ligand is bis-diethylenetriammine. An example of such a
coordination complex is bis-diethylenetriamine cobalt III[3].

Standard addition

The method of standard addition is a type of quantitative analysis approach often

used in analytical chemistry whereby the standard is added directly to the aliquots
of analyzed sample. This method is used in situations where sample matrix also
contributes to the analytical signal, a situation known as the matrix effect, thus
making it impossible to compare the analytical signal between sample and standard
using the traditional calibration curve approach.[4]

Applications

Standard addition is frequently used in chemical instrumental analysis such

as atomic absorption spectroscopy and gas chromatography.[2]
Suppose that the concentration of silver in samples of photographic waste is to be
determined by atomic-absorption spectrometry. Using the calibration curve
method, an analyst could calibrate the spectrometer with some aqueous solutions
of a pure silver salt and use the resulting calibration graph in the determination of
the silver in the test samples. This method is only valid, however, if a pure aqueous
solution of silver, and a photographic waste sample containing the same
concentration of silver, give the same absorbance values. In other words, in using
pure solutions to establish the calibration graph it is assumed that there are no
‘matrix effects’, i.e. no reduction or enhancement of the silver absorbance signal
by other components. In many areas of analysis such an assumption is frequently
invalid. Matrix effects occur even with methods such as plasma spectrometry,
which have a reputation for being relatively free from interferences.

Procedure

A typical procedure involves preparing several solutions containing the same

amount of unknown, but different amounts of standard. For example, five 25 mL
volumetric flasks are each filled with 10 mL of the unknown. Then the standard is
added in differing amounts, such as 0, 1, 2, 3, and 4 mL. The flasks are then diluted
to the mark and mixed well.

The idea of this procedure is that the total concentration of the analyte is the sum
of the unknown and the standard, and that the total concentration varies linearly. If
the signal response is linear in this concentration range, then a plot similar to what
is shown above is generated.

Standard addition is used in quantitative analysis of chemicals. It is a calibration

method that involves adding an additional amount of the substance of interest to a
sample when a one-off or infrequently performed analysis is required.
An analyst usually divides the unknown sample into two portions, so that a known
amount of the analyte (a spike) can be added to one portion. These two samples,
the original and the original plus spike, are then analyzed. The sample with the
spike will show a larger analytical response than the original sample due to the
additional amount of analyte added to it.

The difference in analytical response between the spiked and unspiked samples is
due to the amount of analyte in the spike. This provides a calibration point to
determine the analyte concentration in the original sample.

The procedure is suitable when, for example, due to matrix effects the analytical
response for an analyte in a complex sample may not be the same as for the analyte
in a simple standard. In this case, calibration with a working curve would require
standards that closely match the composition of the sample.

For routine analyses it is feasible to prepare or purchase realistic standards, e.g.

NIST standard reference materials. For diverse and one-of-a-kind samples,
however, this procedure is time consuming and often impossible.

An alternative calibration procedure is the standard addition method as outlined at

the beginning of the page.

What is Job’s Method?

Job’s method is an analytical technique we can use to determine the stoichiometry

of a binding event by keeping the molar concentrations of reactants constant. This
method is named after the scientist Paul Job, who developed the technique in 1928.

Let us consider an example to understand the method. Consider a reaction mixture

which has two chemical species (B and D) that can bind with each other. The
stoichiometry for this binding reaction can be obtained using the Job’s method.
This means we don’t know exactly how much of B binds with D, or vice versa.
Using this method, we can find these exact amounts. For this determination, we
have to keep the sum of the molar concentrations of binding partners constant.
However, their molar fractions may vary. Therefore, we can run an experiment in
order to get readings for the mole fraction and the physical property that we are
going to measure. i.e. UV absorbance.

Within chemistry, a Job plot, otherwise known as the method of continuous

variation or Job's method, is a method used in analytical chemistry to determine
the stoichiometry of a binding event. The method is named after Paul Job and is
also used in instrumental analysis and advanced chemical equilibrium texts and
research articles. Job first published his method in 1928, while studying the
associations of ions in solution.[6] By plotting the UV absorbance of a solution
of Tl(NO3)/NH3 against the mole fraction of Tl(NO3), he produced a graph which
provided information about the equilibrium complexes present in solution.

A simple Job Plot showing how a physical property (P) changes upon changing the
mole fraction of compound A (ΧA).

In solutions where two species are present (i.e. species A and species B), one
species (A) may bind to the other species (B). In some cases, more than one A will
bind with a single B. One way to determine the amount of A binding to B is by
using a Job plot.

In this method, the sum of the molar concentrations of the two binding partners
(e.g. a protein and ligand or a metal and a ligand) is held constant, but their mole
fractions are varied. An observable that is proportional to complex formation (such
as absorption signal or enzymatic activity) is plotted against the mole fractions of
these two components.
χA is the mole fraction of compound A and P is the physical property being
measured to understand complex formation. This property is most oftentimes UV
absorbance.[2]

The maximum (or minimum) on the plot corresponds to the stoichiometry of the
two species if sufficiently high concentrations are used.[3] The plot also provides
insight to understand the equilibrium constant (Keq) of complex formation. A
greater curvature leads to a more evenly distributed equilibrium, while a more
triangle-shaped plot signifies a large Keq.[2] Further, after determining the
equilibrium constant, we can determine what complexes (ratio of A and B) are
present in solution.[4] In addition, the peak of the Job Plot corresponds to the mole
fraction of ligands bound to a molecule, which is important for studying ligand
field theory.[5] An early work of I. Ostromisslensky describes essentially this
approach.[6]

Requirements

There are several conditions that must be met in order for Job's method to be
applicable.[7] Firstly, the property being studied must vary in direct proportion to
the concentration of the species. In the case of UV-visible spectroscopy, for
example, this means that the system must conform to the Beer-Lambert law. In
addition, the total concentration of the two binding partners, the pH and ionic
strength of the solution must all be maintained at fixed values throughout the
experiment.

Finally, there must be only one complex in solution which predominates over all
others under the conditions of the experiment. This requirement means that only
systems with high association constants, or systems in which only one
stoichiometry can form, are suitable for analysis by Job plot. As such, the use of
the Job plot in supramolecular chemistry has been advised against.[8]

Limitations

1) This method is applicable to one type of equilibria i.e., only one type of
complex formation in the solution.

2) This is applicable to moderate stable complexes; it means it cannot be applied to

very weak complexes.

3) If the complexes are colourless, then spectrophotometric method cannot be used.

Measure the absorbance of prepared series of solution, according to Lambert's -
Beer's law.

4) pH and ionic strength must be maintained constant

Difference Between Job’s Method and standard Method

The key difference between Job’s method and standard method is that in Job’s

method, the molar concentrations of reactants are held a constant, while in mole
ratio method, the molar concentration of a reactant is kept constant and the molar
concentration of other reactants varies.

Job’s method is a process we can use in analytical chemistry to determine

the stoichiometry of binding of different chemical species. Mole ratio method is an
alternative method for the Job’s method. However, both techniques are useful in

References

1. ^ Harris, Daniel C. (2003). Quantitative Chemical Analysis 6th Edition.

New York: W.H. Freeman.
2. ^ Bader, Morris (1980). "A systematic approach to standard addition
methods in instrumental analysis". Journal of Chemical Education. 57 (10):
703. Bibcode:1980JChEd..57..703B. doi:10.1021/ed057p703.

3. ^ Bruce, Graham R. (June 1999). "Estimates of Precision in a Standard

Addition Analysis". Journal of Chemical Education. 76 (6): 805–
807. Bibcode:1999JChEd..76..805B. doi:10.1021/ed076p805.

4. ^ Job, Paul (1928). "Formation and Stability of Inorganic Complexes in

Solution". Annales de Chimie. 10. 9: 113–203.

5. ^ Jump up to:a b Renny, J. S.; Tomasevich, L. L.; Tallmadge, E. H.; Collum,

D. B. (2013). "Method of Continuous Variations: applications of job plots to
the molecular associations in organometallic chemistry". Angew Chem Int
Ed Engl. 46: 11998–2013.

6. ^ Huang, C.Y. (1982). "Determination of Binding Stoichiometry by the

Continuous Variation Method: The Job Plot". Methods in Enzymology. 87:
509–525.

7. ^ Facchiano, A.; Ragone, R. (2003). "Modification of Job's method for

determining the stoichiometry of protein – protein complexes". Analytical
Biochemistry. 313: 170–172. doi:10.1016/s0003-2697(02)00562-6.

8. ^ Hauser, A (2004). "Ligand Field Theoretical Considerations". Adv Polym

Sci. 233: 49–58.

9. ^ Ostromisslensky, Iwan (January 1911). "Über eine neue, auf dem

Massenwirkungsgesetz fußende Analysenmethode einiger binären
Verbindungen". Berichte der deutschen chemischen Gesellschaft. 44 (1):
268–273. doi:10.1002/cber.19110440141. ISSN 0365-9496.
10.^ MacCarthy, Patrick; Zachary D. Hill (February 1986). "Novel Approach to
Job's Method". Journal of Chemical Education. 63 (2): 162–167.
Bibcode:1986JChEd..63..162H. doi:10.1021/ed063p162.

11.^ Brynn Hibbert, D.; Thordarson, Pall (2016-10-25). "The death of the Job
plot, transparency, open science and online tools, uncertainty estimation
methods and other developments in supramolecular chemistry data
analysis". Chem. Commun. 52 (87): 12792–12805. doi:10.1039/c6cc03888c.
ISSN 1364-548X. PMID 27779264.

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