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Coordination Complex Complexes or Coordination Compounds Are Molecules That Posess A Metal Center
Coordination Complex Complexes or Coordination Compounds Are Molecules That Posess A Metal Center
Coordination Complex Complexes or Coordination Compounds Are Molecules That Posess A Metal Center
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].
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
Applications
Procedure
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.
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.
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.
References
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.
12.