Chem 3rd Year
Chem 3rd Year
Chem 3rd Year
the net change in crystal energy resulting from the orientation of d orbitals of a transition
metal cation inside a coordinating group of anions also called ligands.
A major feature of transition metals is their tendency to form complexes. A complex may be
considered as consisting of a central metal atom or ion surrounded by a number of ligands.
The interaction between these ligands with the central metal atom or ion is subject to
crystal field theory.
Crystal field theory was established in 1929 and treats the interaction of metal ion and
ligand as a purely electrostatic phenomenon where the ligands are considered as point
charges in the vicinity of the atomic orbitals of the central atom. Development and
extension of crystal field theory taken into account the partly covalent nature of bonds
between the ligand and metal atom mainly through the application of molecular orbital
theory. Crystal field theory is often termed ligand field theory.
When transition metals are not bonded to any ligand, their d orbitals degenerate that is
they have the same energy. When they start bonding with other ligands, due to different
symmetries of the d orbitals and the inductive effect of the ligands on the electrons, the d
orbitals split apart and become non-degenerate.
t2g– set of three orbitals (dxy, dyz and dxz) with lower energy
eg – set of two orbitals (dx2-y2 and dz2) with higher energy
t2– set of three orbitals (dxy, dyz and dxz) with higher energy
e – set of two orbitals (dx2-y2 and dz2) with lower energy
The crystal field splitting in a tetrahedral complex is intrinsically smaller in an octahedral
filed because there are only two thirds as many ligands and they have a less direct effect of
the d orbitals. The relative stabilizing effect of e set will be -6Dq and the destabilizing effect
of t2 set will be +4Dq
For example, the net change in energy for d5 and d10 systems will be zero as shown below.
d0 0 0 0 0
d1 4 4 6 6
d2 8 8 12 12
d3 12 12 8 (18)*
d4 6 16 4 (24)*
d5 0 20 0 (20)*
d6 4 24 6 (16)*
d7 8 18 12 12
d8 12 12 8 8
d9 6 6 4 4
d10 0 0 0 0
Thus, the crystal field splitting depends on the field produced by the ligand and the charge
on the metal ion. An experimentally determined series based on the absorption of light
by coordination compound with different ligands known as spectrochemical series has been
proposed. Spectrochemical series arranges ligands in order of their field strength as:
I– < Br– < Cl– < SCN– < F– < OH– < C2O42- < H2O < NCS– < EDTA4- < NH3 < en < CN–< CO
Filling of d-orbitals takes place in the following manner; the first three electrons are
arranged in t2g level as per the Hund’s rule. The fourth electron can either enter into
the t2g level giving a configuration of t2g4eg0 or can enter the eg orbital giving a configuration
of t2g3eg1. This depends on two parameters magnitude of crystal field splitting, Δ o and
pairing energy, P. The possibilities of the two cases can better be explained as
Δo > P – Electron enters in the t2g level giving a configuration of t2g4eg0. Ligands
producing this configuration are known as strong field ligands and form low spin
complexes.
Δo < P – Electron enters in the eg level giving a configuration of t2g3eg1. Ligands
producing this configuration are known as weak field ligands and form high spin
complexes.
The magnitude of the crystal field splitting (Δ) dictates whether a complex with four, five,
six, or seven d electrons (in an octahedral complex) is high spin or low spin, which affects its
magnetic properties, structure, and reactivity. Large values of Δ (i.e., Δ > P) yield a low-spin
complex, whereas small values of Δ (i.e., Δ < P) produce a high-spin complex. The
magnitude of Δ depends on four factors: the valence of the metal, the principal quantum
number of the metal (and thus its location in the periodic table), the geometry, and the
nature of the ligand(s).
Increasing the valence of a metal ion has two effects: the radius of the metal decreases and
ligands are more strongly attracted to it due to Coulombic attraction. Both factors decrease
the metal–ligand distance, which in turn causes the ligands to interact more strongly with
the d-orbitals. Consequently, the magnitude of Δo increases as the valence of the metal
increases. Typically, Δo for a M(III) is about 50% greater than for the M(II) of the same
metal; for example, for [V(H2O)6]2+, Δo = 11,800 cm−1; for [V(H2O)6]3+, Δo = 17,850 cm−1.
For a series of complexes of metals from the same group in the periodic table with the
same charge and the same ligands, the magnitude of Δo increases with increasing principal
quantum number: Δ (3d) < Δ (4d) < Δ (5d). The data for hexaammine complexes of the
trivalent Group 9 metals illustrate this point:
The number of ligands in a complex as well as how well the ligand geometry overlaps with
the d orbitals is also a factor in the magnitude of the crystal field splitting. For example,
comparing octahedral and tetrahedral geometries the octahedral geometry has 6 ligands,
and those 6 ligands overlap directly with the two d orbitals that lie along the
axes, dx2−y2��2−�2 and dz2��2. The tetrahedral geometry has fewer ligands than
octahedral, and those ligands overlap less ideally with the ligands that lie between the
axes, dxy���, dxz���, and dyz���. Because of this the crystal field splitting of a
tetrahedral complex is generally less than half ( 49 49 than an octahedral complex with the
same metal and ligands. For example [FeCl4]- has a Δt = 5,200 cm-1 and [FeCl6]3- has a Δo =
11,600 cm-1.
In crystal field theory ligands are all modeled as negative point charges, which means that
all ligands should behave identically. Experimentally, it is found that the Δ o observed for a
series of complexes of the same metal ion depends strongly on the nature of the ligands.
For a series of chemically similar ligands, the magnitude of Δo decreases as the size of the
donor atom increases. For example, Δo values for halide complexes generally decrease in
the order F > Cl > Br > I because smaller, more localized charges, such as we see for F,
interact more strongly with the d-orbitals of the metal. In addition, a small neutral ligand
with a highly localized lone pair, such as NH3, results in significantly larger Δo values than
might be expected. Because the lone pair points directly at the metal ion, the electron
density along the M–L axis is greater than for a spherical anion such as F. The
experimentally observed order of the crystal field splitting energies produced by different
ligands is called the spectrochemical series.
Ligands are classified as strong field or weak field based on the spectrochemical series:
weak field I-< Br- < Cl-< SCN- < F-< OH- < ox-2< ONO < H2O < SCN- < NH3 < en < NO2 < CN-, CO
strong field
Note that SCN and NO2 ligands are represented twice in the above spectrochemical series
since there are two different Lewis base sites (e.g., free electron pairs to share) on each
ligand (e.g., for the SCN ligand, the electron pair on the sulfur or the nitrogen can form the
bond to a metal). The specific atom that binds in such ligands is underlined. Ligands on the
weak field end of the series (halogens, OH, H2O) will tend to form high spin complexes and
ligands on the strong field end of the series (CN, CO, NO2) will tend to form low spin
complexes. Intermediate ligands in the midle of the series could form high or low spin
complexes depending on other factors.
Organometallic Compounds are chemical compounds which contain at least one bond
between a metallic element and a carbon atom belonging to an organic molecule. Even
metalloid elements such as silicon, tin, and boron are known to form organometallic
compounds which are used in some industrial chemical reactions.
The catalysis of reactions wherein the target molecules are polymers or pharmaceuticals
can be done with the help of organometallic compounds, resulting in an increase in the rate
of the reactions.
Generally, the bond between the metal atom and the carbon belonging to the organic
compound is covalent in nature. When metals with relatively high electropositivity (such as
sodium and lithium) form these compounds, a carbanionic nature is exhibited by the carbon
which is bound to the central metal atom.
The bond between the metal and the carbon atom is often highly covalent in nature.
Most of the organometallic compounds exist in solid states, especially the
compounds in which the hydrocarbon groups are aromatic or have a ring structure.
The compounds consisting of highly electropositive metals such as sodium or lithium
are very volatile and can undergo spontaneous combustion.
In many cases, organometallic compounds are found to be toxic to humans
(especially the compounds that are volatile in nature).
These compounds can act as reducing agents, especially the compounds formed by
highly electropositive metals.
From the points given above, it can be observed that the properties of organometallic
compounds differ from the other based on the properties of the metals that constitute
them.
Applications
Organometallic Compounds have a broad range of applications in the field of chemistry.
Some of them are given below-
Reduction
All organometallic compounds are potential reducing agents, and those of the
electropositive elements are very strong reducing agents because the metal gives
up electrons to the carbon, resulting in a polar M―C bond with a partial positive charge on
the metal and a negative charge on the carbon. Organometallic compounds of highly
electropositive elements such as lithium, sodium, and aluminum ignite spontaneously and
sometimes explode on contact with air or other oxidizing agents. The useful organometallic
reagents Li(CH3), Zn(CH3)2, B(CH3)3, and Al2(CH3)6 are spontaneously flammable in air
(pyrophoric). Accordingly, techniques have been developed to handle these and other
pyrophoric compounds. Glass reaction vessels sealed from the atmosphere and purged
with nitrogen gas are commonly used for handling air-sensitive organometallic compounds
in the laboratory. Large quantities of pyrophoric compounds such as Al2(C2H5)6 are routinely
handled with ease in the chemical industry by using closed metal reactors for the
production of these and other much less reactive compounds. Organometallic compounds
have reduced reactivity when the metallic component is not highly electropositive and
when the metal is completely surrounded by attached groups. For example, elevated
temperatures are required to initiate combustion with Si(CH3)4 and Sn(CH3)4, and at room
temperature they can be handled in air.
Carbanion character
alkyllithium and Grignard reagents
Highly reactive organometallic reagents, such as alkyllithium and Grignard reagents (LiR and
RMgX, respectively), have multiple synthetic applications.(more)
The partial negative charge of an organic group bonded to a highly active metal results in a
distinctive pattern of reactivity that is frequently referred to as nucleophilic
or carbanion character. Thus, organometallic compounds containing highly active
(electropositive) metals, such as lithium, magnesium, aluminum, and zinc, react rapidly and
completely with water, liberating a hydrocarbon in the process. For example, dimethylzinc
liberates methane gas along with solid zinc hydroxide.Zn(CH3)2 + 2H2O → Zn(OH)2 + 2CH4
The above hydrolysis of dimethylzinc can be viewed as a transfer of a slightly acidic H + from
water to the strongly basic carbanion CH3− in dimethylzinc.
Most of the organometallic compounds are coordination compounds that consist of one or
more ligands attached to the metal M through M-C bonds. The rules governing their
nomenclature are therefore similar to those naming of coordination compounds. In the case
of organometallic compounds few additional rules are observed.
1. The ligands (without the prefixes mono, di, tri etc.) are named in alphabetical order
irrespective of the charge present on them.
2. The presence of hydrocarbon ligands in the coordination sphere is indicated by the
names of their radicals (methyl, ethyl etc.).
3. In case of unsaturated molecules or groups, the ligand is named with the prefix η n.
Metallic elements of group 2,13,14,15 as well as the transition metals with fully filled d-
orbitals such as Zn, Cd and Hg produces organometallic compounds where the bonding of
metal atoms to carbon atoms occurs via sigma (σ) bond.
Organometallic compounds which are loosely bound are called electron deficient and occur
in polymeric forms that fall under this category. These compounds can be regarded as a
halfway between the σ bonded organometallic compounds of Sn, Pb etc. and ionic
organometallic compounds of alkali metals. Elements which have a high tendency to form
multicentre organometallic compounds are Li, Br, Mg, B and Al.
Eg. Ferrocene
1. Direct method
Magnesium reacts with alkyl or aryl halide in ether to give Grignard reagent which is an
organometallic compound.
3. Transmetallation method
It involves the replacement of one metal by another. It is achieved by the action of more
electropositive metal such as zinc with a compound having metal with low electropositivity.
Due to the lanthanide contraction property of mercury (Hg), it becomes more electropositive
than zinc (Zn).
In such a reaction, the alkyl group migrates to the more electronegative metal.
The carbon atom and the metal are usually bonded through covalent bonds.
Mostly when the compounds have aromatic hydrocarbon groups or a ring structure,
the organometallic compound exists in solid states.
Volatile organometallic compounds are found toxic to humans.
They act as reducing agents.
Organometallic compounds have many applications in the field of chemistry. Some of them
are listed below:
Organolithium Compounds
What is Chromatography?
Chromatography is the technique for the separation, purification, and testing of
compounds.
The term “chromatography” is derived from Greek, chroma meaning, “colour,” and
graphein meaning “to write.”
In this process, we apply the mixture to be separated on a stationary phase (solid or liquid)
and a pure solvent such as water or any gas is allowed to move slowly over the stationary
phase, carrying the components separately as per their solubility in the pure solvent.
Table of Contents
Principles of Chromatography
Types of Chromatography
Related Topics on Chromatography
What is Differential Extraction?
Applications of Chromatography
Frequently Asked Questions
Principles of Chromatography
Chromatography is a separation method where the analyte is combined within a liquid or
gaseous mobile phase., which is pumped through a stationary phase. Usually one phase is
hydrophilic and the other is lipophilic. The components of the analyte interact differently
with these two phases. Depending on their polarity they spend more or less time
interacting with the stationary phase and are thus retarded to a greater or lesser extent.
This leads to the separation of the different components present in the sample. Each
sample component elutes from the stationary phase at a specific time called as retention
time. As the components pass through the detector their signal is recorded and plotted in
the form of a chromatogram.
Types of Chromatography
The four main types of chromatography are
1. Adsorption Chromatography
In the process of adsorption chromatography, different compounds are adsorbed on the
adsorbent to different degrees based on the absorptivity of the component. Here also, a
mobile phase is made to move over a stationary phase, thus carrying the components with
higher absorptivity to a lower distance than that with lower absorptivity. The main types of
chromatographic techniques that are used in industries are given as under.
The plate used for this process is known as chrome plate. The solution of the mixture to be
separated is applied as a small spot at a distance of 2 cm above one end of the plate. The
plate is then placed in a closed jar containing a fluid termed as an eluant, which then rises
up the plate carrying different components of the mixture to different heights.
3. Column Chromatography
Column chromatography is the technique used to separate the components of a mixture
using a column of suitable adsorbent packed in a glass tube, as shown in the figure below.
The mixture is placed on the top of the column, and an appropriate eluant is made to flow
down the column slowly.
Depending upon the degree of adsorption of the components on the wall adsorbent
column, the separation of the components takes place. The component with the highest
absorptivity is retained at the top, while the other flow down to different heights
accordingly.
Column Chromatography
4. Partition chromatography
The most common hetero atoms found on a cyclic ring are Oxygen (O), Nitrogen (N) and Sulphur (S).
Example:
Nucleic Acid that is present in the body responsible for storing and expressing genetic information, is an
example of a Heterocyclic compound.
Essential micronutrient, Vitamins is also an example of a heterocyclic compound.
The majority of drugs, pesticides, dyes, and plastics are examples of heterocyclic compounds.
Based on the number of heteroatoms present, we can further classify them into two categories:
Based on the number of heteroatoms present, we can further classify them into two categories:
Based on the number of heteroatoms present, we can further classify them into two categories:
Based on the number of heteroatoms present, we can further classify them into two categories:
Here, we put a spot at the base of the chromatographic paper with the mixture to be
separated and as the solvent rises up this paper, the components are carried to different
degrees depending upon their retention on the paper. The components are thus separated
at different heights.
Related Topics on Chromatography
Adsorption Chromatography
Thin Layer Chromatography
Column Chromatography
Partition Chromatography
Applications of Chromatography
The organic compound is later recovered by the process of distillation or evaporation. The
process of continuous extraction is used in cases when the solubility of the compound is
less in the organic solvent.
Applications of Chromatography
In bio analytical chemistry, chromatography is mainly used for the separation, isolation and
purification of proteins from complex sample matrices. In cells for example, proteins occur
alongside numerous other compounds such as lipids and nucleic acids. In order to be
analysed, these proteins must be separated from all the other cell components. Then the
proteins of interest might have to be isolated from other proteins and purified further.