Wednesday, January 30, 2013

Hapticity

              Hapticity is a term describing how a group of contiguous atoms are bonded to a central atom of a coordination compound. Each atom of the contiguous group is bound only once to the central atom. The Hapticity of a ligand is indicated by the Greak character ' eta ' . 'eta' denotes the number of contiguous atoms of the ligand that are bound to the metal.
Example :
             Ferrocene is a molecule with two cyclopentadienyl rings bound to a central iron m olecule. Five contiguous carbon atoms are bound to the central iron atom, the hapticity is five.

Pi Back Bonding

           Pi back bonding also called Pi back donation. In this bond electrons move from an atomic orbital on one atom to Pi * antibonding orbital on another atom or ligand. Mostly common in organo-metallic chemistry of transition metals with multi-atomic ligand such as carbon monoxide , ethylene or the nitrosonium cations. Electrons from the metals are used to bond to the ligand, in the process relieving the excess negative charge.

Dipolar Bond

         A dipolar bond is covalent bond between the two atoms where one of the atom provides both electrons that form the bond. A dipolar bond also known as dative covalent bond or coordinate bond is a kind of 2c - 2e bond.
        When Lewis base donates a pairs of electrons to a Lewis acid that time dipolar bonds are formed. This description of bonding is a characteristic of valence bond theory.It has no place in molecular orbital theory or ligand field theory. 

Tuesday, January 29, 2013

Bond Order

          Bond order is the number of chemical bonds between a pairs of atom. In a covalent bond between two atoms, an single bond has a bond order of one, a double bond has a bond order of two, a triple bond has a bond order of  3 and so on.
Example :

  • Determine the bond order of hydrogen gas ; H2
  • H - H   Bond order is one.

VSEPR Theory ( Valance Shell Electron Pair Repulsion )


BASIC ASSUMPTIONS :
  1. The electron pair in the valence shell around the central atom of a molecule repel each other and tend to orient in space so as to minimize the repulsion and maximize the distance between them.
  2. There are two types of valence shell electron pairs .
  • Bond pairs
  • Lone pairs
Bond pairs are shared 2 atoms and are attracted by 2 nuclei. Hence they occupy less space and cause less repulsion.
Lone pairs are not involved in bond formation and are in attraction with only one nucleus. hence they occupy more space. As a result the lone pair causes more repulsion.
The order of repulsion between the different types of electron pairs is as follows:
Lone pairs - Lone pairs > Lone pair - Bond pair > Bond pair - Bond pair.

Note :
     Bond pairs are usually represented by a solid line, where as the lone pairs are represented by a lobe with 2 electrons.

  1. In VSEPR theory the multiple bonds are treated as if they where single bond. The electron pairs in multiple bonds are treated collectively as a super pair. The repulsion caused by bonds increases with increase in the number of bonded pairs between two atoms. ie : The triple bond causes more repulsion than the double bond which turn causes more repulsion than single bond. 
  2. The shape of molecules can be predicted from the number and types of valence shell electron pairs around the central atom. When the valence shells of central atom contains only bond pairs. The molecules assumes symmetrical geometry due to even repulsion between them. However the symmetry disorted when there are also lone pairs along with bond pairs due to uneven repulsion forces.
  3. Primary and secondary effects on bond angle and shape :
  •  The bond angle decreases due to the presence of lone pairs, which cause more repulsion on the bond pairs and as a result the bond pairs tend to come closer.
  • The repulsion between electron pairs increase with increase in electro negativity of central atom and hence the bond angle is increases. The bond pairs are closer and thus by shortening the distance between them, which turn to increase the repulsion.Hence the bond tends to move away from each other.
The bond pairs tend to move away from each other since the distance between them is shortened as they are more localized on more electronegativity central atom.
However the bond angle decreases when the electronegativity of the ligand atoms are more than that of central atom. There is increase in distance between bond pairs since they are closer to ligand atoms. Due to this they tend to move closer resulting in the decrease in bond angle.
The bond pairs tend to come closer since the distance between them is increases as they are more localized on more electronegative ligand atoms.
The bond angle decrease with increase in the size of central atom.
On smaller central atoms the bond pairs are closer and hence tend to move away from each other so as to minimize repulsion. Hence bond angle will be more.
On bigger atoms, the bond pairs are distant from each other and hence there is less repulsion. They tend to move closer and thus by decrease the bond angle. However the bond angle in the size of the ligand atoms, which surrounded the central atom.
There is less repulsion between smaller ligand atoms and they can move closer to each other and decrease the bond angle.
There is more repulsion between bigger ligand atoms and hence they tend to move away from each other and the bond angle is increases.
The bond angles are also changed when multiple bonds are present.It is due to uneven repulsion.
  1. when there are two or more resonance structures, the VSEPR theory is applicable to any of such contributing structure. 

Periodic Table Trends

Moving Left To Right :

  • Atomic radius decreases.
  • Ionization energy increases.
  • Electronegativity decreases.
Moving Top To Bottom :
  • Atomic radius Increases
  • Ionization energy decreases
  • Electronegativity decreases.

Electronegativity

                 Electronegativity is the measure of the attraction of an atom from the electron in a chemical bond. The higher electronegativity of an atom , the greater attraction for bonding electron. Electronegativity is related to ionization energy.

  • Electrons with low ionization energy have low electronegativity . Because their nuclei do not exert a strong attractive force on electrons.
  • Electrons with high ionization energies have high electronegativity due to the strong pill exerted on electrons by the nucleus.
                 In a group the electronegativity decreases as atomic number increases. As a result increase distance between the valence electron and nucleus. ( greater atomic radius )

Example :
  • Electropositive (ie: low electronegativity) element is cesium.
  • High elecgtronegativity element is fluorine.