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Hybridization involving d Orbitals


In dsp2 (pronounced as d-s-p two) one d orbital, one s orbitals and two p orbital mix together to give four equivalent degenerate dsp2 hybrid orbitals. These four orbitals lie in a plane with bond angles 90° with respect to each other (Fig. 1.55). In dsp2, d orbital belongs to penultimate shell.
s + p + p + d of the same atom

Formation of dsp2 Hydrid Orbitals

 

Example
[Ni(CN)4]2- Hybridization Scheme
Electronic configuration of 28Ni : 1s22s22p63s23p63d84s2
In the given ion, nickel exists in the + 2 oxidation state.
Thus Electronic configuration of 26Ni2+: 1s22s22p63s23p63d8
The electronic configuration of Ni2+ in free state and that existing in the complex ion are as follows.


            3d                                               3d       

Bonding
The four : CN- ions form coordinate bonds with the four empty dsp2 hybrid orbitals of Ni2+ forming planar complex. 
sp3d : In sp3d (pronounced as s-p three d) , one s orbital three p orbitals and one d orbital mix together to give five degenerate sp3d hybrid orbitals. These five orbitals are directed to the corners of trigonal bipyramid—three are in the same plane making angle 120° with each other, fourth and fifth are directed perpendicular to the plane (one above and the other below)
s + p + p + p+ d     of the same atom

Formation of sp3d Hybrid Orbitals
Example
Phosphorous Pentachloride

Hybridization Scheme
Electronic configuration of 15P:  1s22s22p63s23px13py13pz1
Phosphorus pentachloride has triangular bipyramid geometry. So, phosphorus involves sp3d hybridization. The electronic configuration of P in the free state and that existing in the compound are as follows.

In PCl5, each P—Cl bond is formed by the overlapping of sp3d(P) and 3pz(cl) orbitals. The structure of PCl5 is

sp3d2 or d2sp3 Hybridization
In sp3d2 (pronounced as s-p three d two) or d2sp3 (pronounced as d two s-p three) one s orbital, three p orbitals and two d orbitals mixed together to give six equivalent sp3d2 or d2sp3 hybrid orbitals. These six orbitals are directed to the corners of a regular octahedron—four are in the same plane making angle 90° with each other, fifth and sixth are directly perpendicular to the plane (one above and the other below).

s + p + p + p + d + d of the same atom

 

Formation of sp3d2 Hybrid Orbitals

Example  
Sulphur Hexafluoride
Hybridization Scheme
Electronic configuration of 16S: 1s22s22p63s23px23py13pz1
Sulphur hexafluoride has regular octahedral geometry So, sulphur involves sp3d2 hybridization. The electronic configuration of S in the free state and that existing in the compound is shown in the following.

In SF6, each S—F bond is formed by the overlapping of sp3d2(S) and 2pz(F) orbitals. The structure of SF6 is

Table Describes the Six Kinds of Hybridization 
Type of atomic orbitals being mixed Resultant hybrid orbitals Bond angle between hybrid orbitals Examples of molecules Shape of molecules

One s + one p

sp

180° 

BeCl2,HgCl2
BeH2, C2H2  



Linear

One s + two p

sp2

120° 

 

BF3, BCl3,CO, NO,C2H4


Plane triangle

One s + three p

sp3  

109°28' 

CH4, NH, NH3, H2O,ClO,SnCl4


Tetrahedron

One s + two p
        + one d

dsp2 

90° 

[Ni(CN)4]2-  [PtCl4]2-



Square planar

One s + three p
     + one d

sp3d

90°, 120° 

PF5, PCl5


Trigonal bipyramidal

One s + three p
     + two d

sp3d2 

90° 

SF6, CrF, Co(NH3)


Octahedron





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