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Understanding Hybridization and Molecular Orbitals in Organic Chemistry, Study notes of Chemistry

The concept of hybridization in organic chemistry, focusing on the involvement of d-orbitals in the third and later periods, and the different types of hybridization such as sp3d and sp3d2. It also covers multiple carbon-carbon bonds, the trigonal planar electron arrangement, and the limitations of lewis's theory. Examples of molecules like clf3, benzene, acetylene, and the importance of molecular orbital theory.

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2021/2022

Uploaded on 09/12/2022

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9.12 Hybrids Including d-Orbitals
d-orbitals can be involved in the hybridization
at central atoms from the third or later periods
of the table which form expanded octets
sp3d-hybridization a combination of one s,
three pand one dorbitals (used to describe the
trigonal bipyramidal e-arrangement)
sp3d2-hybridization a combination of one s,
three pand two dorbitals (used to describe the
octahedral e-arrangement)Fig. 9.37, 9.38
Identification of the hybridization scheme
draw the Lewis structure and identify the electron
arrangement
use the following correspondence
Example: What is the hybridization at the Cl
atom in ClF3.
1. Lewis structure: ntot=28, nrem=22, nneed=20
nneed<nrem 2extra e-(place at the central atom)
trigonal
bipyramidal e-
arrangement
sp3d -
hybridization
2. 2lone pairs + 3bonded atoms = 5
9.13 Multiple Carbon-Carbon Bonds
In molecules with more than one central atom,
the hybridization is determined individually for
each central atom
Example: Benzene, C6H6
Each Catom in benzene has a trigonal
planar electron arrangement (0lone
pairs + 3bonded atoms = 3)
sp2-hybridization for all Cs
The σσ-skeleton is formed by the sp2hybrids of the Cs
and the s-orbitals of the Hs
Three ππ-bonds are formed from the sideways overlap of
the unhybridized p-orbitals of the Cs
The resonance spreads the ππ-bonds over the entire ring
The molecule is flat, because such geometry provides for
the best overlap between the p-orbitals
Fig. 9.44, 9.45, 9.46
pf2

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9.12 Hybrids Including d-Orbitals

  • d -orbitals can be involved in the hybridization

at central atoms from the third or later periods

of the table which form expanded octets

  • sp^3 d-hybridization – a combination of one s ,

three p and one d orbitals (used to describe the

trigonal bipyramidal e-^ arrangement )

  • sp^3 d^2 -hybridization – a combination of one s ,

three p and two d orbitals (used to describe the

octahedral e-^ arrangement )

Fig. 9.37, 9.

  • Identification of the hybridization scheme
    • draw the Lewis structure and identify the electron arrangement
    • use the following correspondence

Example: What is the hybridization at the Cl

atom in ClF 3.

1. Lewis structure: ntot=28, nrem=22, nneed=

nneed<nrem ⇒⇒ 2 extra e-^ (place at the central atom)

⇒ trigonal

bipyramidal e-

arrangement

⇒ sp^3 d -

hybridization

2. 2 lone pairs + 3 bonded atoms = 5

9.13 Multiple Carbon-Carbon Bonds

  • In molecules with more than one central atom,

the hybridization is determined individually for

each central atom

Example: Benzene, C 6 H 6

Each C atom in benzene has a trigonal planar electron arrangement ( 0 lone pairs + 3 bonded atoms = 3 ) ⇒ sp^2 -hybridization for all Cs

The σσ -skeleton is formed by the sp^2 hybrids of the C s and the s-orbitals of the H s Three ππ -bonds are formed from the sideways overlap of the unhybridized p - orbitals of the C s The resonance spreads the ππ -bonds over the entire ring The molecule is flat , because such geometry provides for the best overlap between the p-orbitals

Fig. 9.44, 9.45, 9.

Example: Acetylene, C 2 H 2

H–C ≡≡ C–H (linear e-^ arrangement for both C s) ⇒ sp-hybridization for both C s

σσ -skeleton – formed by the sp hybrids of C and the s-orbitals of H Two ππ -bonds at 90º to each other – formed by the sideways overlap of the unhybridized p - orbitals of the C s

Fig. 9.47, 9.

  • Internal rotation in molecules
    • allowed around single bonds (the overlap between the orbitals is preserved during rotation)
    • not allowed around double bonds (rotation disturbs the parallel alignment of the p-orbitals and reduces their overlap, the ππ -bond breaks)

Example:

C 2 H 6 - rot. is allowed C 2 H 4 - rot. is not allowed

Fig. 9.40 Fig. 9.

Molecular Orbital Theory

9.14 The Limitations of Lewis’s Theory

  • Lewis’s theory fails in describing:
    • electron-deficient compounds – have too few electrons ( B 2 H 6 , Diborane – must have at least 7 bonds ( 14 e- ) to bond the 8 atoms, but has only 12 valence e- )
    • radicals – odd electron species ( NO , 11 e- s)
    • paramagnetism – attraction to magnetic fields characteristic for substances with unpaired e- s ( O 2 , is paramagnetic, but has no unpaired e- s in its Lewis structure) - The molecular orbital theory resolves these

problems by introducing molecular orbitals

  • similar to the atomic orbitals, but spread throughout the whole molecule
  • can be occupied by no more than 2 electrons with opposite spins – Pauli exclusion principle (explains the significance of e-^ pairs)
  • can be occupied by single electrons (provides explanations of odd-electron species and paramagnetic properties)