Chapter 5 Bonding in polyatomic molecules

Polyatomic species: contains three or more atoms

Three approaches to bonding in diatomic molecules 1. Lewis structures 2. Valence bond theory 3. Molecular orbital theory

Orbital hybridization - sp

sp _ hybrid =

1 ( 2 s + 2 px ) 2

sp _ hybrid =
Hybrid orbitals generated by mixing the characters of atomic orbitals

1 ( 2 s 2 px ) 2

Orbital hybridization sp2

sp 2 _ hybrid =

1 2 2 s + 2 px 3 3

sp 2 _ hybrid =

1 1 1 2 s 2 px + 2 p y 3 6 2

sp 2 _ hybrid =

1 1 1 2 s 2 px 2 p y 3 6 2

sp3 hybrid orbitals one s and three p atomic orbitals mix to form a set of four orbitals with different directional properties

sp 3 _ hybrid = sp 3 _ hybrid =

1 2 s + 2 px + 2 p y + 2 p z 2 1 2 s + 2 p x 2 p y 2 p z 2

) )

sp 3 _ hybrid = sp 3 _ hybrid =

1 2 s 2 p x + 2 p y 2 p z 2 1 2 s 2 p x 2 p y 2 p z 2

) )

sp3d hybrid orbitals one s, three p, and one d atomic orbitals mix to form a set of five orbitals with different directional properties

[Ni(CN)5]3-

Valence bond theory multiple bonding in polyatomic molecules

Valence bond theory multiple bonding in polyatomic molecules

Valence bond theory multiple bonding in polyatomic molecules

Molecular orbital theory: ligand group orbital approach in triatomic molecules

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Molecular orbital theory: BF3

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Consider the S3 operation (=C3h) on the pz orbitals in the F3 fragment.

C3 2 2 S3 3 S3 C3 3 S3 1 Unique, S32
The resulting wavefunction contributions from the S3 and S32 operations are 3 and 2, respectively.

1 S3 2 Unique, S3 1

3 h

2 S3 2

1 S3 2 2 3

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BF3 3 Resonance Structures

The presence of the resonance contributions account for the partial double bond character in BF3

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SF6

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Find number of unchanged radial 2p orbitals that are unchanged under each Oh symmetry operation. 1 C2 Note the C2 axis bisect the planes containing 4 p orbitals. The C2 axis contains no 2p orbitals.

4 6

C2

E 6

C3 0

C2 0

C4 2

C2 i S4 (C42) 2 0 0

S6 0

h 4

d 2

Use the reduction formula to find the resulting symmetries: a1g, t1u, eg Could derive the equations for the LGOs for the F6 fragment.

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1 ( 1 + 2 + 3 + 4 + 5 + 6 ) 6 1 (t1u )1 = ( 1 6 ) 2 1 (t1u ) 2 = ( 2 4 ) 2 1 (t1u )3 = ( 3 5 ) 12 (eg )1 = (2 1 2 3 4 5 + 2 6 ) 12 1 (eg ) 2 = ( 2 3 + 4 5 ) 2

(a1g ) =

Three-center twoelectron interactions

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