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Molecular Geometry and Bonding Theories

Molecular Geometry and Bonding Theories

The overall shape of a molecule is determined by its bond angles

AB2

AB2

AB3

AB4

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Valence Shell Electron Pair Repulsion Theory

VSEPR: the best arrangement of a given number of electron pairs is the one that minimizes the repulsions among them.

VSEPR:The Effect of Nonbonding Electrons and Multiple Bonds on Bond Angles

Nonbonding electron pairs exert greater repulsive forces on adjacent electron pairs and thus tend to compress the angles between the bonding pairs
Nonbonding electron pairs 2 Nonbonding electron pairs

109. 5

107

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Methane (CH4)

Ammonia (NH3)

Water (H2O)

VSEPR:The Effect of Nonbonding Electrons and Multiple Bonds on Bond Angles

Multiple bonds, like nonbonding electron pairs, exert a greater repulsive force on adjacent electron pairs than do single bonds.

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Formaldehyde (H2CO)

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VSEPR: Geometries of Molecules with Expanded Valence Shells

When the central atom of an ABn molecule is from the third period of the periodic table and beyond, the atom may have more than four electron pairs around it.

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VSEPR: Geometries of Molecules with Expanded Valence Shells

Note: because nonbonding electron pairs exert larger repulsion than bond pairs, 12 they always occupy the equatorial positions in AB5 molecules

VSEPR: Geometries of Molecules with Expanded Valence Shells

Note: the placement of a single nonbonding electron pair in an AB6 molecule is arbitrary. The placement of two nonbonding pairs must be on opposite sides of 13 the octahedron.

Tetrahedral

H H C H

H C

.. O ..

H
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Now Wait Just a Dipole Moment!

= Qr, where is the dipole moment in
Debyes (3.33 x 10-30 C-m/D), Q is the charge at each end of the molecule and r is the distance between the charges

Given that the dipole moment for HCl ( ) = 1.03 D how much separation of charge exists between the H and Cl atoms. = Qr 1.03D ( 3.33 x 10-30 C-m/D) = Q (1.36 A) (1x 10-10m/A)

Q = 2.52 x 1020C
%Q = (2.52 x 1020C/1.6 x 10-19C)x 100 = 15.8
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Dipole Moment: The Polarity of Polyatomic Molecules

The polarity of a molecule is dependent upon both the polarities of the bonds and the geometry of the molecule

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Covalent Bonding and Orbital Overlap: Valence Bond Theory

Valence Bond Theory unifies Lewis notion of electron-pair bonds and the quantum notion of atomic orbitals.

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Covalent Bonding and Orbital Overlap: Valence Bond Theory

-bonds: results from the overlapping of two s-orbitals, one from each atom.
-bonds appear to be weaker than -bonds!

-bonds

-bonds

Formaldehyde (H2CO)
-bonds: result from the overlapping of two p-orbitals, one from each atom. These covalent bonds are constructed from overlapped regions above and below the internuclear axis
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Covalent Bonding and Orbital Overlap: Hybrid Orbitals :F : Be F : : 1s2 2s2 2p5

1s2 2s2

2p5

In order for an overlap to occur Beryllium must provide unpaired electrons. This is accomplished by promoting one of the 2S electrons

1s2 2s1

1s2 2s2

In order for each of the bonds to be identical, the 2s1 and 2p1 orbitals become hybridized

1s2

2sp

: 2p1 2p

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Large lobes of sp hybrid orbitals

Be

Fluorine 2p orbitals

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1s2

2s 2

2p1

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Covalent Bonding and Orbital Overlap: Hybrid Orbitals (sp2, BF3)

In order for an overlap to occur Boron must provide 3 unpaired electrons. This is accomplished by promoting one of the 2S electrons

1s2 2s1

2p1

In order for each of the bonds to be identical, the 2s1 and 2p1 orbitals become hybridized

1s2

2sp2

2p

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1s2 2s2
109. 5

2p1
promote

hybridize

1s2

sp3

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Covalent Bonding and Orbital Overlap: Hybrid Orbitals (sp3d, PF5)

3s2
Phosphorous Pentafluoride (PF4)

3p3
promote

3d

3s2

3p3

3d
hybridize

Atoms in the third period and beyond can use their d orbitals

3sp3d

3d

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Hybrid Orbitals and Multiple Bonds: Getting a Piece of the ,

Consider the molecular geometry of ethylene:

1s2 2s2

2p2
promote

1s2 2s1

2p3
hybridize

1s2

sp2

2p
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Note that the bond angles are probably trigonal planar. This suggests an sp2 configuration with one electron remaining in an unhybridized 2p orbital

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Hybrid Orbitals and Multiple Bonds: Getting a Piece of the ,

Consider the molecular geometry of acetylene

1s2 2s2

2p2
promote

1s2 2s1

2p3
hybridize

1s2

sp

2p2

Note that the bond angles are probably linear. This suggests an sp configuration 32 with each of the two remaining electrons located in unhybridized 2p orbital

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Hybrid Orbitals and Multiple Bonds: Delocalized Bonding

In noncyclic compounds, bonding electrons are localized

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Hybrid Orbitals and Multiple Bonds: Delocalized Bonding

Cyclic compounds resonate, in these cases the bonds are delocalized

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Molecular Orbitals: Its Quantum Time!

antibonding orbitals

bonding orbitals

Contour Representations

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2p 2p

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