Later in the semester, we will be studying bimolecular substitution reactions.

In the reaction shown below, the strong base HO will react with an empty orbital of the C-Br bond. What does this orbital look like? From which direction do you think the HO will react with the C-Br bond?

Topic 1 Orbitals and Bonding

Structure of organic molecules 1) Where are the electrons in a bond? 2) If electrons are added to a molecule/bond where will they go? 3) How are bonds arranged around an atom in a molecule? To 1) 2) 3) 4) 5) answer these questions: Atomic Structure and orbitals Hybrid Orbitals Covalent Bonds Molecular orbital theory Electronegativity

Atomic Orbitals

Atomic orbitals (AOs) describe the state of electrons about an atom: Energy Spatial distribution Correlation with another electron (i.e., occupancy empty, halffilled, filled) Atomic orbitals are determined by 4 quantum numbers: n - principal quantum number; l - related to shape m - related to orientation; s - spin

1s
n=1,l=0 m=0,s=1/2

2s
n=2,l=0 m=0,s=1/2

2px
n=2,l=1 m=-1,s=1/2

2py
n=2,l=1 m=-0,s=1/2

2pz

n=2,l=1 m=+1,s=1/2

Atomic Orbitals

1s

2s

2px

2py

2pz

The (+) or () signs indicate the mathematical signs of the equations. A node is the point/surface at which opposite signs of the wave function are separated. The probability of finding an electron at a node is zero.

The signs of the orbital lobes can also be represented by shading.

2s Energy

2pxyz

1s

2s

2px

2py

2pz

1s

The 2p Orbitals

Notice that the p orbitals are 0 at the origin and change sign this is called a node. What happens when a positive and negative wave interact?

a. They move towards each other because positive and negative charges attract each other. b. They cancel each other out

The Octet Rule

Electronegativity increases to the right and up

Molecular Orbital Theory

Molecular orbital describes electron density on molecule Can be approximated as a linear combination of atomic orbitals (LCAO) Number of atomic orbitals = number of molecular orbitals Molecular Orbitals of H2

Bonding molecular orbital - electrons concentrated between nuclei and shield nuclei from each other

Antibonding molecular orbital - no electron density between nuclei - nuclei repel each other.

Behavior of Waves

Molecular Orbital Theory - H2

Bonding Molecular Orbital

Antibonding Molecular Orbital

Constructive Interference

Destructive Interference

Molecular Orbitals Methane

Hybrid Orbitals
Hybrid orbitals have different spatial arrangements.
sp sp 2py 2pz
Non-bonding

180

sp linear

sp hybrid
Non-bonding

Be - 1s22s2 H - 1s1

120

2s 2px 2py 2pz

sp2 sp2 sp2 2py

sp2 trigonal planar sp2 hybrid

Starting AOs

109.5

B - 1s22s22p1 H - 1s1 H

sp3 sp3 sp3 sp3

sp3 hybrid

sp3 tetrahedral

C - 1s22s22p2 H - 1s1

Hybrid Orbitals
Non-bonding 120

sp2 sp2 sp2 2py

sp2 trigonal planar

B - 1s22s22p1 H - 1s1

sp2 hybrid

Non-bonding

180

sp sp 2py 2pz

sp linear

sp hybrid

Be - 1s22s2 H - 1s1

Penicillin G

The molecule below is called a pyrrole. The geometry at nitrogen is trigonal planar.

What is the hybridization at nitrogen? A. sp B. sp2 C. sp3 D. dsp3

In what orbital are the electrons of the lone pair of nitrogen?

A. sp B. sp3 C. p

D. s