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Theories of Bonding and Structure CHAPTER 10 Chemistry: The Molecular Nature of Matter, 6 th edition By Jesperson , Brady, & Hyslop. CHAPTER 10: Bonding & Structure. Learning Objectives VESPR theory: Determine molecular geometry based on molecular formula and/or lewis dot structures. - PowerPoint PPT Presentation
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Theories of Bonding and Structure
CHAPTER 10
Chemistry: The Molecular Nature of Matter, 6th editionBy Jesperson, Brady, & Hyslop
2
CHAPTER 10: Bonding & Structure
Learning Objectives VESPR theory:
Determine molecular geometry based on molecular formula and/or lewis dot structures.
Effect of bonded atoms & non-bonded electrons on geometry Molecular polarity & overall dipole moment
Assess overall dipole moment of a molecule Identify polar and non-polar molecules
Valence Bond Theory Hybridized orbitals Multiple bonds Sigma vs pi orbitals
Molecular Orbital Theory Draw & label molecular orbital energy diagrams Bonding & antibonding orbitals Predict relative stability of molecules based on MO diagrams
3
Molecular Geometry Basic Molecular Geometries
Jesperson, Brady, Hyslop. Chemistry: The Molecular Nature of Matter, 6E
Linear3 atoms
Trigonal Planaror
Planar Triangular
4 atoms
Tetrahedral:5 atoms
Trigonal Bipyramidal6 atoms
Octahedral:7 atoms
4
VESPR Definition
Jesperson, Brady, Hyslop. Chemistry: The Molecular Nature of Matter, 6E http://chemistry-desk.blogspot.com/2011/05/prediction-of-shape-of-molecules-by.html
Valence Shell Electron Pair Repulsion ModelElectron pairs (or groups of electron pairs) in the valence shell of an atom repel each other and will position themselves so that they are far apart as
possible, thereby minimizing the repulsions.
Electron pairs can either be lone pairs or bonding pairs.
Tetrahedral arrangement of electron pairsBent geometry
5
VESPR Definition
Jesperson, Brady, Hyslop. Chemistry: The Molecular Nature of Matter, 6E
Valence Shell Electron Pair Repulsion ModelElectron pairs (or groups of electron pairs) in the valence shell of an atom repel each other and will position themselves so that they are far apart as
possible, thereby minimizing the repulsions.
Text uses “electron domain” to describe electron pairs:
Bonding domain: contains electrons that are shared between two atoms. So electrons involved in single, double, or triple are
part of the same bonding domain.
Nonbonding Domain: Valence electrons associated with one atom, such as a lone pair, or a unpaired electron.
6
VESPR Basic Examples
Jesperson, Brady, Hyslop. Chemistry: The Molecular Nature of Matter, 6E
2 bonding domains
3 bonding domains
4 bonding domains
5 bonding domains
6 bonding bonding domains
7
VESPR When Lone Pairs or Multiple Bonds Present
Jesperson, Brady, Hyslop. Chemistry: The Molecular Nature of Matter, 6E
Including lone pairs: • Take up more space around central atom • Effect overall geometry • Counted as nonbonded electron domains
Including multiple bonds (double and triple) • For purposes of determining geometry focus on the number
of atoms bonded together rather then the number of bonds in between them: ie, treat like a single bond.
• Treat as single electron bonding domain
8
VESPR Electrons that are Bonding & Not Bonding
Jesperson, Brady, Hyslop. Chemistry: The Molecular Nature of Matter, 6E
Bonding Electrons – More oval in shape – Electron density focused
between two positive nuclei.
Nonbonding Electrons– More bell or balloon shaped– Take up more space – Electron density only has positive
nuclei at one end
9
VESPR 3 atoms or lone pairs
Jesperson, Brady, Hyslop. Chemistry: The Molecular Nature of Matter, 6E
Number of Bonding Domains
3
2
Number of Nonbonding Domains
0
1
Molecular Shape
Planar Triangular(e.g. BCl3)All bond angles 120
NonlinearBent or V-shaped(e.g. SnCl2)
Bond <120
Structure
10
VESPR 4 atoms or lone pairs
Jesperson, Brady, Hyslop. Chemistry: The Molecular Nature of Matter, 6E
Number of Bonding Domains
4
3
2
Number of Nonbonding Domains
0
1
2
Molecular Shape
Tetrahedron(e.g. CH4)All bond angles 109.5
Trigonal pyramidal(e.g. NH3)Bond angle less than 109.5
Nonlinear, bent(e.g. H2O)Bond angle less than109.5
Structure
11
VESPR 5 atoms or lone pairs
Jesperson, Brady, Hyslop. Chemistry: The Molecular Nature of Matter, 6E
90
120
Trigonal Bipyramidal• Two atoms in axial position
– 90 to atoms in equatorial plane
• Three atoms in equatorial position– 120 bond angle to atoms
in axial position– More room here– Substitute here first
12
VESPR 5 atoms or lone pairs
Jesperson, Brady, Hyslop. Chemistry: The Molecular Nature of Matter, 6E
Number of Bonding Domains
5
4
Number of Nonbonding Domains
0
1
Molecular Shape
Trigonal bipyramid(e.g. PF5)Ax-eq bond angles 90Eq-eq 120
Distorted Tetrahedron, or Seesaw(e.g. SF4)Ax-eq bond angles < 90
Structure
13
5 atoms or lone pairs
Jesperson, Brady, Hyslop. Chemistry: The Molecular Nature of Matter, 6E
• Lone pair takes up more space• Goes in equatorial plane• Pushes bonding pairs out of way• Result: distorted tetrahedron
VESPR
14
VESPR 5 atoms or lone pairs
Jesperson, Brady, Hyslop. Chemistry: The Molecular Nature of Matter, 6E
Number of Bonding Domains
3
2
Number of Nonbonding Domains
2
3
Molecular Shape
T-shape(e.g. ClF3)Bond angles 90
Linear(e.g. I3
–)Bond angles 180
Structure
15
VESPR 6 atoms or lone pairs
Jesperson, Brady, Hyslop. Chemistry: The Molecular Nature of Matter, 6E
Number of Bonding Domains
6
5
Molecular Shape
Octahedron(e.g. SF6)
Square Pyramid(e.g. BrF5)
StructureNumber of Nonbonding Domains
0
1
16
VESPR 6 atoms or lone pairs
Jesperson, Brady, Hyslop. Chemistry: The Molecular Nature of Matter, 6E
Number of Bonding Domains
4
Number of Nonbonding Domains
2
Molecular Shape
Square planar(e.g. XeF4)
Structure
17
VESPR Determining 3-D Structures
Jesperson, Brady, Hyslop. Chemistry: The Molecular Nature of Matter, 6E
1. Draw Lewis Structure of Molecule– Don't need to compute formal charge– If several resonance structures exist, pick only one
2. Count electron pair domains– Lone pairs and bond pairs around central atom– Multiple bonds count as one set (or one effective pair)
3. Arrange electron pair domains to minimize repulsions• Lone pairs
– Require more space than bonding pairs– May slightly distort bond angles from those predicted.– In trigonal bipyramid lone pairs are equatorial – In octahedron lone pairs are axial
4. Name molecular structure by position of atoms—only bonding electrons
Molecular Polarity Polar Molecules
Jesperson, Brady, Hyslop. Chemistry: The Molecular Nature of Matter, 6E
18
• Have net dipole moment– Negative end– Positive end
• Polar molecules attract each other.– Positive end of polar molecule attracted to
negative end of next molecule.– Strength of this attraction depends on
molecule's dipole moment– Dipole moment can be determined
experimentally• Polarity of molecule can be predicted by taking
vector sum of bond dipoles• Bond dipoles are usually shown as crossed
arrows, where arrowhead indicates negative end
19
Molecular Polarity Molecular Shape & Polarity
Jesperson, Brady, Hyslop. Chemistry: The Molecular Nature of Matter, 6Ehttp://wps.prenhall.com/wps/media/objects/3081/3155729/blb0903.html
• Many physical properties (melting and boiling points) affected by molecular polarity
• For molecule to be polar:– Must have polar bonds
• Many molecules with polar bonds are nonpolar - Possible because certain
arrangements of bond dipoles cancel
- For molecules with more than two atoms, must consider the combined effects of all polar bonds
20
Molecular Polarity Symmetrical Nonpolar Molecules
Jesperson, Brady, Hyslop. Chemistry: The Molecular Nature of Matter, 6E
• Symmetrical molecules – Nonpolar because bond dipoles cancel
• All five shapes are symmetrical when all domains attached to them are composed of identical atoms
21
Molecular Polarity Symmetrical Nonpolar Molecules
Jesperson, Brady, Hyslop. Chemistry: The Molecular Nature of Matter, 6E
Cancellation of Bond Dipoles In Symmetrical Trigonal Bipyramidal and Octahedral Molecules
• All electron pairs around central atom are bonding pairs and • All terminal groups (atoms) are same• The individual bond dipoles cancel
22
Molecular Polarity Polar Molecules
Jesperson, Brady, Hyslop. Chemistry: The Molecular Nature of Matter, 6E
Molecule is usually polar if – All atoms attached to central atom are NOT same Or, – There are one or more lone pairs on central atom
23
Molecular Polarity Polar Molecules
Jesperson, Brady, Hyslop. Chemistry: The Molecular Nature of Matter, 6E
Water and ammonia both have non-bonding domains Bond dipoles do not cancel Molecules are polar
24
Molecular Polarity Polar Molecules: Exception
Jesperson, Brady, Hyslop. Chemistry: The Molecular Nature of Matter, 6E
Exception to these general rules for identifying polar molecules:
Nonbonding domains (lone pairs) are symmetrically placed around central atom
25
ProblemSet A
1. For the following molecules: a. Draw a lewis dot structure.b. Determine the molecular geometry at each central atom.c. Identify the bond angles.d. Identify all polar bonds: δ+ / δ-e. Assess the polarity of the molecule & indicate the overall
dipole moment if one exists
AsF5 AsF3 SeO2
GaH3
ICl2- SiO4-4
TeF6
26
VB Theory Review: Modern Atomic Theory of Bonding
Jesperson, Brady, Hyslop. Chemistry: The Molecular Nature of Matter, 6E
Modern Atomic Theory of Bonding is based on wave mechanics and gave us:
– Electrons and shapes of orbitals– Four quantum numbers– Heisenberg uncertainty principle
• Electron probabilities– Pauli Exclusion Principle
27
VB Theory Valence Bond Theory & Molecular Orbital Theory
Jesperson, Brady, Hyslop. Chemistry: The Molecular Nature of Matter, 6E
Valence Bond Theory• Individual atoms, each have their own orbitals and orbitals
overlap to form bonds• Extent of overlap of atomic orbitals is related to bond strength
Molecular Orbital Theory • Views molecule as collection of positively charged nuclei
having a set of molecular orbitals that are filled with electrons (similar to filling atomic orbitals with electrons)
• Doesn't worry about how atoms come together to form molecule
28
VB Theory Valence Bond Theory & Molecular Orbital Theory
Jesperson, Brady, Hyslop. Chemistry: The Molecular Nature of Matter, 6E
Both Theories:• Try to explain structure of molecules, strengths of
chemical bonds, bond orders, etc.• Can be extended and refined and often give same
results
Valence Bond Theory Bond between two atoms formed when pair of electrons with paired (opposite) spins is shared by two overlapping atomic orbitals
29
VB Theory H2
Jesperson, Brady, Hyslop. Chemistry: The Molecular Nature of Matter, 6E
H2 bonds form because 1s atomic valence orbital from each H atom overlaps
30
VB Theory F2
Jesperson, Brady, Hyslop. Chemistry: The Molecular Nature of Matter, 6E
• F2 bonds form because atomic valence orbitals overlap• Here 2p overlaps with 2p• Same for all halogens, but different np orbitals
31
VB Theory HF
Jesperson, Brady, Hyslop. Chemistry: The Molecular Nature of Matter, 6E
HF involves overlaps between 1s orbital on H and 2p orbital of F
1s 2p
32
VB Theory H2S
Jesperson, Brady, Hyslop. Chemistry: The Molecular Nature of Matter, 6E
Predicted 90˚ bond angle is very close to experimental value of 92˚.
• Assume that unpaired electrons in S and H are free to form paired bond
• We may assume that H—S bond forms between s and p orbital
33
VB Theory Need to Change Approach to Explain Bonding in CH4
Jesperson, Brady, Hyslop. Chemistry: The Molecular Nature of Matter, 6E
Example: CH4 C 1s 22s 22p 2 and H 1s 1
• In methane, CH4 – All four bonds are the same– Bond angles are all 109.5°
• Carbon atoms have– All paired electrons except two unpaired 2p– p orbitals are 90° apart– Atomic orbitals predict CH2 with 90° angles
34
VB Theory Hybridization
Jesperson, Brady, Hyslop. Chemistry: The Molecular Nature of Matter, 6E
• Mixing of atomic orbitals to allow formation of bonds that have realistic bond angles.– Realistic description of bonds often requires combining
or blending two or more atomic orbitals• Hybridization just rearranging of electron probabilities
Why do it? • To get maximum possible overlap• Best (strongest) bond formed
35
VB Theory Hybrid Orbitals
Jesperson, Brady, Hyslop. Chemistry: The Molecular Nature of Matter, 6E
• Blended orbitals result from hybridization process• Hybrid orbitals have
– New shapes– New directional properties– Each hybrid orbital combines properties of parent atomic
orbitals
36
VB Theory Hybrid Orbitals
Jesperson, Brady, Hyslop. Chemistry: The Molecular Nature of Matter, 6E
• Symbols for hybrid orbitals combine the symbols of the orbitals used to form them– Use s + p form two sp hybrid orbitals– Use s + p + p form three sp 2 hybrid orbitals
• One atomic orbital is used for each hybrid orbital formed
• Sum of exponents in hybrid orbital notation must add up to number of atomic orbitals used
37
VB Theory Hybrid Orbitals
Jesperson, Brady, Hyslop. Chemistry: The Molecular Nature of Matter, 6E
Mixing or hybridizing s and p orbital of same atom results in two sp hybrid orbitals
Two sp hybrid orbitals point in opposite directions
38
VB Theory Ex: sp Hybridized Orbitals: BeH2
Jesperson, Brady, Hyslop. Chemistry: The Molecular Nature of Matter, 6E
• Now have two sp hybrid orbitals • Oriented in correct direction for
bonding• 180 bond angles
– As VSEPR predicts and– Experiment verifies
• Bonding = – Overlap of H 1s atomic
orbitals with sp hybrid orbitals on Be
39
VB Theory Hybrid Orbitals
Jesperson, Brady, Hyslop. Chemistry: The Molecular Nature of Matter, 6E
Hybrid Atomic Orbitals Used Electron Geometry
sp s + p LinearBond angles 180°
sp2 s + p + p Trigonal planarBond angles 120°
sp3 s + p + p + p TetrahedralBond angles 109.5°
sp3d s + p + p + p + d Trigonal BipyramidalBond angles 90° and 120°
sp3d2 s + p + p + p + d + d OctahedralBond angles 90°
40
VB Theory Bonding in BCl3
Jesperson, Brady, Hyslop. Chemistry: The Molecular Nature of Matter, 6E
• Overlap of each half- filled 3p orbital on Cl with each half-filled sp2 hybrid on B
Forms three equivalent bonds
Trigonal planar shape 120 bond angle
41
VB Theory
Jesperson, Brady, Hyslop. Chemistry: The Molecular Nature of Matter, 6E
Overlap of each half- filled 1s orbital on H with each half-filled sp3 hybrid on carbon
Forms four equivalent bonds Tetrahedral geometry 109.5 bond angle
Bonding in CH4
42
VB Theory Hybrid sp Orbitals
Two sp hybrids
Three sp2 hybrids
Four sp3 hybrids
Linear
Planar Triangular
Tetrahedral
All angles 120
All angles 109.5
Jesperson, Brady, Hyslop. Chemistry: The Molecular Nature of Matter, 6E
43
VB Theory Expanded Octet Hybridization
Jesperson, Brady, Hyslop. Chemistry: The Molecular Nature of Matter, 6E
Hybridization When Central Atom has More Than Octet• If there are more than four equivalent bonds on central atom, then must add
d orbitals to make hybrid orbitalsWhy? • One s and three p orbitals means that four equivalent orbitals is the most you
can get using s and p orbitals alone
So, only atoms in third row of the periodic table and below can exceed their octet• These are the only atoms that have empty d orbitals of same n level as
s and p that can be used to form hybrid orbitals• One d orbital is added for each pair of electrons in excess of standard
octet
44
VB Theory Expanded Octet Hybridization
Jesperson, Brady, Hyslop. Chemistry: The Molecular Nature of Matter, 6E
45
VB Theory Hybridization in Molecules with Lone Pairs
Jesperson, Brady, Hyslop. Chemistry: The Molecular Nature of Matter, 6E
CH4 sp3 tetrahedral geometry 109.5° bond angleNH3
107° bond angleH2O
104.5° bond angle• Angles suggest that NH3 and H2O both use sp3 hybrid orbitals in
bonding• Not all hybrid orbitals used for bonding e–
– Lone pairs can occupy hybrid orbitals• Lone pairs must always be counted to determine geometry
46
VB Theory Ex: H2O Hybridization
Jesperson, Brady, Hyslop. Chemistry: The Molecular Nature of Matter, 6E
47
VB Theory Multiple Bonds
Jesperson, Brady, Hyslop. Chemistry: The Molecular Nature of Matter, 6E
• So where do extra electron pairs in multiple bonds go?– Not in hybrid orbitals– Remember VSEPR, multiple bonds have no
effect on geometry• Why don’t they effect geometry?
Two types of bond result from orbital overlap• Sigma () bond
– Accounts for first bond• Pi () bond
– Accounts for second and third bonds
48
VB Theory Sigma () Bonds
Jesperson, Brady, Hyslop. Chemistry: The Molecular Nature of Matter, 6E
• Head on overlap of orbitals• Concentrate electron density concentrated most
heavily between nuclei of two atoms• Lie along imaginary line joining their nuclei
s + s
p + p
sp + sp
49
VB Theory Pi () Bonds
Jesperson, Brady, Hyslop. Chemistry: The Molecular Nature of Matter, 6E
• Sideways overlap of unhybridized p orbitals • Electron density divided into two regions
– Lie on opposite sides of imaginary line connecting two atoms
• Electron density above and below bond.
No electron density along bond axis
bond consists of both regions
Both regions = one bond
50
VB Theory Pi () Bonds
Jesperson, Brady, Hyslop. Chemistry: The Molecular Nature of Matter, 6E
• Can never occur alone– Must have bond
• Can form from unhybridized p orbitals on adjacent atoms after forming bonds
• bonds allow atoms to form double and triple bonds
51
VB Theory Multiple Bonds Ex: Ethene (C2H4)
Jesperson, Brady, Hyslop. Chemistry: The Molecular Nature of Matter, 6E
• Each carbon is – sp
2 hybridized (violet)– has one unhybridized p
orbital (red)
• C=C double bond is– one bond (sp
2 – sp 2 )
– one bond (p – p)
p—p overlap forms a C—C bond
52
VB Theory Conformations
Jesperson, Brady, Hyslop. Chemistry: The Molecular Nature of Matter, 6E
• C—C single bond has free rotation around the C—C bond
• Conformations– Different relative
orientations on molecule upon rotation
53
VB Theory Conformations Ex: Pentane, C5H12
Jesperson, Brady, Hyslop. Chemistry: The Molecular Nature of Matter, 6E
54
VB Theory Properties of -Bonds
Jesperson, Brady, Hyslop. Chemistry: The Molecular Nature of Matter, 6E
• Can’t rotate about double bond
• bond must first be broken before rotation can occur
55
Ex: Bonding in Formaldehyde
Jesperson, Brady, Hyslop. Chemistry: The Molecular Nature of Matter, 6E
• C and O each – sp 2 hybridized
(violet)– Has one
unhybridized p orbital (red)
C=O double bond is one bond (sp2 – sp2) one bond
(p – p)
Unshared pairs of electrons on oxygen in sp2 orbitals
sp2—sp2 overlap to form C—O bond
VB Theory
56
Bonding in Ethyne, C2H2
Jesperson, Brady, Hyslop. Chemistry: The Molecular Nature of Matter, 6E
Each carbon is sp hybridized (violet) Has two unhybridized p
orbitals, px and py (red)
CC triple bond one bond
sp – sp two bonds
px – px
py – py
VB Theory
57
VB Theory Ex: Bonding in N2
Jesperson, Brady, Hyslop. Chemistry: The Molecular Nature of Matter, 6E
Each nitrogen sp hybridized (violet) Has two unhybridized p orbitals,
px and py (red)NN triple bond one bond
sp – sp two bonds
px – px
py – py
58
ProblemSet B
2. What is the hybridization of oxygen in OCl2? 3. For the species and XeF4O, determine the following:
a. electron domain geometry (geometry including non-bonding pairs)
b. molecular geometryc. Hybridization around central atomd. Polarity
4. How many and bonds are there in CH2CHCHCH2, and what is the hybridization around the carbon atoms?
5. Draw & list the bonding orbitals for HCN.
59
ProblemSet B
2. sp3
3. XeF4O: octahedral, square pyramid, sp3d2, polar
4. 9, 2, sp2
5. HCN: C will be create a σ bond to H and N with sp2 hybridized orbitals and use 2 p orbitals to participate in 2 π bonds with N. N will participate in the σ bond with C with an sp2 hybridized orbital, the other will hold the N lone pair, and then N will use 2 p orbitals to π bond with C.
60
MO Theory Molecular Orbital Theory
Jesperson, Brady, Hyslop. Chemistry: The Molecular Nature of Matter, 6E
1. Molecular orbitals are associated with entire molecule as opposed to one atom
2. Allows us to accurately predict magnetic properties of molecules
3. Energies of molecular orbitals determined by combining electron waves of atomic orbitals
Molecular Orbital Theory Views molecule as collection of positively charged nuclei having a set of molecular orbitals that are filled with electrons (similar
to filling atomic orbitals with electrons)Doesn't worry about how atoms come together to form
molecule
61
MO Theory Bonding Molecular Orbitals
Jesperson, Brady, Hyslop. Chemistry: The Molecular Nature of Matter, 6E
• Come from various combinations of atomic orbital wave functions
• For H2, two 1s wave functions, one from each atom, combine to make two molecular orbital wave functions
1sA + 1sB Combined Bonding MO
Constructive interference of waves Energy of bonding MO lower than atomic orbitals
62
MO Theory * Antibonding Molecular Orbitals
Jesperson, Brady, Hyslop. Chemistry: The Molecular Nature of Matter, 6E
• Destructive interference of the 1s waves• Energy of the bonding molecular orbital is higher
than energy of parent atomic orbitals
• Number of atomic orbitals used must equal number of molecular orbitals
• Other possible combination of two 1s orbitals: 1sA – 1sB
63
Summary of MO from 1s Atomic Orbital
Jesperson, Brady, Hyslop. Chemistry: The Molecular Nature of Matter, 6E
• Bonding molecular orbital– Electron density builds up between nuclei– Electrons in bonding MOs tend to stabilize molecule
• Antibonding molecular orbital– Cancellation of electron waves reduces electron density
between nuclei– Electrons in antibonding MOs tend to destabilize molecule
MO Theory
64
MO Theory MO Diagram for H2
Jesperson, Brady, Hyslop. Chemistry: The Molecular Nature of Matter, 6E
65
MO Theory Rules for Filling in MO Energy Diagrams
Jesperson, Brady, Hyslop. Chemistry: The Molecular Nature of Matter, 6E
1. Electrons fill lowest-energy orbitals that are available– Aufbau principle applies
2. No more than two electrons, with spin paired, can occupy any orbital
– Pauli exclusion principle applies3. Electrons spread out as much as possible, with spins unpaired,
over orbitals of same energy– Hund’s rules apply
66
MO Theory Bond Order
Jesperson, Brady, Hyslop. Chemistry: The Molecular Nature of Matter, 6E
• Measure of number of electron pairs shared between two atoms
• H2 bond order = 1• A bond order of 1 corresponds to a single bond
67
MO Theory MO Diagram for He2
Jesperson, Brady, Hyslop. Chemistry: The Molecular Nature of Matter, 6E
• Four electrons, so both and * molecular orbitals are filled
• Bond order
• There is no net bonding• He2 does not form
68
2p Molecular Orbitals
Jesperson, Brady, Hyslop. Chemistry: The Molecular Nature of Matter, 6E
MO Theory
MO Theory 2nd Row Periodic Table MO Diagrams
Jesperson, Brady, Hyslop. Chemistry: The Molecular Nature of Matter, 6E
69
Li2 N2 2p Lower in energy than 2p
O2, F2 and Higher 2p Lower in energy than 2p
Can ignore filled 1s bonding & antibonding and focus on valence electrons
70
MO Theory MO Diagram for Li2
Jesperson, Brady, Hyslop. Chemistry: The Molecular Nature of Matter, 6E
2p Lower in Energy than 2p
LiLiLi2
Diamagnetic as no unpaired spinsBond order = (2 – 0)/2
= 1
71
MO Theory MO Energy Diagram for F2
Jesperson, Brady, Hyslop. Chemistry: The Molecular Nature of Matter, 6E
F electron configuration = [He]2s22p5 Bond order = (8 – 6)/2
= 1
F – F single bond stable molecule
Diamagnetic as no unpaired spins
FFF2
2p Lower in Energy than 2p
72
MO Theory Heteronuclear Diatomic Molecules
Jesperson, Brady, Hyslop. Chemistry: The Molecular Nature of Matter, 6E
• If Li through N 2p below 2p • If O, F and higher atomic number, then 2p below 2p Example
– BC both are to left of N • so 2p below 2p
– OF both are to right of N • so 2p below 2p
– What about NF?• Each one away from O so average is O and 2p below 2p
73
MO Theory B-C and N-F
Jesperson, Brady, Hyslop. Chemistry: The Molecular Nature of Matter, 6E
2p lower 2p lower
BC NFNumber of valence e = 3 + 4 = 7 Number of valence e = 5 + 7 = 12
Bond Order = (5 – 2)/2 = 1.5 Bond Order = (8 – 4)/2 = 2
74
MO Theory N-O
Jesperson, Brady, Hyslop. Chemistry: The Molecular Nature of Matter, 6E
• Bond Order for NO tricky• N predicts 2p lower
• O predicts 2p lower• Have to look at experiment • Shows that 2p is lower
2p lower
Number of valence e = 5 + 6 = 11
Bond Order = (8 – 3)/2 = 2.5
75
MO Theory N-O+ and N-O–
Jesperson, Brady, Hyslop. Chemistry: The Molecular Nature of Matter, 6E
NO+ NO• Same diagram• Different number
of e–
• NO+ has 11 – 1 = 10 valence e
Bond order = (8 – 2)/2 = 3
• NO has11 + 1 = 12 valence e
Bond order = (8 – 4)/2 = 2
76
MO Theory Relative Stability of N-O, N-O+ and N-O–
Jesperson, Brady, Hyslop. Chemistry: The Molecular Nature of Matter, 6E
• Recall that as bond order increases, bond length decreases, and bond energy increases
Molecule or ion
Bond Order
Bond Length (pm)
Bond Energy (kJ/mol)
NO+ 3 106 1025
NO 2.5 115 630
NO 2 130 400
So NO+ is most stable form Highest bond order, shortest and strongest bond
77
ProblemSet C
6. What is the MO Energy Diagram for B2? How many unpaired electrons does B2 have?
7. What is the bond order & number of unpaired electrons in
8. Draw the MO Energy Diagram for BN.
78
Bonding VB vs MO Theory
Jesperson, Brady, Hyslop. Chemistry: The Molecular Nature of Matter, 6E
• Neither VB or MO theory is entirely correct– Neither explains all aspects of bonding– Each has its strengths and weaknesses
• MO theory correctly predicts unpaired electrons in O2 while Lewis structures do not
• MO theory is a difficult because even simple molecules have complex energy level diagrams
• MO theory is a difficult because molecules with three or more atoms require extensive calculations
79
Bonding VB vs MO Theory
Jesperson, Brady, Hyslop. Chemistry: The Molecular Nature of Matter, 6E
Successes of VB Theory• Based on simple Lewis structures and related geometric figures• Three dimensional structures based on electron domains without massive
calculations• Simple hybrid orbitals invoked where experimental evidence shows the need• Integer bond orders are often correct
Successes of MO Theory• MO theory is particularly successful in explaining paramagnetism of B2 and O2
– One electron each in 2px and 2py (for B2)
– One electron each in *2px and *2py (for O2)
80
Resonance VB Theory Treatment of Resonance
Jesperson, Brady, Hyslop. Chemistry: The Molecular Nature of Matter, 6E
• Formate anion, HCOO–
• C has three electron domains (all bonding pairs) so – sp2 hybridized; trigonal planar
• Each O has three electron domains (one bonding pair and two lone pairs) – so sp2 hybridized; trigonal planar
81
Resonance VB Theory Treatment of Resonance
Jesperson, Brady, Hyslop. Chemistry: The Molecular Nature of Matter, 6E
• Have two resonance structures• Have lone pair on each O atom in unhybridized p
orbitals as well as empty p orbital on C• Lewis theory says
– Lone pair on one O – Use lone pair of other O to form (pi) bond– Must have two Lewis structures
82
Resonance MO Theory Treatment of Resonance
Jesperson, Brady, Hyslop. Chemistry: The Molecular Nature of Matter, 6E
Bonding MO delocalized over all three atoms
This is also our resonance hybrid picture This is the best view of what actually occurs and can be
obtained from both VB and MO theory
83
Resonance MO / VB Theory Treatment of Resonance:Benzene
Jesperson, Brady, Hyslop. Chemistry: The Molecular Nature of Matter, 6E
• Six C atoms, each sp2 hybridized (3 bonds)• Each C also have one unhybridized p orbital (6 total)• So six MOs, 3 bonding and three antibonding• So three bonds
84
Resonance MO / VB Theory Treatment of Resonance: Benzene
Jesperson, Brady, Hyslop. Chemistry: The Molecular Nature of Matter, 6E
• Can write benzene as two resonance structures• But actual structure is composite of these two• Electrons are delocalized • Have three pairs of electrons delocalized over six C atoms • Extra stability is resonance energy• Functionally, resonance and delocalization energy are the same
thing