William H. Brown Christopher S. Foote Brent L.

Iverson Eric Anslyn

http://academic.cengage.com/chemistry/brown

Chapter 1 Covalent Bonding and Shapes of Molecules

William H. Brown Beloit College 1-1

Organic Chemistry
The study of the compounds of carbon. Over 10 million compounds have been identified.
About 1000 new ones are identified each day!

C is a small atom.
It forms single, double and triple bonds. It is intermediate in electronegativity (2.5). It forms strong bonds with C, H, O, N, and many metals.

1-2

Schematic View of an Atom

A small dense nucleus, diameter 10-14 - 10-15 m, which contains positively charged protons and most of the mass of the atom. An extranuclear space, diameter 10-10 m, which contains negatively charged electrons.

1-3

Some useful terms

Shell: Define the probability of finding the e- in various regions of the space. The energy of the ein the shells is quantized Quantization: only specific values of energy are possible. The shells can ONLY occur at quantized energy in which three effects balance each other: electrostatic attraction, electrostatic repulsion and the wavelike nature of e- that prefers to be delocalized Delocalization: spreading of electron density over a large volume of space (away from the nuclei)
1-4

Electron Configuration of Atoms

Electrons are confined to regions of space called principal energy levels (shells).
Each shell can hold 2n2 electrons (n = 1,2,3,4......).

N u mb er of Relative En ergies Electrons S hell of Electrons S hell Can Hold in Thes e Shells h igh er 32 4 18 3 8 2 2 1 low er

1-5

Electron Configuration of Atoms

Shells are divided into subshells called orbitals, which are designated by the letters s, p, d, f........
s (one per shell) p (set of three per shell 2 and higher) d (set of five per shell 3 and higher) .. The distribution of Orbitals in Shells
S hell 3 2 1 O rb itals Contain ed in Th at S hell 3s , 3p x , 3p y , 3p z, p lu s five 3d orbitals 2s , 2p x , 2p y , 2p z 1s

1-6

Electron Configuration of Atoms

Aufbau (Build-Up) Principle:
Orbitals fill in order of increasing energy from lowest energy to highest energy.

Pauli Exclusion Principle:

No more than two electrons may be present in an orbital. If two electrons are present, their spins must be paired.

Hunds Rule:
When orbitals of equal energy are available but there are not enough electrons to fill all of them, one electron is added to each orbital before a second electron is added to any one of them; the spins of the electrons in degenerate orbitals (same energy) should be aligned.
1-7

Electron Configuration of Atoms

The pairing of electron spins

1-8

Electron Configuration of Atoms

1-9

Electron Configuration
Energy-level diagram: A pictorial designation of where electrons are placed in an electron configuration. For example, the energy-level diagram for the ground-state electron configuration of carbon is 1s2 2s2 2p2. For chlorine: 1s2 2s2 2p6 3s2 3p5.
3p 2p Energy 2s Energy 3s

2p 2s

1s

Energy-level diagram for carbon (atomic number 6)

1s

Energy-level diagram for chlorine (atomic number 17)

1-10

Approximate order of filling orbitals with electrons

E

5p 4d 5s 4p 3d 4s 3p 3s 2p 2s 1s

1-11

The Concept of Energy

In the discussion of energy-level diagrams, lines are drawn on the diagram to depict relative energies. Energy: The ability to do work. The higher in energy an entity, the more work it can perform. Potential energy: Stored energy. Unstable structures have energy that is waiting to be released if given the opportunity. When the energy is released, work is done, such as, burning gasoline to drive the pistons in an internal combustion engine that propels the automobile.
1-12

The Concept of Energy

In the ground state of carbon, electrons are placed in accordance with the quantum chemistry principles (aufbau, Hunds rule, Pauli exclusion principle, etc.) that dictate the lowest energy form of carbon. If we place the electrons in a different manner (as for example with one electron in the 2s and three electrons in the 2p) we would have a higher energy level referred to as an excited state. When the electrons are rearranged back to the ground state, energy is released.
1-13

The Concept of Energy

Electrons in the lowest energy orbital, 1s, are held tightest to the nucleus and are the hardest to remove from the atom. First ionization energy: The energy needed to remove the most loosely held electron from an atom or molecule.

1-14

Lewis Dot Structures (Simple bonding theories)

Lewis electron-dot diagrams are very simplified but very useful models for analyzing bonding in molecules Valence electrons are those in the outer shell of an atom and they are the electrons involved in chemical reactions and bonding The Lewis symbol is the elements symbol plus one dot per valence electron

.. . ... S
[Ne]3s23p4
1-15

Lewis Dot Structures

Table 1.4. Lewis Dot Structures for Elements 1-18

1A
H

2A

3A

4A

5A
. .N : . . .P : .

6A
. :O: . . :S : .

7A
. :.. : F :Cl : : .

8A
He

. . .
Be

Li

: :

: :

:N e : :A r : : :

Na

Mg

Al

. Si : .

: :

. B

. C: .

1-16

Lewis Model of Bonding

Atoms interact in such a way that each participating atom acquires an electron configuration that is the same as that of the noble gas nearest it in atomic number. An atom that gains electrons becomes an anion. An atom that loses electrons becomes a cation. The attraction of anions and cations leads to the formation of ionic solids. This ionic interaction is often referred to as an ionic bond. An atom may share electrons with one or more atoms to complete its valence shell; a chemical bond formed by sharing electrons is called a covalent bond. Bonds may be partially ionic or partially covalent; these bonds are called polar covalent bonds
1-17

Electronegativity
Electronegativity:
A measure of an atoms attraction for the electrons it shares with another atom in a chemical bond.

Pauling scale
Generally increases left to right in a row. Generally increases bottom to top in a column.

1-18

Some important EN values

H 2,2 Li 1,0 Na 0,9 K 0,8 Rb 0,8 Cs 0,8 Be 1,6 Mg 1,3 Ca 1,0 Sr 0,9 Ba 0,9
1-19

* B 2,0 Al 1,6 Sc 1,4 Y 1,2 C 2,5 Si 1,9 Ge 2,0 Sn 1,9 N 3,0 P 2,2 As 2,2 Sb 2,0 O 3,5 S 2,6 Se 2,5 Te 2,1 F 4,0 Cl 3,2 Br 3,0 I 2,7 * * Kr 3,3 Xe 3,0

Formation of Ions
A rough guideline:
Ions will form if the difference in electronegativity between interacting atoms is 1.9 or greater. Example: sodium (EN 0.9) and fluorine (EN 4.0) We use a single-headed (barbed) curved arrow to show the transfer of one electron from Na to F.

Na

Na

In forming Na+F-, the single 3s electron from Na is transferred to the partially filled valence shell of F.
Na(1 s 22s 22p 63s 1) + F(1s 2 2s 2 2p 5 ) Na + (1s 22s 22p 6) + F-(1s 2 2s 2 2p 6 )

1-20

Covalent Bonds
The simplest covalent bond is that in H2
The single electrons from each atom combine to form an electron pair.
H
+

H-H

H 0 = -435 kJ (-104 kcal)/mol

The shared pair functions in two ways simultaneously; it is shared by the two atoms and fills the valence shell of each atom.

The number of shared pairs

One shared pair forms a single bond Two shared pairs form a double bond Three shared pairs form a triple bond
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Polar and Nonpolar Covalent Bonds

Although all covalent bonds involve sharing of electrons, they differ widely in the degree of sharing. We divide covalent bonds into
nonpolar covalent bonds and polar covalent bonds.
D i fference in El ectron eg ati vity Betw een Bo nded Ato ms Less than 0.5 0.5 to 1.9 Greater than 1.9

Typ e of Bond N on pol ar cov alent Pol ar co valent Io ns f orm

1-22

Polar and Nonpolar Covalent Bonds

An example of a polar covalent bond is that of H-Cl. The difference in electronegativity between Cl and H is 3.0 - 2.1 = 0.9. We show polarity by using the symbols + and -, or by using an arrow with the arrowhead pointing toward the negative end and a plus sign on the tail of the arrow at the positive end.
+ H Cl H Cl

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Polar Covalent Bonds

Bond dipole moment ():
A measure of the polarity of a covalent bond. The product of the charge on either atom of a polar bond times the distance between the two nuclei. The table shows average bond dipole moments of selected covalent bonds.
Bond Dipole Bond (D ) Bond Dipole Bond (D ) Bond D ipole Bond (D)

H-C H-N H-O H-S

0.3 1.3 1.5 0.7

C-F C-Cl C-Br C-I

1.4 1.5 1.4 1.2

C-O C=O C-N -C=N

0.7 2.3 0.2 3.5

1-24

Octet Rule

Atoms tend to gain, lose or share electrons until they are surrounded by eight valence electrons (i.e., until they resemble a noble gas) Molecules share pairs of electrons in bonds and may also have lone pairs

:O
H

:
H

O :

:
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Drawing Lewis Structures

1. Sum the valence electrons from all atoms For anions add one electron for each negative charge For cations subtract one electron for each positive charge 2. Connect atoms with single bonds (except for simple molecules it has to be determined experimentally) 3. 4. Complete octets for atoms bonded to central atom (except H - 2e) Place leftover electrons on central atom, even if this goes beyond octet

5. If not enough electrons to provide octet to central atom, try multiple bonds
(alternative methods can be found in different books )

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Lewis Structures - Table 1.8

H-O-H H 2 O (8) Water H C C H H C2 H 4 (12) Ethylene H H-C C-H C2H 2 (10) Acetylen e H-N-H H N H 3 (8) Ammonia H H-C-H H CH 4 (8) Meth ane H C O H CH 2O (12) Formald ehyde H O H-Cl HCl (8) Hyd rogen ch loride O C O H

H 2CO 3 (24) Carbonic acid

In neutral molecules hydrogen has one bond. carbon has 4 bonds and no lone pairs. nitrogen has 3 bonds and 1 lone pair. oxygen has 2 bonds and 2 lone pairs. halogens have 1 bond and 3 lone pairs.

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Formal Charge
Formal charge: The charge on an atom in a molecule or a polyatomic ion.

- Apparent electronic charge of each atom in a Lewis structure (or the charge an atom would have if electron pairs were shared equally) - Each atom owns one e- of a bonding pair - A purely covalent model

1-28

Formal Charge
To derive formal charge
1. Write a correct Lewis structure for the molecule or ion. 2. Assign each atom all its unshared (nonbonding) electrons and one-half its shared (bonding) electrons. 3. Compare this number with the number of valence electrons in the neutral, unbonded atom.
Formal charge N umber of = valence electrons in th e neutral, un bonded atom All One h alf of un shared + all sh ared electrons electrons

4. The sum of all formal charges is equal to the total charge on the molecule or ion.
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Formal Charge

Formal charge

N umber of = valence electrons in th e neutral, un bonded atom

All One h alf of un shared + all sh ared electrons electrons

-1 C

0 N

C: (4 valence electrons) - (2 non bonding + 3 bonding) = -1 N: (5 valence electrons) - (2 non bonding + 3 bonding) = 0

1-30

Formal Charge

Formal Charge

+1

-1

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Formal Charge
Example: Draw Lewis structures, and show which atom in each bears the formal charge.
(a) NH2 + (d) CH3 NH3 (b) HCO3 (e) HCOO

(c) CO3

2-

(f) CH3 COO

1-32

Apparent Exceptions to the Octet Rule

Molecules that contain atoms of Group 3A elements, particularly boron and aluminum.
6 electrons in the valence shells of boron and aluminum
: : F: :F : : B :F: :

: Cl : : Cl : : Al : Cl : :

Boron trifluoride

Aluminum chloride

1-33

Apparent Exceptions to the Octet Rule

Expanded shells (hypervalence)
When it is impossible to write a structure consistent with the octet rule increase the number of electrons around the central atom
Cl Cl P Cl Cl Cl

10e around P

Only for elements from 3rd row (P, S) and heavier, which can make use of empty d orbitals

(Maximum 18e: 2s, 6p, 10d)

1-34

Apparent Exceptions to the Octet Rule

The P in trimethylphosphine obeys the octet rule by having three bonds and one unshared pair. A common depiction of phosphoric acid, however, has five bonds to P, which is explained by invoking the use of 3d orbitals to accommodate the additional bonds.
: Cl : : : : : P Cl : : : Cl : : :O: H- O-P- O-H : O-H Phosphoric acid :
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CH3 -P- CH 3 CH3 Trimethylphosphine

: Cl

: : : :

: Cl

Phosphorus pentachloride

Functional Groups
Functional group: An atom or group of atoms within a molecule that shows a characteristic set of physical and chemical properties. Functional groups are important for three reasons; they are:
1. the units by which we divide organic compounds into classes. 2. the sites of characteristic chemical reactions. 3. the basis for naming organic compounds.

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Alcohols
Contain an -OH (hydroxyl) group bonded to a tetrahedral carbon atom.
H H -C-O-H Fu nctional group : : H-C-C-O-H H H Ethan ol (an alcohol)

Ethanol may also be written as a condensed structural formula.

CH3 -CH2 -OH or CH3 CH2 OH

1-37

Alcohols
Alcohols are classified as primary (1), secondary (2), or tertiary (3) depending on the number of carbon atoms bonded to the carbon bearing the -OH group.

H CH3 -C-OH H A 1 alcohol

H CH3 -C-OH CH3 A 2 alcohol

CH3 CH3 -C-OH CH3 A 3 alcohol

1-38

Alcohols
There are two alcohols with molecular formula C3H8O.
HHH H-C-C-C-O-H H HH H HOH H C-C-C-H HH H or CH3 CH2 CH2 OH a 1 alcohol

or

OH CH3 CHCH3 a 2 alcohol

1-39

Amines
Contain an amino group; an sp3-hybridized nitrogen bonded to one, two, or three carbon atoms.
An amine may be 1, 2, or 3.
: CH3 N H H Methylamine (a 1 amine) : : CH3 N H CH3 Dimethylamine (a 2 amine) CH3 N CH3 CH3 Trimethylamine (a 3 amine)

1-40

Aldehydes and Ketones

Contain a carbonyl (C=O) group.
: O: C H O CH3 -C- H :O: C O CH3 -C- CH 3

Functional Acetaldehyde (an aldehyde) group

Functional group

Acetone (a ketone)

1-41

Carboxylic Acids
Contain a carboxyl (-COOH) group.
O C O H Fu nctional group :O: CH3 -C-O-H : :

or CH3 COOH or CH3 CO2 H

Acetic aci d (a carboxy li c acid )

1-42

Carboxylic Esters
Ester: A derivative of a carboxylic acid in which the carboxyl hydrogen is replaced by a carbon group.

O C O Functional group

O CH3 - C-O- CH 2 -CH3

Ethyl acetate (an ester)

1-43

Carboxylic Amide
Carboxylic amide, commonly referred to as an amide: A derivative of a carboxylic acid in which the OH of the -COOH group is replaced by an amine.
O C N Fu nctional group O CH3 -C-N-H H Acetamid e (a 1 amid e)

The six atoms of the amide functional group lie in a plane with bond angles of approximately 120.

1-44

Valence Shell Electron Pair Repulsion Theory (VSEPR)

(a very approximate but very useful way of predicting molecular shapes)

Electrons in molecules appear in bonding pairs or lone pairs Each pair of electrons repels all other pairs Molecules adopt geometries with electron pairs as far from each other as possible

Electron pairs define regions of space where they are likely to be: Between nuclei for bonding pairs Close to one nucleus for lone pairs those regions are called electron domains 1-45

Valence Shell Electron Pair Repulsion Theory (VSEPR)

Geometries of electron domains

1-46

Valence Shell Electron Pair Repulsion Theory (VSEPR)

Molecular Geometries

1-47

Valence Shell Electron Pair Repulsion Theory (VSEPR)

Lone pairs are larger than bonding pairs

1-48

VSEPR Model
Example: predict all bond angles for these molecules and ions.
( a ) N H4 + ( e ) CH 3 CH = CH 2 ( h) CH3 CH O ( b ) CH3 NH 2 ( f ) H 2 CO 3 ( i) CH 3 COOH ( d ) CH3 OH ( g ) HCO 3 ( j ) BF4 -

1-49

Polar and Nonpolar Molecules

To determine if a molecule is polar, we need to determine
if the molecule has polar bonds and the arrangement of these bonds in space.

Molecular dipole moment (): The vector sum of the individual bond dipole moments in a molecule.
reported in Debyes (D)

1-50

Electrostatic Potential (elpot) Maps

Relative electron density distribution in molecules is important because it allows us to identify sites of chemical reactivity.
Many reactions involve an area of relatively high electron density on one molecule reacting with an area of relatively low electron density on another molecule. It is convenient to keep track of overall molecular electron density distributions using computer graphics.

1-51

Electrostatic Potential (elpot) Maps

In electrostatic potential maps (elpots) (charge
densities are easily computed by programs such as spartan) Areas of relatively high calculated electron density are shown in red. Areas of relatively low calculated electron density are shown in blue. Intermediate electron densities are represented by intermediate colors.

1-52

Polar and Nonpolar Molecules

These molecules have polar bonds, but each molecule has a zero dipole moment.

F O C O F
Carbon dioxide =0D Boron trifluoride =0D

Cl B F Cl Cl C Cl

Carbon tetrachloride =0D

1-53

Polar and Nonpolar Molecules

These molecules have polar bonds and are polar molecules.
direction of dip ole moment O H H H H Ammonia = 1.47D N H direction of dip ole moment

Water = 1.85D

1-54

Polar and Nonpolar Molecules

Formaldehyde has polar bonds and is a polar molecule.

direction of dip ole moment

O H C H

Formaldehyde = 2.33 D

1-55

Quantum or Wave Mechanics

Albert Einstein: E = h (energy is quantized) light has particle properties. Louis deBroglie: wave/particle duality
= h m

Erwin Schrdinger: wave equation wave function, : A solution to a set of equations that depicts the energy of an electron in an atom. each wave function is associated with a unique set of quantum numbers. each wave function represents a region of threedimensional space and is called an orbital. 2 is the probability of finding an electron at a given point in space.
1-56

Quantum or Wave Mechanics

Characteristics of a wave associated with a moving particle. Wavelength is designated by the symbol .

1-57

Quantum or Wave Mechanics

For most aspects of organic chemistry, it is best to consider the wavelike properties of electrons. In this course, we concentrate on wave functions and shapes associated with s and p orbitals because they are the orbitals most often involved in covalent bonding in organic compounds. When we describe orbital interactions, we are referring to interactions of waves. Waves interact constructively or destructively (adding or subtracting). When two waves overlap, positive phasing adds constructively with positive phasing. Positive and negative phasing add destructively, meaning they cancel.

1-58

Shapes of Atomic s and p Orbitals

All s orbitals have the shape of a sphere with the center of the sphere at the nucleus. Figure 1.8 (a) Calculated and (b) cartoon representations showing an arbitrary boundary surface containing about 95% of the electron density.
1-59

Shapes of Atomic s and p Orbitals

Figure 1.9 (a) Three-dimensional representations of the 2px, 2py, and 2pz atomic orbitals computed using the Schrdinger equation. Nodal planes are shaded.

1-60

Shapes of Atomic s and p Orbitals

Figure 1.9(b) Cartoon representations of the 2px, 2py, and 2pz atomic orbitals.

1-61

Molecular Orbital Theory

MO theory begins with the hypothesis that electrons in atoms exist in atomic orbitals and electrons in molecules exist in molecular orbitals.

1-62

Molecular Orbital Theory

Rules:
Combination of n atomic orbitals (mathematically adding and subtracting wave functions) gives n MOs (new wave functions). MOs are arranged in order of increasing energy. MO filling is governed by the same rules as for atomic orbitals: Aufbau principle: fill beginning with LUMO (lowest unoccupied molecular orbital) Pauli exclusion principle: no more than 2e- in a MO Hunds rule: when two or more MOs of equivalent energy are available, add 1e- to each before filling any one of them with 2e-.
1-63

Molecular Orbital Theory

Figure 1.10 MOs derived from combination by (a) addition and (b) subtraction of two 1s atomic orbitals.

1-64

Bonding-Combined VB&MO
Bonding molecular orbital: A MO in which electrons have a lower energy than they would have in isolated atomic orbitals. Sigma () bonding molecular orbital: A MO in which electron density is concentrated between two nuclei along the axis joining them and is cylindrically symmetrical.

1-65

Covalent Bonding-Combined VB & MO

Antibonding MO: A MO in which electrons have a higher energy than they would in isolated atomic orbitals. Sigma star () antibonding molecular orbital: A MO in which population with electrons actually causes repulsion of the nuclei involved.

1-66

Covalent Bonding-Combined VB & MO

Figure 1.11 A MO energy diagram for H2. (a) Ground state and (b) lowest excited state.

1-67

VB: Hybridization of Atomic Orbitals

A principle of VB theory is that bonds are created by the overlap of atomic orbitals.
Therefore in VB theory, bonds are localized between adjacent atoms rather than delocalized over several atoms as in MO theory. The VB model correlates with Lewis pictures where two electrons are visualized between atoms as a bond. However, localization of bonds between atoms presents the following problem: - In forming covalent bonds, atoms of C, N, and O use 2s and 2p atomic orbitals. - If these atoms used these orbitals to form bonds, we would expect bond angles of approximately 90. - However, we rarely observe these bond angles. 1-68

VB: Hybridization of Atomic Orbitals

What we find instead are bond angles of approximately 109.5 in molecules with only single bonds, 120 in molecules with double bonds, and 180 in molecules with triple bonds. To account for the observed bond angles, Linus Pauling proposed that atomic orbitals for each atom should be thought of as first combining to form new atomic orbitals, called hybrid orbitals, which then interact to form bonds by overlapping with orbitals from other atoms. Hybrid orbitals are formed by combinations of atomic orbitals by a process called hybridization. Mathematically, this is accomplished by combining wave functions for the 2s and 2p orbital.
1-69

VB: Hybridization of Atomic Orbitals

The number of hybrid orbitals formed is equal to the number of atomic orbitals combined. Elements of the 2nd period form three types of hybrid orbitals, designated sp3, sp2, and sp. The mathematical combination of one 2s atomic orbital and three 2p atomic orbitals forms four equivalent sp3 hybrid orbitals.
Energy 2p sp3 2s

sp 3 Hybridization, with electron population for carbon to form four single bonds
1-70

VB: Hybridization of Atomic Orbitals

Figure 1.12 sp3 Hybrid orbitals. (a) Computed and (b) cartoon three-dimensional representations. (c) Four balloons of similar size and shape tied together, will assume a tetrahedral geometry.

1-71

VB: Hybridization of Atomic Orbitals

Figure 1.13 Orbital overlap pictures of methane, ammonia, and water.

1-72

VB: Hybridization of Atomic Orbitals

The mathematical combination of one 2s atomic orbital wave function and two 2p atomic orbital wave functions forms three equivalent sp2 hybrid orbitals.
Energy 2p 2p sp2 2s

sp 2 Hybridization, with electron population for carbon to form double bonds

1-73

VB: Hybridization of Atomic Orbitals

Figure 1.14 sp2 Hybrid orbitals and a single 2p orbital on an sp2 hybridized atom.

1-74

VB: Hybridization of Atomic Orbitals

Consider BH3. VSEPR tells us that BH3 is trigonal planar, with 120 H-B-H bond angles. In BH3 the unhybridized 2p orbital is empty.

1-75

VB: Hybridization of Atomic Orbitals

The mathematical combination of one 2s atomic orbital and one 2p atomic orbital gives two equivalent sp hybrid orbitals.
Energy 2p 2p sp 2s

sp Hybridization, with electron population for carbon to form triple bonds

1-76

VB: Hybridization of Atomic Orbitals

Figure 1.16 sp Hybrid orbitals and two 2p orbitals on an sp hybridized atom.

1-77

Combining VB & MO Theories

VB theory views bonding as arising from electron pairs localized between adjacent atoms. These pairs create bonds. Further, organic chemists commonly use atomic orbitals involved in three hybridization states of atoms (sp3, sp2, and 2p) to create orbitals to match the experimentally observed geometries. How do we make orbitals that contain the electrons and that reside between adjacent atoms? For this, we turn back to MO theory.

1-78

Combining VB & MO Theories

To create orbitals that are localized between adjacent atoms, we add and subtract the atomic orbitals on the adjacent atoms, which are aligned to overlap with each other. Consider methane, CH4. The sp3 hybrid orbitals of carbon each point to a 1s orbital of hydrogen and, therefore, we add and subtract these atomic orbitals to create molecular orbitals. As with H2, one resulting MO is lower in energy than the two separated atomic orbitals, and is called a bonding orbital. The other is higher in energy and is antibonding.
1-79

Combining VB & MO Theories

Figure 1.17 Molecular orbital mixing diagram for creation of any C-C bond.

1-80

Combining VB & MO Theories

This approach is used to create C-H bonds. CH3CH3 contains 1 C-C bond and 6 C-H bonds.

1-81

Combining VB & MO Theories

A double bond uses sp2 hybridization. Consider ethylene, C2H4. Carbon and other second-period elements use a combination of sp2 hybrid orbitals and the unhybridized 2p orbital to form double bonds.

1-82

Combining VB & MO Theories

Figure 1.21 MO mixing diagram for the creation of any C-C bond.

1-83

Combining VB & MO Theories

A carbon-carbon triple bond consists of one bond formed by overlap of sp hybrid orbitals and two bonds formed by the overlap of parallel 2p atomic orbitals.

1-84

Covalent Bonding of Carbon

Groups Bonded to Carbon 4 Orbital Hybridization sp 3 Predicted Bond Angles 109.5 Types of Bonds to Each Carbon four bonds

Example

Name Ethane

H H H-C- C- H H H H H C C H H H- C C- H

sp

120

three bonds and one bond two bonds and two bonds

Ethene

sp

180

Ethyne

1-85

Resonance
For many molecules and ions, no single Lewis structure provides a truly accurate representation.
O: H3 C C : :O: :O :

and -

H3 C C : O:

Ethanoate ion (acetate ion)

1-86

Resonance
Linus Pauling - 1930s
Many molecules and ions are best described by writing two or more Lewis structures. Individual Lewis structures are called contributing structures. Connect individual contributing structures by doubleheaded (resonance) arrows. The molecule or ion is a hybrid of the various contributing structures.

1-87

Resonance
Examples: equivalent contributing structures.
:

:O: :N O: : :N

N itrite ion (equivalent con trib uting s tru ctures)

O: CH3 :O :: C

: O :CH3 O: : C

O: : O ::

A cetate ion (equ ivalen t contributin g s tru ctures)

Resonance lowers overall electronic energy (stabilizes)

1-88

Resonance
Curved arrow: A symbol used to show the redistribution of valence electrons. In using curved arrows, there are only two allowed types of electron redistribution:
from a bond to an adjacent atom. from a lone pair on an atom to an adjacent bond.

Electron pushing is a survival skill in organic chemistry.

learn it well!
1-89

Resonance
Split quickly in groups of 4 Read hand-out (chemical activity 3, part B. model 4 &5) Work on the critical thinking questions (10-14) You have 15 min We will discuss the questions in 5 min

1-90

Resonance
All contributing structures must
1. have the same number of valence electrons. 2. obey the rules of covalent bonding: no more than 2 electrons in the valence shell of H. no more than 8 electrons in the valence shell of a 2nd period element. 3. differ only in distribution of valence electrons; the position of all nuclei must be the same. 4. have the same number of paired and unpaired electrons.

1-91

Resonance
The carbonate ion
Is a hybrid of three equivalent contributing structures. The negative charge is distributed equally among the three oxygens as shown in the elpot.

1-92

Resonance
Preference 1: filled valence shells
Structures in which all atoms have filled valence shells contribute more than those with one or more unfilled valence shells.
CH3

+ O

CH3 O

+ C

H Greater contribution; both carbon and oxygen have complete valence shells

H Lesser contribution; carbon has only 6 electrons in its valence shell

1-93

Resonance
Preference 2: maximum number of covalent bonds
Structures with a greater number of covalent bonds contribute more than those with fewer covalent bonds.
CH3 + O

CH 3 O

+ C

H Greater contribution (8 covalent bonds)

H Lesser contribution (7 covalent bonds)

1-94

Resonance
Preference 3: least separation of unlike charge
Structures with separation of unlike charges contribute less than those with no charge separation.
O: CH3 -C- CH3 Greater contribution (no separation of unlike charges)
: :O: -

CH3 -C- CH3 Lesser contribution (separation of unlike charges)

1-95

Resonance
Preference 4: negative charge on the more electronegative atom.
Structures that carry a negative charge on the more electronegative atom contribute more than those with the negative charge on a less electronegative atom.
O C H3 C CH3 (a) Less er con trib ution (1) H3 C O C CH3 (b) Greater contribu tion (2) H3 C O C CH3 (c) S hould n ot be d raw n

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Resonance

-1 S C N

-1
S C N

+1
S C

-2 N

Favored structure provides minimum formal charges places negative formal charges on more electronegative atoms implies smaller separation of charges

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Bond Lengths and Bond Strengths

Name Ethane Formula
H H H- C- C-H C-H H H

Bond
C-C

Orbital Overlap

Bond Length (pm)

sp 3-sp 3 sp 3-1s sp 2-sp 2, 2p-2p sp 2-1s sp -sp , two 2 p-2p sp -1s

153.2 111.4 133.9 110.0 121.2 109.0

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H C C H

C-C C-H

Ethene
H

Ethyne

C-C H-C C-H C-H

Covalent Bonds & Shapes of Molecules

End Chapter 1
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