Chapter 1 Concepts and Models in Organic Chemistry

General discussion of some overall concepts in organic chemistry.

Chapter 1 Problems
Problems each worth 5 pts. 1, 4, 6, 14, 16, 21

What is a model?
A representation of the real Details of the model are only as useful as they are helpful to explain observations. When a model does not explain observations it must be modified or thrown out.

Modern Models
How do we arrive at Models
Imagination Creativity Desire to explain what we observe

Often quantitative in order to explain observations from instruments.

Examples of Models.
Lewis dot diagrams Tinker Toy Models Dreiding Models CPK space filling models Quantum Mechanical Models

How do we know what a molecule look like?

Imagination
Not very quantitative Helps sharpen understanding

Graphic representation of quantitative models.

Ethane Model
Different views

Each has a use.

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Molecular dimensions.
How do we get the molecular dimensions of molecules?
X-ray Electron and Neutron diffraction
Only on solids Give nuclei positions of heavy atoms

Microwave
Usually low MW molecules
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Bond Lengths and Angles

Represent the inter-nuclei distances as points in space The electron density extends out from these points.
Molecule
CH3 F CH3C l CH3 Br CH3I

rC-H
1.105 1.096 1.11 1.096

r C-X
1.385 1.781 1.939 2.139

<H-C-H
109 54 110 52 111 12 111 50
o o o o

<H-C-X
109 2 108 0 107 14 106 58
o o o o

van der Waals Radius

Ionic Radius(ri)
from the distance between ions in a crystal changes with charge on the ion

Covalent Radius (rc )

1/2 the distance between two atoms of the same element

van der Waals Radius (rvdW )

atomic distances in the crystal
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Covalent Radii
Functions of charge.
C4+ 0.15A while C4- 2.60A

Depends on bonding
C bonded to four groups 0.772A C double bonded 0.67A

Effective Radii for groups of atoms.

CH3 2.0A
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Atomic Volume and Surface

Atomic volumes can be calculated from values in Table 1.3 (p.8) Butane
2xCH 3 = 2x17.12 = 34.24 2x CH2 = 2x10.23 = 20.46 total=54.7cm3/mole

Theory cal = 99.91 A3 = 60.14 cm3/mole

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Heats of Formation
o is the difference in enthalpy between the compound and the elements in their standard state.
m C(grap hite) + n/2 H2 (gas ) C mHn H
o f

Obtained from heats of combustion data.

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Heats of Combustion
H o when the compound is burned with excess O 2
Cm Hn + ( m + n/4) O2 m CO2 + n/2 H2O Ho = heat of compustion

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General case
C(graphi te) + O2(gas) CO2(gas) H or = Hof (CO2) H2(gas) + 1/2 O2(gas) H or = Hof (H 2O) Combining these quations. H of (Cm Hn) = m Hof (CO 2) + n/2 Hof (H2O) - Ho(combustion) (CmH n) H 2O (liquid)

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Corrections
Change of phase
heat of vaporization for liquids heat of sublimation for solids Temperature corrections

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Example From Book

O + 8 O2 O H f (H2 O) = -68.32 Kcal/mol
o o o

6 CO2 + 4 H2 O

H = -735.9 K cal/mol

H f (CO2 ) = -94.05 Kcal/mol

o o c ombustion

H f (cyclohexanedione) = 4 H f (H2 O) + 6 H f (CO2) - H

(cyclohexanedion

Ho f (cyclohexanedione) = 4 (68.32) + 6 (94.05) - (-735.9) = -101.68 Kcal/mol Correction of solid to gas H

o sub

= +21.46 Kcal/mol

Ho f (cyclohexanedione) = -101.68 Kcal/mol + 21.46 = -80.22 Kcal/mol

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Differences Between Compounds

You can use heats of reactions if you go to a common product.
CH3 H CH3 H H CH3 CH3 H

-28.6 Kcal/mol

-27.6 Kcal/mol

CH3CH2CH2CH3

Tran more stable than cis by 1 Kcal/mol

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Principle Additivity
The property of a molecule can be estimated from the the parts (bonds or groups). If you know the contribution from a group in one molecule you can use it in another calculation.
CH3CH2CH2CH3 Hof = -30.4 Kcal/mol CH3CH2CH2CH2CH3 Hof = -35.1 Kcal/mol

H of (CH2) = -35.1 - -30.4 Kcal/mol = -4.7 Kcal/mol

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Table 1.5 Bond Increments to H o f

How well does this method work? CH 4 cal -15.32 found -17.89 Kcal/mol Ethane
6 C-H and 1 C-C 6 (-3.83) + 1 (2.73) = -20.25 Kcal/mol Found -20.24 (not bad)

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Problem
Calculated values
CH3 CH3CHCH3 10 (-3.83) 3 (2.73) = -30.11 Kcal/mol CH3CH2CH2CH3 10 (-3.83) 3 (2.73) = -30.11 Kcal/mol

They are the same Obs. -32.4 Kcal/mol and -30.4 Kcal/mol respectively.
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Group Increments (Table 1.7)

Group contributions allow for different bond types. CH3
CH3CHCH3 3 CH 3 = 3 (-10.8) 1 CH = -1.9 = -34.3 Kcal/mol CH3 CH2CH2CH3 2 CH 3 = 2 (-10.8) 2 CH 2 = 2 (-4.5) = -29.6 Kcal/mol

Obs. -32.4 Kcal/mol and -30.4 Kcal/mol respectively (better?)

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Limitation
Group increments do not consider strain contribution
CH3 CH3CHCH2CH2CH3 3 CH3 = 3 (-10.8) 2 CH2 = 2 (-4.5) 1 CH = 1 (-1.9) =-42.04 Kcal/mol (exp. -41.66) H CH3 CH3 H H CH2 CH3 1 gausche interatction 0.8

Correction -42.04 + 0.8 = -41.24 (better)

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Bond Dissociation Energies

The energy needed to break the bond.
Homolytic
A B A B H
o r

Hetrolytic
A B A B H
o r

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Using Bond Dissociation Energies

Example
CH3CH3 + H2 2 CH4 DHo = 104.2 Kcal/mol H2 2H

CH3CH3

2 CH3

DHo = 88 Kcal/mol

2 CH3

+ 2 H

2 CH4

2 DHo = 2 (-104 Kcal/mol)

Ho = 2(-104. Kcal/mol) + 104.2 + 88 = -15.8 Kcal/mol A check Hor = 2 Hof (CH4) - Hof(CH 3CH3) - Hof(H 2) = 2(-17.9) - (-20.2) - 0 = -15.6 Kcal/mol

This calculation does not say anything about how fast the reaction occurs.

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Bonding Models
What holds molecules together?
Groups of atoms find they are a lower energy when they are associated with each other. They are bonded. Electrostatic attractions.
Na
+

Cl

NaCl energy

Covalent bond
H H H H

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Models
Lewis Model
For some reason atoms (first row) are in a low energy state if the have 8 electrons around them. Why? -1 -2 -3
Ne F O N

Electron transfer between atoms of different electronegativity

F Cs F
-1

Cs

+1

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Covalent Bond
Both atoms have the same EN
F F F F

Bonding only involves outer shell electrons (valence shell electron)

P 1s2 2s2 2p6 3s2 3p3 core valence electrons

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Dipole Moment
Vector sum of the dipole moments of the bonds.
= charge (esu) X distance (cm) = Debye (D)
+0.1 esu

A B 1.5A

-0.1 es u

= 0.1 (4.8 x 10-10esu) 1.5 A(1 x 10-8cm/A) = 0.72 x 10-18 esu cm = 0.72 Debye (D)

Dipole moments useful in understanding properties.

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Which Molecules Have Dipole Moments?

CH 3 Cl H H Cl H CH3 H CH 3 H

Cl CH3 CH 2CH 2OH

Cl

Cl

O O O

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Bond Polarity
Bond polarity comes from unequal sharing of bonding electrons.
Polar Bond = Covalent part + ionic part
% Ionic character = 2 (1 + 2) (100)

molecule =covalent + ionic

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Electronegativity
Unequal sharing of electrons between atoms of a bond. Pauling Electronegativity Scale
Compares bond dissociation energies of like atoms with those of unlike atoms. H2 and Cl2 (104.2 + 58)/2 = 81.1 Kcal/mol HCl 103.2 (larger due to ionic character)
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Table 1.8
Other EN scales
Pauling, p Mullikin, m Allen, spec Nagel, Benson, x (I+A)/2

Which EN scale to use depends on application.

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Bonding
Valence Bond Theory (VB)
Bring together of atoms which share electrons.

Molecular Orbital Theory (MO)

Bring together nuclei which are held together by electrons.

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H2 Molecule
Two Hydrogen atoms
H1s H1s

We can write the equations for a 1s orbital. Wave functions = c a(1) b(2)
1

2 = c a(2) b(1) VB = c a(2) b(1) + c a(2) b(1)

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LCAO Method
Linear C ombinations of Atomic O rbitals
1 = c1 a(1) + c2 b(1) 2 = c1 a(2) + c2 b(2)
MO = 1 2 = c12 a(1) a(2) + c22 b(1) b(2) + c1c2[a(1)b(2) + a(2)b(1)

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Comparison
VB is simpler and is incorporated into the MO wave function LCAO method has ionic contribution As terms are added to either model they both give better answers and they become very much alike.

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Energy Levels
The MO model generates the orbital and the energies of the orbitals.
AO MO AO

Energy

H H-H H

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Methane
Atomic Orbital view. 1s2 2s22p2 This model predicts
CH2 with a bond angle of 90 o
Energy p s

AO

s Carbon

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Observation
Methane is CH4. Need new model with 4 unpaired electrons. Two possible solutions
unpair one of the s electrons and put it in a p orbital. Completely reorganize the orbital.

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Hybridization
A model that can be used to explain what we observe. Based on AOs
Linear Combination of an s and three p orbitals Higher in energy than an s but lower than a p.

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Energy

Energy

sp3

s Carbon

Hybridized

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LCAO
Four AOs must yield 4 MOs
sp3 = 1/2( C2s + C2px + C2py + C2pz) sp3 = 1/2( C2s - C2px - C2py + C2pz) sp3 = 1/2( C2s + C2px - C2py - C2pz) sp3 = 1/2( C2s - C2px + C2py - C2pz)

There is an error in the book

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Shape and Orientation

The electron distribution must have the characteristics of both s (spherical) and p (node) orbitals. The four new electron distributions (orbitals) will orient as far away from each other as possible. Toward the corners of a tetrahedron.
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Photoelectron Spectroscopy
Measures the energy of electrons ejected from a molecule when hit by a photon. Binding energy = photon energy - emitted photon energy
h = T + E B

Methane shows >290 ev (C1s) and two more bands, 23.0 ev and 12.7 ev. (Two types of orbitals)
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Orbital Symmetry
The MOs must be symmetric or antisymmetric with respect to the AOs (basis set). The sigma bond resulting from the C sp 3 and H 1s do not have the symmetry of the s an p orbital.

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New Approach
Consider all the AOs of C and 4 Hs. Select symmetric or anti-symmetric linear combination. If we ignore the C1s electrons there should be 4 bonding and 4 non-bonding orbitals.

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Orbitals and Energies

-13.30708 Kcal/mol -28.87874 Kcal/mol

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VSEPR Theory
Valence Shell Electron Pair R epulsion Theory
Electrons in orbitals will take on a geometry that has the electrons as far away from each other as possible.

2 sp 3 sp 2 4 sp 3

180 deg. 120 deg. 109.5 deg.

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Methyl Chloride
Predicted bond angles
H-C-H 109.5 o H-C-Cl 109.5o

Experimental
H-C-H 110o 52 H-C-Cl 108o 0

Why?
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VSEPR Explanation
Cl more EN than Carbon. Draws electon density toward Cl. C-H bond shorter. The electron density is shifted toward the Cl so the Hs repel each other more than in methane making H-C-H bond angle greater. The H are attracted to the Cl so the H-C-Cl bond angle is smaller
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MO Explanation
The HOMOs show significant bonding between the Cl and C-H bond

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Variable Hybridization
Because of the EN of chlorine the methyl chloride molecule will be less symmetric. The C-Cl bond will have more p character which results in the C-H bond having more s character. C-H shorter and H-C-H angle larger.

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Hybridization Parameter
For a bond sp n is the hybridization parameter. 2 = n For an sp3 the fractional s and p character are
%s= 1 1+ 2i %p= 2i 1+ 2i

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Interorbital Angles
Based on hybridization model 1 + a b cos ab = 0 Angle A-C-B 1 + a2 cos aa = 0 Angle A-C-A

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Methyl Chloride (again)

Two bond angles H-C-H and H-C-Cl Relationship between these two angles
3 sin ab = 2 (1 - cos a a
2

If we know one we can calculate the other. If H-C-Cl is 108 o then cos = 1 - 3 sin
2 ab aa

cos aa = 1 -

3 (sin (108))2 2

aa = 110 o
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Carbon Orbital
Orbital to H.
sp2.86
a2 = -1 cos aa = 2.86

The other C orbital to Cl

3 1 1 + 2.86 + 1 1 + b2 =1

b2 = 3.50

sp3.5
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Curved Bonds
Consider CH2Cl2
Measured Cl-C-Cl 111o 47; H-C-H 112 o 0 Cal. C to Cl orbital sp 2.69; C to H sp3.37 or a bond angle of 107. The bond angle does not fit experimental.

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Are Bonds Straight Lines Between Nuclei?

Electron density may lie outside the line between two nuclei. Internuclear bond angle - defined by nuclear positions Interorbital bond angle - defind by the direction the orbital leaves the atom.

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Bent Bonds
Best example cyclopropane
C H C C H Interatomic 115.1o

C-H hybridization sp2.36 which would make the C-C sp2.69 which would predict an interorbital angle of 111.8 o; > 60 o.
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Measurable Properties
Hybridization parameter can not be measured directly but it can be correlated to some measurable parameters. J13C-H (cps) = 500/ (1 - 2) rC-H = 1.1597 - 10-4 J13C-H log krel = 0.129 J13C-H - 15.9

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, Model for Ethene

Carbon is sp 2 hybridized H-C bond is shorter than normal because bond has more s character C-C bond has two parts; from overlap of two C sp 2 hybrids and a from overlap of two p orbital. H-C-H 120 o and the same for H-C-C. C-C shorter, more s character
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Energy Diagram
Hybrid Orbitals of Carbon MO's Hybrid Orbitals of Carbon

p sp2 PE to H 1s

p sp2 to H 1s

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Bent Bond Model

Pauling Carbons are sp 3 with two sp 3 from each carbon overlapping to for two bent bonds.
H C H C H H

Predicts planar but bond angles of 109.5

o
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Acidity of Hydrocarbons
Hydrocarbons are weak acids.
R H + B R
-

+ HB

Ka =

[R-] [HB+ ] [RH] [B]

Ethane 10 -42, ethene 10-36.5, ethyne 10-25

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Why?
The anion stability follows the s character of the orbital that the resultant anion exist in. sp 3 anion less stable than sp 2 which is less stable than sp. Therefore, alkanes less acidic than alkenes which are less acidic than alkynes
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Bent Bond Rationalization

The bent bond pulls the electron pair of the anion closer to the center of the internuclear axis of the C-C bond.
H H H ? H H H H 60 O H H 0O

Less electron pair -- electron pair repulsion

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Which Model is Correct?

Neither! Both models are useful and must be used with care. Usually they converge on the same solution when considered in great detail.

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