lecture from monday ch14c, 4/9/12 topics covered: -functional groups -chemdraw, chem3d (computer...
TRANSCRIPT
Lecture from Monday
Ch14C, 4/9/12
Topics covered:-Functional groups-ChemDraw, Chem3D (computer modeling)-Hybridization picture of H2C=C=CH2 (allene)-Drawing resonance structures (Klein handout)-Assessing “good” vs. “bad” resonance structures-Introduction to Conjugation (Part 1 of 2)
Practice Problems for Hybridization
CH3 O1. Identify the functional groups present in the molecule
2. Identify the hybridization of every atom (solutions available in Klein, Problem 4.12)
3. Build a model in 3D to visualize what the molecule actually looks like
C C C
H
H H
H1. Draw out the hybridized orbitals for this molecule.
2. Are the 4 hydrogens all in the same plane? This problem illustrates the power of being able to predict 3-D structure by understanding the principles of hybridized orbitals
RHN
Intro to Functional GroupsFurther reading:- A basic intro in Klein, Sec. 5.1 (p. 84-85)- A detailed list of functional groups in Appendix A of the Thinkbook (p. 326)
R OH
OCarboxylic acid
R O
O
R' Ester
R H
O
R and R' = a simple carbon substituent (i.e. methyl, cyclohexyl, benzene, etc.). In examples below, R and R' can be the same or different substituents
Aldehyde
R R'
O Ketone
R OH Alcohol
R NH2 Amine (1o)
Alkene
Alkyne
Benzene ring
R X Alkyl halide
R O R' Ether
R-SH Thiol
R S R' Sulfide
R S S R' DisulfideR NH2
O
R NH
O
R'or Amide
R H
NR'
Imine
R' Amine (2o)
R N R'
R''
Amine (3o)
R Cl
OAcid chloride
R C N Nitrile
R NO
O
Nitro
R O
O
R'
O
Acid anhydride
OHPhenol
Practice Problems for Hybridization
CH3 O alkyne
ketone
alkene
benzene ringAcetylsalicylic acid (Aspirin)- used to treat headaches
O
OH
O
O CH3
carboxylic acid
ester
O
O
CH3
NH2
HN
H3C O
O
H3C
H3C
Oseltamivir (Tamiflu)- used to treat flu (e.g. H5N1)
ester
amine
amide
ether alkene
Penicillin G- antibiotic produced by the Penicillium fungus
N
HN
O
S Me
Me
OHO
O
Ph
amide
carboxylic acid
amide
sulfide
Made using ChemDraw and Chem3DPrograms available on computers in UCLA Science Learning Center (Young 4335 and others)Intro tutorial to how to use ChemDraw: http://www.chem.umass.edu/~samal/267/chemdraw.pdf
CH3 O
Vollhardt, Figure 14-4 (p. 618)
•So, the hydrogens of allene are NOT in the same plane, but are instead in two planes. •This is not something we might have been able to predict just from looking at the Lewis structure
IUPAC name: propanedieneCommon name: allene H
C
H
C C
H
H
C O C O
Which Resonance Contributor Represents Reality?
The carbon monoxide case:
Neither contributor fully represents CO
Resonance hybrid: A weighted average or blend of resonance contributors; the most accurate representation of the electronic structure of a molecule.
Peach Plum
“True” structure:
Nectarine
Your friend asks you to describe what a nectarine is because he’s never seen or eaten one… (Klein, Sec 2.1)
C O C OX
Which Resonance Contributor Represents Reality?
Once upon a study break...
Real creatureFantasy creaturesNeither fully represents reality A unicorn-dragon hybrid?
The carbon monoxide case:
Neither contributor fully represents CO
Resonance hybrid: A weighted average or blend of resonance contributors; the most accurate representation of the electronic structure of a molecule.
X
Drawing the Resonance Hybrid
Example: Draw the resonance hybrid for acetate ion, CH3CO2-.
2. Draw the features that are the same for all contributors• Sigma and pi bonds, lone pairs, and formal charges
3. Add features that are not the same for all contributors
CH3 O
O
CH3 O
O
CH3 O
O
CH3 O
O
1. Draw contributors
•Partial (shared) pi bonds shown as ----•Partial (shared) charges shown as + or - CH3 O
O
Resonance hybrid
Do All Contributors Have Equal Importance?Is a rhinoceros more unicorn or more dragon?
contributor “stability” = resemblance to reality = contribution to hybrid
Therefore we need contributor preference (“stability”) rules:
As the number and/or magnitude of rules violations ,
= importance of individual contributor
= contribution to resonance hybrid
Resonance Contributor Preference Rules
Rule #1: The most important contributor has the maximum number of atoms with full valence shells.
Rule #1 is more influential than all the other preference rules.
Rules #2-6 have no particular order of preference.
Open valence shell on carbonLess important contributor
Example: H2C OHH2C OH
In some cases it may not be possible for all atoms to have full valence shells.
For practice: see Klein Sec 2.8
Resonance Contributor Preference Rules
Rule #2: The most significant contributor has the maximum number of covalent bonds.
Three covalent bondsLess important contributor
Example: C
H
H
O C
H
H
O
Resonance Contributor Preference Rules
Rule #3: The most significant contributor has the least number of formal charges.
No formal chargesMore important contributor
Two formal chargesLess important contributor
Example: C
H
H
O C
H
H
O
Resonance Contributor Preference Rules
Rule #4: If a contributor must have formal charge(s), the most important contributors has these charges on the atom(s) that can best accommodate them.
Carbon EN = 2.5Less important contributor
Oxygen EN = 3.5More important contributor
•Negative formal charges best on atoms of high electronegativity O- better than C-
•Positive formal charges best on atoms of low electronegativity C+ better than O+
•Minimize formal charge magnitude +1 better than +2
H3C CH2
O
H3C CH2
O
H3C CH2
O
Resonance Contributor Preference Rules
Rule #5: Resonance interaction (i.e., pi bond) is strongest between atoms in the same row of the periodic table.•Usually CNOF
•Usually outweighs electronegativity considerations (rule #4)
F, C both 2nd rowMore important contributorEven though EN F > EN Cl
C 2nd row; Cl 3rd rowLess important contributor
Example:F C Cl
H
F C Cl
H
Resonance Contributor Preference Rules
Rule #6: Other factors (such as aromaticity) that we will encounter later.
Violations to the resonance contributor preference rules exist, but are uncommon.
Resonance Structure Examples
N O N O
Reasonable Resonance Structure
Unreasonable Resonance Structure
N O
H
- positive charge on oxygen, but oxygen doesn't have even have octet
- has formal charges, but at least octet rule is satisfied and charges are distributed on the appropriate atom (based on EN)
OH
OH
H
OH
H
H
H
- one carbon doesn't have full octet- two carbons directly adjacent both have negative charge
- all atoms have complete octet
Nitro Compounds
Napoleon's Buttons, Chap 5: Nitro Compounds
4 KNO3 (s) + 7 C(s) + S (s) 3 CO2 (g) + 3 CO (g) + 2 N2 (g) + K2CO3 (s) + K2S (s)- potassium nitrate- saltpeter- "Chinese snow"
carbon (e.g. wood charcoal)
sulfur carbon dioxide
carbon monoxide
nitrogen potassium carbonate
potassium sulfide
shockwave of gas (6000 meters per sec for TNT)
CH3
NO2
OHO
NH2
Chemical Formula: C7H7NO2
p-nitro toluene(explosive)
p-amino benzoic acid (PABA)(not explosive)- sunscreens
CH3
NO2
NO2O2N
trinitrotoluene (TNT)- patented by Alfred Nobel (Nobel Prize)
O
O
O
NO2
NO2
NO2
Nitroglycerin
body chemistry
N=O
nitric oxide- dilates blood vessels- treatment of heart disease angina pectoris
2 NH4NO3 (s) 2 N2 (g) + O2 (g) + 4 H2O (g)
ammonium nitrate (fertilizer)
O
O
O
O
NO2
NO2
NO2
O2N
pentaerythritol tetranitrate (PETN)- plastic explosive
N
R
O
ONitro functional group
What does this molecule have to do with resonance?
Conjugated Molecules - Part 1 Lecture Supplement page 28
What is Conjugation?
For any molecule best structure = lowest energy
Lowest energy from minimizing electron repulsion and maximizing p orbital overlap•Maximum p orbital overlap allows...
Square planar or tetrahedral? Staggered or eclipsed?
MethaneH
CH H
HH
H
CH
H
What are these?}ResonanceConjugationAromaticity
•Familiar examples: Which structure is lowest energy?
EthaneH
C C
HH
H
HH
C C
HH
H
H H
H
What is Conjugation?Case #1: Relative stability of C4H6 isomers
• Restriction: Hof comparisons only valid among isomers
4 C (graphite) + 3 H2 (g) Hof = 29.9 kcal mol-1
4 C (graphite) + 3 H2 (g) Hof = 47.7 kcal mol-1
More stable isomer
Isomers
•Isomers: Same molecular formula, different structure
• Importance: Lower Hof = more stable isomer
•Heat of formation (enthalpy of formation; Hof): Hypothetical enthalpy change when a
substance is synthesized from elements in their standard states
29.9
30.7
32.0 C C CH3H3C
37.5
91.8 1,2-butadiene (an allene)
s-cis-1,3-butadiene
45.8
C C CH2CH3H
s-trans-1,3-butadiene
47.7
64.6
67.7
H2C C C
CH3
H
1,3-dienes
E n t h a l p y o f f o r m a t i o n ( H o f ) , k c a l m o l - 1 ( c a l c u l a t e d )
0.0 4 C (graphite) + 3 H2 (g)
What is Conjugation?
Why this order?•Ring strain?
No ring strain
•Position of pi bonds?
Two pi bonds
One pi bondRing strain
Two pi bonds
No ring strain
•Number of pi bonds?
Case #1: Relative stability of C4H6 isomers
Alternating pi-sigma-pi bonds
What is Conjugation?
Case #2: Catalytic Hydrogenation of 1,3-Dienes versus 1,4-Dienes
Thermodynamics
•Lose: H-H sigma bond, C-C pi bond
•Gain: 2 x C-H sigma bond
•Sigma bonds usually stronger than pi bonds
•Therefore catalytic hydrogenation is exothermic (H < 0)
H = -30 kcal mol-1Example: CC
H
CH3CH2
H
H
H2
PtCCH3CH2
H
C
H
H
H
H
Catalytic hydrogenation: Addition of H2 to a pi bond with a catalyst
What is Conjugation?Case #2: Catalytic hydrogenation of 1,3-dienes versus 1,4-dienes
H = -65.1 kcal mol-1H = -56.5 kcal mol-1
1,3-butadiene more stable than 2-butyne
E n t h a l p y ( H ; k c a l m o l - 1 )
C CH3C CH3
Same molecule = same enthalpy (H)
+ 2 H2
+ 2 H2
•Observation: H (1,3-butadiene butane) < H (2-butyne butane) by 8.6 kcal/mol
•Conclusion: Lowest H (for catalytic hydrogenation) belongs to most stable isomer
How can we use catalytic hydrogenation to probe C4H6 isomer stability?
•Fact: 1,3-butadiene more stable than 2-butyne
What is Conjugation?Case #2: Catalytic hydrogenation of 1,3-dienes versus 1,4-dienes
•Use H (cat H2) to compare pi-sigma-pi (1,3-diene) versus pi-sigma-sigma-pi (1,4-diene)
H = -30 kcal mol-1
Predict: H = 2 x (-30) = -60 kcal mol-1Observe: H = -60 kcal mol-1Conclusion: No special stability for 1,4-diene
1,4-Pentadiene (a 1,4-diene)
1-Pentene (alkene energy benchmark)
1,3-Butadiene (a 1,3-diene) Predict: H = -60 kcal mol -1 if stability = 1,4-dieneObserve: H = -56.5 kcal mol-1 3.5 kcal mol-1 less than expectedConclusion: 1,3-diene more stable than 1,4-diene.
2 H2
Pt1
23
4
2 H2
Pt12
34
5
General observation: 1,3-dienes more stable than similar 1,4-dienes
H2
Pt
The experiment
Lecture from Wed, 4/11/12
-Conformations of 1,3-butadiene (s-cis vs. s-trans)-Discussion of how dihedral angle relates to extent of p-orbital overlap-Resonance picture of 1,3-butadiene correlates well to physical properties-Conjugated molecules and color
C
CH
HCH
C
H
H
H
C
CC
H
HCH
H
H
H
1,3-Butadiene: A Closer Look
What is origin of special 1,3-diene stability?
Major conformation? Torsional strain: s-trans < s-cis
Stability: s-trans > s-cis
Planarity: Nearly always planar
s-cis*5%
s-trans95%
C
CC
H
HCH
H
H
H
2.21 Å
C
CH
HCH
C
H
H
H
2.50 ÅK eq > 1
* s-cis = two pi bonds, separated by sigma bond, in cis arrangement
29.5
30
30.5
31
31.5
32
0 10 20 30 40 50 60 70 80 90 100 110 120 130 140 150 160 170 180
E n e r g y ( k c a l m o l - 1 )
C=C-C=C Dihedral angle (degrees)
1,3-Butadiene: A Closer LookRotation around Csp2 - Csp2 bond:
Pi bondsperpendicular
Barri
er to
rota
tion
Highest energy point
Conclusion: More than just torsional strain is at work
Angle between planes formed by three atoms each
Energy difference between most and
least stable conformations
0 o 90 o
180 o
H
H
H
H
C
CH
HCH
C
H
H
H
1,3-Butadiene: Resonance Model
What is the origin of this extra stability, planarity, and barrier to rotation?
C
CH
HCH
C
H
H
H
C
CH
HCH
C
H
H
H
Resonance hybrid
C
CH
HCH
C
H
H
H
explains barrier to rotation
explains planarity
Resonance hybrid observations •Partial C2-C3 pi bond
•C2-C3 pz orbital overlap
Resonance is often a strong influence on molecular structure, so start there
1,3-Butadiene: Resonance Model
The resonance model looks useful, but simplistic. Is it accurate?
C2-C3 barrier to rotation (kcal mol-1)
C2-C3 bond length (Å)
1,3-ButadieneModel molecules
1.54 1.33
4.5 ~60
Conclusion:
1.48
7.5
Resonance model is accurate despite its simplicity
The resonance model predicts...
Molecule is more stableMolecule is less stable
•Pi electrons have longer wavelength
•No significant resonance •Has some resonance
1,3-Butadiene: Resonance ModelHow does resonance explain why a 1,3-diene is more stable than a 1,4-diene?
1,3-diene1,4-diene
CC C C
C
H
H H
H
HH
H H
CC
H H
C
H
CCH
H H
H
He- e-
•Pi electrons have shorter wavelength
CC C C
C
H
H H
H
HH
H H
CC
H H
C
H
CCH
H H
H
H
•Pi electrons confined between two carbons •Pi electrons roam over four carbons
E = hc/ so wavelength = energy
Discussion of Handout:“p orbital overlap: Resonance, Conjugation, and
Aromaticity”
Conjugated Molecules - Part 2Lecture Supplement page 37
chlorophyll a
CH3
CH3
CH3CH3
CH3CH3
CH3
CH3
H3C
H3C
CH3 CH3
CH3 CH3 CH3
H3C CH3
H3C CH3
CH3
lycopene
-carotene
NN
NN
CH3
CH3
CH3H3C
H3CO
O OR
Mg2+
H3C
CH3
CH3CH3CH3CH3
O
O
R =
Part 1 Summary
•...more resonance•...more electron delocalization•...lower electron energy
Consequences of p orbital overlap•Atoms with p orbitals must be planar•Partial pi bond(s)•Barrier to rotation
more stable thanExample:
Adjacent, overlapping p orbitals allows for...
Greater stability
H NH2
O
Extra Stability Limited to 1,3-Dienes?
Amide resonance contributors:
Pi electron delocalizationprovides increased stability
H NH2
O
Amide resonance hybrid:
H NH2
O
•1,3-diene has four adjacent p orbitals
•Three adjacent p orbitals is enough to provide extra stability
Example: An amide
Extra Stability Limited to 1,3-Dienes?Another special stabilization example: An amide
•Predict: Four attachments = sp3
•sp3 lacks p orbital needed for resonance•Therefore sp2 to accommodate resonance•Therefore sp2 to increase stability
I thought hybridization is controlled only by the number of attachments?!•Energy causes geometry; geometry causes hybridization
Influenced by electron repulsion, resonance, etc.
Resonance hybridH NH2
O
Nitrogen hybridization?
H NH2
O
C
N
O
H
H
H
C C C CH
H
H
HH
H
Extra Stability Limited to 1,3-Dienes?More adjacent p orbitals = larger electron “playground”
An amide has three adjacent, parallel p orbitals:
Compare with 1,3-butadiene: Four adjacent, parallel p orbitals:
Build your own model
Build your own model
C
N
O
H
H
H
p orbital overlap forms pi bonds
C C C CH
H
H
HH
H
In general: Adjacent, parallel p orbitals improve molecular stability
Sigma bonds
p orbital overlap gives delocalized pi bonds
Conjugation: Special stability provided by electron delocalization in three
or more adjacent, parallel, overlapping p orbitals.
Conjugation: A DefinitionFinally!
Decrease in electron energy
Not limited to pi-sigma-pi(four carbon pz orbitals)
Consequences of Conjugation
Conjugation influences widespread
•Chemical reactivity: Is molecule reactive or inert?
•Molecular structure: Is a molecule (or portion of molecule) flat? Is bond rotation hindered?
•Physical properties: Color
•Etc.
O
CH3
CH3
CH3
O
CH3
HO
CH3
CH3
H
O
CH3
HO
CH3
CH3
H
O
CH3
HO
CH3
CH3
Consequences of Conjugation
•Influences distribution of products in chemical reaction
•Reaction products: stability = amount produced
•Example: Determine major product of this reaction:
- H2O
Ten conjugated p orbitals Six conjugated p orbitalsMore stable Less stable
Produced in greatest amount
O
CH3
CH3
CH3
or
Which product isomer is more stable?
Consequence #1: More extensive conjugation = greater stability
N
O
H R
Consequences of Conjugation
•Resistance to conformational change (barrier to rotation)
More stable Less stable
Barrier to rotation and planarity critical to protein function.
N
O
H
RN
O
H R
Resonance hybrid
Barrier torotation
Planar
Less torsional strain More torsional strain
Consequence #2: Partial pi bond character
•Example: Amide linkage between two amino acids in a protein
•Causes planarity of atoms conjugated p orbitals
Consequences of Conjugation
Consequence #3: Highly conjugated molecules may be colored
Examples:
Chlorophyll Lycopene -Carotene
Origin of color: •Some portion of visible (white) light spectrum is absorbed
•Brain perceives remaining light as color
So how does molecular structure control energy of photons absorbed?
molecular orbitals as descriptors of conjugated systems
Recall: Here is how we described the atomic orbitals of one carbon atom
2p
2s
sp3
hybridizationsp3
4 atomic orbitals in 4 hybrid atomic orbitals out
Here: The number of molecular orbitals is equal to that of the component p orbitals (which is the number of carbon atoms with a p orbital)
example: 1,3-butadiene
4 p atomic orbitals in 4 molecular orbitals out
four 2p atomic orbitals
2p
1
2
3
4
HOMO
LUMO the lower this gap, the longer the wavelength absorbed
Consequences of ConjugationHow does molecular structure control energy of photons absorbed?
•Molecule absorbs photon (h)
E
E l e c t r o n e n e r g y
Lowest UnoccupiedMolecular Orbital
(LUMO)
Highest OccupiedMolecular Orbital
(HOMO)
Absorb photon (E = h)
Ground state Excited state
•Electron is excited to higher energy molecular orbital
•Energy of photon absorbed must equal HOMO/LUMO orbital energy difference (E)
Controlled by electron energies
Consequences of ConjugationHow does molecular structure control energy of photons absorbed?
number of conjugated p orbitals E•WhenE low enough, photons of visible light absorbed•Unabsorbed portion of visible light spectrum perceived as color
P h o t o n e n e r g y
Photon absorbed Observed color
Ultraviolet (UV)
Visible light
YellowOrange
RedVioletIndigoBlue
Green
Colorless
VioletIndigoBlue
GreenYellowOrange
Red
Consequences of ConjugationHow does molecular structure control energy of photons absorbed?
Example Molecules
Four conjugated p orbitalsE = ultraviolet
Perceived color = colorless
1,3-Butadiene
Six conjugated p orbitalsE = ultraviolet
Perceived color = colorless
1,3,5-Hexatriene
Eight conjugated p orbitalsE = ultraviolet
Perceived color = colorless
Styrene
YellowOrange
RedVioletIndigoBlue
Green
VioletIndigoBlue
GreenYellowOrange
Red
Consequences of ConjugationHow does molecular structure control energy of photons absorbed?
Example Molecules
Twelve conjugated p orbitalsPhotons of h = E are indigo
Perceived color = orange
Ten conjugated p orbitalsPhotons of h = E are violet
Perceived color = yellow
Retinal
O
Retinol (vitamin A)
OH
YellowOrange
RedVioletIndigoBlue
Green
VioletIndigoBlue
GreenYellowOrange
Red
Consequences of ConjugationHow does molecular structure control energy of photons absorbed?
Example Molecules
22 conjugated p orbitalsPhotons of h = E are blue
Perceived color = red
H3C CH3
CH3 CH3 CH3
CH3 CH3 CH3
CH3H3C
LycopeneNot conjugated
Not conjugated
YellowOrange
RedVioletIndigoBlue
Green
VioletIndigoBlue
GreenYellowOrange
Red
Friday’s topic: Aromaticity (pre-read!!!)
1,3-Butadiene: A Closer LookRotation around the C2-C3 bond•The s-cis conformation is planar
Indicates movie to play
•Filename: s-cis change perspective.mov
1,3-Butadiene: A Closer LookRotation around the C2-C3 bond•Perpendicular conformation has lowest torsional strain
•Filename: s-cis to perpendicular.mov
1,3-Butadiene: A Closer LookRotation around the C2-C3 bond•The s-trans conformation is planar
•Filename: perpendicular to s-trans_prof.mov