Chapter

 3  

Stabilizing  Effects  in  Hydrocarbon  Chemistry    

The  goal  of  this  chapter:  

 
•  Iden=fy  the  presence  of  strained  stabilized  systems  
 
•  Predict  quan=ta=ve  values  of  strain/stabiliza=on  based  on  
chemical  equa=ons  or  other  methods  (e.g.,  Benson  Increments)  
3.  Strain/Stabiliza=on  of  Organic  Molecules  

Hf298 (kcal/mol)

-20.04

-25.02 Alkane  heats  of  forma2on  

-30.03
increase  in  regular  pa7erns  
 
-35.08 ~  -­‐5  kcal/mol  for  each  CH2  
 
-39.90 Basis  for  Benson  and  other  
group  increment  schemes  
-44.85

-49.90

Chapter  3  
3.  Strain/Stabiliza=on  of  Organic  Molecules  

6*(-4.93) = -29.58 kcal/mol - Calculated

-29.43 kcal/mol - Experiment
(CH2)6

How should one derive other group increments?

- = (CH3)2
n-octane cyclohexane
H3C-(CH2)6-CH3 (CH2)6
-49.90 kcal/mol -29.58 kcal/mol -20.32 kcal/mol

~ -10 kcal/mol per CH3

Rela2onships  between  heats  of  forma2on  assist  in  

our  understanding  of  alkane  thermochemistry  
Chapter  3  
3.  Strain/Stabiliza=on  of  Organic  Molecules  

H H

C - 3 (CH3)
CH3 C
H 3C CH3
isobutane
(CH3)3CH 3 * (-10.02 kcal/mol) -2.01 kcal/mol
-32.07 kcal/mol -30.06 kcal/mol ~ -2 kcal/mol group increment

CH3

C - 4 (CH3) C
CH3
H 3C CH3
neopentane
(CH3)4C 4 * (-10.02 kcal/mol) -0.06 kcal/mol
-40.14 kcal/mol -40.08 kcal/mol ~ 0 kcal/mol group increment

Deriva2on  of  addi2onal  group  increments  

Chapter  3  
3.  Strain/Stabiliza=on  of  Organic  Molecules  
H H
H CH3 H CH3
or
H 3C H H CH3 2 "skew"
interactions
CH3 CH3
"skew"
interaction

This unfavorable interactions must also be corrrected in group increment schemes

2 skews 1 skew

- = 1 skew

-41.02 kcal/mol -41.66 kcal/mol +0.64 kcal/mol

Positive value indicative of destabilization (strain)

Some  alkanes  are  strained  from  unfavorable  steric  

interac2ons,  which  increases  their  heat  of  forma2on  
Chapter  3  
3.  Strain/Stabiliza=on  of  Organic  Molecules  

H 3C CH3
CH3 Which of these compounds is more strained?
H 3C
Why?
CH3 What are their respective heats of formation?
H 3C
H 3C CH3

Chapter  3  
3.  Strain/Stabiliza=on  of  Organic  Molecules  

H
H 3C CH3 H 3C CH3 2 skew interactions
CH3
H 3C H CH2CH2CH3 -53.67 kcal/mol

CH3

CH3 4 skew interactions

H 3C
H 3C CH3 -52.61 kcal/mol

Remember:  Think  in  3-­‐dimensions!  

Chapter  3  
3.  Strain/Stabiliza=on  of  Organic  Molecules  
H H AlBr3 H H
H2, cat. low temp.

H H H H
mixture of isomers expt Hf -58.13
10 x -5 = -50
Thermal  
4 x -2 = -8 rearrangement  of  
Benson = -58 kcal/mol
-12 kcal/mol anthracene  to  
AlBr3
driving force
higher temp. tetramethyl-­‐  
CH3
adamantane  
AlBr3 AlBr3  
even higher temp.
even higher temp.
Benson  helps  to  
4 x -10 = -40
3 x -10 = -30
1 x -10 = -10
understand  
7 x -5 = -35
6 x -5 = -30
4x0=0
1 x -2 = -2
8 x -5 = -40
5 x -2 = -10 reac2ons  also.  
3x0=0
Benson = -70 kcal/mol Benson = -60 kcal/mol
2 skew = +2
Benson = -65 kcal/mol

Chapter  3  
3.  Strain/Stabiliza=on  of  Organic  Molecules  

2 skews 2 skews 2 skews

Acyclic Cyclic Polycyclic

Do  all  of  these  skew  interac2ons  destabilize  systems  to  the  

same  extent?  

Chapter  3  
3.  Strain/Stabiliza=on  of  Organic  Molecules  

2 skews 2 skews 2 skews

Acyclic Cyclic Polycyclic
~1.4 kcal/mol ~2.0 kcal/mol ~3.0 kcal/mol

Systems  have  different  flexibili2es,  which  can  minimize  

“repulsive”  interac2ons.    
Skew  interac2ons  are  less  destabilizing  in  acyclic  and  cyclic  
systems  because  methyl  groups  can  “bend  away”  
Chapter  3  
3.  Strain/Stabiliza=on  of  Organic  Molecules  

H H R H Does  the  size  of  

subs2tuents  always  
influence  the  strain?  
R R H R  
Why  is  the  cis/trans  
H, kcal/mol
isomeriza2on  energy  
R = CH3 -1.0
R = C2H5 -1.0
different  from  t-­‐butyl  
R = i-C3H7 -1.0 than  for  other  bulky  
R = t-C4H9 -10.0 groups  like  isopropyl?  

Chapter  3  
3.  Strain/Stabiliza=on  of  Organic  Molecules  

H H H H Favorable  
arrangements  exist  
H H H 3C CH3 for  all  subs2tuent  
H
H H
H H
H H
H
groups  except  t-­‐
R= CH3 R=C2H5
butyl,  which  has  a  
H-H bumping H-H bumping much  larger  cis/trans  
H H H H
isomer  difference  of  
10  kcal/mol  (versus  1  
H 3C CH3 H 3C CH3 kcal/mol  for  others)  
H 3C CH3 H 3C
CH3H3C
CH3  
H H
Bulky  subs2tuents  
R=i-C3H7 R=t-C4H9
H-H bumping CH3-CH3 bumping aren’t  always  less  
favorable!  
Chapter  3  
3.  Strain/Stabiliza=on  of  Organic  Molecules  

How would the environment affect strain for different R groups?

R R R

R = Me ~ Et ~ iPr << tBu R = Me ~ Et << iPr << tBu R = Me << Et << iPr << tBu

R' R'' R'

H
H H H
H H

Different  environments  result  in  varying  amounts  of  strain  based  

on  subs2tuent  type.  
Degree  of  strain  determined  by  the  number  of  skew  interac2ons.  
Chapter  3  
3.  Strain/Stabiliza=on  of  Organic  Molecules  

-2.04
kcal/mol
-30.03 -32.07 Branching  is  known  to  
kcal/mol kcal/mol stabilize  alkanes  (calimetric  
-1.65
studies  by  Rossini  in  the  
kcal/mol 1930s).  
-35.08 -36.73
kcal/mol kcal/mol
 
What  is  the  physical  origin  of  
-5.06 the  stabiliza2on?  
kcal/mol
-35.08 -40.14
kcal/mol kcal/mol

Chapter  3  
3.  Strain/Stabiliza=on  of  Organic  Molecules  
-2.04
-30.03
kcal/mol At  least  in  part,  this  is  due  to  
-32.07
kcal/mol kcal/mol stabilizing  van  der  Waals  
interac2ons  between  C  and  H  
-1.65
-35.08
kcal/mol atoms  on  1,3-­‐disposed  carbon  
-36.73
kcal/mol kcal/mol atoms.  
-5.06  
-35.08
kcal/mol
-40.14
Computa2onally,  very  sensi2ve  to  
kcal/mol kcal/mol electron  correla2on.  

HF/6-­‐31G*   MP2/6-­‐31G*   Expt  

n-­‐pentane   0.0  kcal/mol   0.0  kcal/mol   0.0  kcal/mol  
2-­‐methylbutane   +0.6  kcal/mol   -­‐1.2  kcal/mol   -­‐1.7  kcal/mol  
neopentane   -­‐1.1  kcal/mol   -­‐5.3  kcal/mol   -­‐5.1  kcal/mol  

Chapter  3  
3.  Strain/Stabiliza=on  of  Organic  Molecules  

3 favorable branching interactions

4 favorable branching interactions

6 favorable branching interactions

1,3-­‐alkyl-­‐alkyl  interac2ons  stabilize  branched  alkanes  over  their  

linear  counterparts.  Alkanes  with  lower  heats  of  forma2on  tend  
to  possess  greater  numbers  of  these  interac2ons.  

Chapter  3  
3.  Strain/Stabiliza=on  of  Organic  Molecules  

isobutane n-butane 1 branch point

3 favorable 1,3-interactions 2 favorable 1,3-interactions

-32.07 kcal/mol -30.03 kcal/mol -2.04 kcal/mol

neopentane n-pentane 3 branch points

6 favorable 1,3-interactions 3 favorable 1,3-interactions
-40.14 kcal/mol -35.08 kcal/mol -5.06 kcal/mol

-1.69 kcal/mol per branch

propane
1 favorable 1,3-interaction
??? kcal/mol

1,3-­‐alkyl-­‐alkyl  interac2ons  are  also  present  in  linear  alkanes.  

These  type  of  branching  interac2ons  were  termed  
“protobranching”  (proto:  being  the  parent  form  of)   Chapter  3  
3.  Strain/Stabiliza=on  of  Organic  Molecules  

1 protobranch

2 protobranches
But how do we determine the
3 protobranches quantitative value of a protobranching
interaction?
4 protobranches

5 protobranches

Isodesmic bond seperation reaction (conceived by John Pople* in the 1970s)

+ CH4 2 C2H 6 2.83 kcal/mol Value of 1 protobranch
Seperate the compound of interest into the simplest two heavy atom bonds.
Balance with methane.

* John Pople was the co-recipient of the 1998 Nobel Prize in Chemistry

1,3-­‐alkyl-­‐alkyl  interac2ons  are  also  present  in  linear  alkanes.  

These  type  of  branching  interac2ons  were  termed  
“protobranching”  (proto:  being  the  parent  form  of)   Chapter  3  
3.  Strain/Stabiliza=on  of  Organic  Molecules  

The  energy  of  protobranching  interac2ons  are  addi2ve  for  n-­‐

alkanes,  but  are  a7enuated  for  branched  systems.  
Chapter  3  
3.  Strain/Stabiliza=on  of  Organic  Molecules  

Changes  in  the  number  of  branches  are  par2cularly  difficult  to  
describe  computa2onally.  Systema2c  devia2ons  are  apparent.   Chapter  3  
3.  Strain/Stabiliza=on  of  Organic  Molecules  

less stable, higher energy than "normal"

"strained" and/or "anti-aromatic"

0 reference standard

"conjugated" and/or "aromatic"

more stable, lower energy than "normal"

What  standard  to  use?  

What  is  “normal”?  
Heats  of  forma2on  are  based  on  elements  in  their  standard  state.  
(graphite  for  C,  H2(gas)  for  H)  
DHf°  of  alipha2cs  are  nega2ve  [C2H6  =  -­‐20.04  kcal/mol]  
DHf°  of  aroma2cs  are  posi2ve  [C6H6  =  19.82  kcal/mol]  
Chapter  3  
3.  Strain/Stabiliza=on  of  Organic  Molecules  

CH   C  
"Standards" for the assessment of strain should be
selected based on "strain-free" structural features. acetyleneic   27.1   27.3  
-bond angles olefinic   8.55   10.19  
-torsional angles
-non-bonded interactions
aroma=c   3.29   5.49  
alipha=c   -­‐2.40   -­‐0.10  
Illustration: (CH)6

Acetylenes: 3 HC CH Hf = 162.6 kcal/mol

(hypothetical,
Olefins: Hf = 51.3 kcal/mol
resonance free)

Aromatics: Hf = 19.8 kcal/mol

(hypothetical,
Aliphatics: Hf = -14.4 kcal/mol
strain free)

Chapter  3  
3.  Strain/Stabiliza=on  of  Organic  Molecules  

CH3
H 3C CH3

H 3C CH3
CH3
C12H18 C12H18
Hf -14.6 kcal/mol -36.0 kcal/mol At the extreme, the
aromatic graphite is
CH3
0.5 kcal/mol more stable
than the aliphatic diamond!

H 3C

C14H20 C14H20
Hf -22.4 kcal/mol -48.8 kcal/mol

Chapter  3  
3.  Strain/Stabiliza=on  of  Organic  Molecules  
Unsaturation Strain

C6H12

-12.9 kcal/mol -30.0 kcal/mol

heats of formation from

group increments

+4.6 kcal/mol
C10H18

-44.0 kcal/mol

-5.8 kcal/mol

Note  that  none  of  these  compounds  are  “strained”  appreciable  

by  angle,  torsional,  or  non-­‐bonded  interac=ons  
 
Double  and  triple  CC  bonds  are  unfavorable  vs  single  CC  bonds!  
Chapter  3  
3.  Strain/Stabiliza=on  of  Organic  Molecules  

Baeyer Strain

60 90

109.49 109.49

109.49 109.49
- 60 - 90
49.49 angle deviation 19.49

Ideal tetrahedral value vs. cyclic rings

Chapter  3  
3.  Strain/Stabiliza=on  of  Organic  Molecules  

Baeyer  strain  of  Cycloalkanes  and  Silacycloalkanes.  

Based  on  Baeyer’s  assump=on  that  all  rings  are  planar.   Chapter  3  
3.  Strain/Stabiliza=on  of  Organic  Molecules  

Strain in Cyclobutane

2.0Å Angle Strain = 19.4 degrees

Torsion Strain = Planar rings have eclipsed bonds

1.55Å

H H
H
H
H -1.3 kcal/mol H
H

"puckers" H H
H H
H H
H
H
1,3 - transannular CC interactions destabilize cyclobutane
(sum of van der Waals radii ~3.2Å)

Chapter  3  
3.  Strain/Stabiliza=on  of  Organic  Molecules  

Determining Strain Energies

Cyclopropane Cyclobutane
3 - CH2 groups 4 - CH2 groups
3 * (-5.0) = -15.0 kcal/mol 4 * (-5.0) = -20.0 kcal/mol
expected heat of formation expected heat of formation

Actual heat of formation = 12.7 kcal/mol Actual heat of formation = 6.8 kcal/mol Benson  group  
12.7 - (-15.0) = 27.7 kcal/mol 6.8 - (-20.0) = 26.8 kcal/mol increments  can  
Ring strain of cyclopropane
be  used  to  derive  
Ring strain of cyclobutane
strain  energies  

-18.3 - (-25.0) = 6.7 kcal/mol Ring strain of cyclopentane

-29.4 - (-30.0) = 0.6 kcal/mol Ring strain of cyclohexane

Chapter  3  
3.  Strain/Stabiliza=on  of  Organic  Molecules  
Homodesmotic Equations*
The  same  values  can  
+ 3 C2H6 3 27.7 kcal/mol
reproduced  directly  
12.7 3(-20.0) 3(-25.0)
using  chemical  
equa=ons  coupled  with  
+ 4 C2H6 4 26.8 kcal/mol
experimental  (or  
6.8 4(-20.0) 4(-25.0)
computa=onally  
determined)  heats  of  
+ 5 C2H6 5 6.7 kcal/mol forma=on.  
-18.3 5(-20.0) 5(-25.0)
 
But  are  these  equa=ons  
+ 6 C2H6 6 0.6 kcal/mol appropriate?  
-29.4 6(-20.0) 6(-25.0)
 
What  about  the  
* a reaction which has: (a) equal numbers of each type of carbon-carbon bond
[C(sp3)-C(sp3), etc.] in reactants and products and (b) equal numbers of each
type of carbon atom (sp3, sp2, sp) with one, two, or three H atoms attached
reference  compounds?  
Chapter  3  
3.  Strain/Stabiliza=on  of  Organic  Molecules  

The "Art" of Balancing Chemical Reactions

no stabilizing propane stabilized

geminal interactions + 3 C2H6 3 by protobranching
in cyclopropane (1,3-alkyl-alkyl interaction)

2 cross-ring
geminal C-C + 4 C2H6 4 4 protobranches
interactions

5 geminal + 5 C2H6 5 5 protobranches

1,3-CC interactions

6 geminal + 6 C2H6 6 6 protobranches

1,3-CC interactions

Chapter  3  
 3.  Strain/Stabiliza=on  of  Organic  Molecules  

Isodesmic* vs. Homodesmotic Approaches The  strain  energy  of  

cyclopropane  
Is  actually  lower  than  
+ 3 C2H6 3 27.7 kcal/mol
indicated  by  equa=on  1    
 
Stabilized by 3*(2.8) = 8.4 kcal/mol
Equa=on  2  gives  a  revised  
value  which  is  free  of  
+ 3 CH4 3 C2H 6 19.2 kcal/mol contamina=on  
 
No stabilization problem because reference The  strain  of  the  carbon  
compounds have no (proto)branching
skeleton  may  be  even  
*a reaction in which all bonds between heavy (non-hydrogen) atoms are seperated into
the simplest (or parent) molecule with the same type of bond
lower  because  of  
torsional  strain  (6  
eclipsed  C-­‐H  bonds)  
Chapter  3  
3.  Strain/Stabiliza=on  of  Organic  Molecules  

This homodesmotic equation + 4 C2H6 4 26.8 kcal/mol

is flawed

2 protobranches 4 protobranches

This isodesmic equation + 4 CH4 4 C2H 6 15.2 kcal/mol

is flawed

2 protobranches 0 protobranches

This equation is + 2 CH4 2 21.0 kcal/mol

properly balanced

2 protobranches 2 protobranches

Chapter  3  
3.  Strain/Stabiliza=on  of  Organic  Molecules  

+ 5 C2H6 5 6.7 kcal/mol

5 protobranches 5 protobranches

+ 6 C2H6 6 0.6 kcal/mol

6 protobranches 6 protobranches

Homodesmo=c  equa=ons  balance  branching  interac=ons  for  

cyclopentane  and  larger  cycloalkanes.  
Chapter  3  
3.  Strain/Stabiliza=on  of  Organic  Molecules  

Conjuga=on  and  hyperconjuga=on  are  known  to  stabilize  

hydrocarbon  systems  containing  mul=ple  bonds.  
 
Prototype hyperconjugated hydrocarbons Prototype conjugated hydrocarbons
(also carbocations)

Antibonding
Partial occupation of
antibonding orbital
H
C C CH2 sigma pi
H
H

Bonding

Chapter  3  
3.  Strain/Stabiliza=on  of  Organic  Molecules  

+ C2H6 + 2.7 kcal/mol

+ C2H6 + 4.9 kcal/mol

Hyperconjuga=on  is  generally  assessed  by  homodesmo=c  

equa=ons  like  these.  
 
Do  the  energies  seem  reasonable?  
 
What  stereoelectronic  effects  are  present  in  each  equa=on?  
  Chapter  3  
3.  Strain/Stabiliza=on  of  Organic  Molecules  

+ C2H6 + 2.7 kcal/mol

1 "ene" hyperconjugation 1 protobranch

Homodesmo=c  
+ C2H6 + 4.9 kcal/mol
assessments  (equa=ons  1  
and  2)  are  imbalanced.  
1 "yne" hyperconjugation 1 protobranch
 
Equa=ons  3  and  4  are  
+ CH4 + 5.5 kcal/mol more  appropriate!  
1 "ene" hyperconjugation
 
+ CH4 + 7.7 kcal/mol

1 "yne" hyperconjugation

Chapter  3  
3.  Strain/Stabiliza=on  of  Organic  Molecules  

-25.9 -29.8 -29.8

+ H2 + H2 - (-25.9)
25.5 -0.4 -30.2
3.9 kcal/mol

"textbook" description
of diene conjugation

-69.6 -69.6 -69.6

+ 2H2 + 2H2 - (-69.6)
109.0 39.4 -30.2 0.0 kcal/mol

???

Are  textbook  defini=ons  of  conjuga=on  energies  correct?  

 
Chapter  3  
3.  Strain/Stabiliza=on  of  Organic  Molecules  

+ 2 3.7 kcal/mol

+ 2 0.0 kcal/mol

Are hyperconjugation and protobranching interactions fully balanced?

+ 2 CH4 2 + 14.8 kcal/mol

+ 2 CH4 2 + 15.1 kcal/mol (27.1 kcal/mol)

More reasonable value,

but requires correction of
12 kcal/mol for differences
in C-H bond hydribidzation

Balancing  all  interac=on  is  cri=cal  for  obtaining  reasonable  

energies,  the  later  values  for  diene  and  diyne  conjuga=on  have  
been  confirmed  by  independent  theore=cal  methods.   Chapter  3  
 
 Mini  Quiz  4  

1.  Using  what  you  have  learned  about  alkane  stabili2es,  rank  the  following  
alkanes  in  order  of  lowest  (most  nega2ve)  to  highest  heat  of  forma2on.  

2.  Write  appropriate  equa2ons  to  es2mate  the  cage  strain  of  tetrahedrane  and  
H
adamantane.   H H C
C
CH
C 2 2

H 2C
HC CH
C C
H C H2
HC CH H
H 2C C
H2
tetrahedrane adamantane
Hint:  Start  with  isobutane  to  balance  “CH”  groups  and  propane  to  balance  “CH2”  groups