ChemWiki - User contributions [en]

Rep:Mod:jotp1357

2009-01-11T21:53:57Z

Jo206: /* Chair and Boat Transition Structures */

== Cope Rearrangement ==

'''anti-hexadiene'''

anti2
HF/3-21G
energy= -231.69253506

point group= Ci with sub group C1

<jmol>
<jmolApplet>
<title>Pentahelicene</title>
<color>blue</color>
<size>300</size>
<script>zoom 80; cpk -25;frame 1; move 10 -20 10 0 0 0 0 0 3; delay 1;</script>
<uploadedFileContents>Anti2mol.mol</uploadedFileContents>
</jmolApplet>
<jmolMenu>
<item><text>Put a script here</text><script>spin on</script></item>
<item><text>Put another script here</text><script>spin off</script></item>
<menuHeight>-1</menuHeight>
</jmolMenu>
<jmolAppletButton>
<color>cyan</color>
<uploadedFileContents>Anti2mol1.mol</uploadedFileContents>
</jmolAppletButton>
</jmol>

'''gauche-hexadiene'''

energy= - 231.69266120
point group= C1 with subgroup C1 aswell.

reoptimised antihexadiene

[[Image:IRspect.jpg]]

experimental values
Sum of electronic and zero-point Energies= -233.070012
Sum of electronic and thermal Energies= -233.062608
Sum of electronic and thermal Enthalpies= -233.061664
Sum of electronic and thermal Free Energies= -233.101686

After reoptimising the anti2 linkage of hexadiene the energy lowered using the B3LYP/6-31G*.
The geometry only changed very slightly, as the bond angles changed from 111.36 to 112.41 for C-C-C and from 124.80 to 124.91 for C=C-C.

=== Chair and Boat Transition Structures ===

'''Chair'''

[[Image:allylvib.jpg]]

the vibration corresponding to the cope rearrangement was at -817.952cm-1 with an intensity of 5.9611.

bond forming= 1.5501
bond breaking= 4.74518

I found if the fragments were positioned more than 2.2 apart eachother then i had problems with running the calcualtion for the transition state. Once i had the bond lengths just lower than 2.2 then the calculation ran smoothly.

After doing the calculation by freezing coordinates method at the fixed bond lengths of 2.2 the chair transition state looked the same as above. Once the bonds were not fixed, the transition state looked changed, looking like the vibration that occurs in the bond breaking/forming. The transition state is showned below.

[[Image:chairmod2.jpg]]

'''Boat'''

Initially the job failed when doing the TS (QST2) until the bond angles and dihedral angles of the reactant and product when changed as the image below shows.

[[Image:REACTPROD.jpg]]

the transition state:

[[Image:boat.jpg]]

the transition state frequency at -839.497cm-1 at 1.607 intensity

[[Image:realboatvib.jpg]]

'''Results Table'''

<br />

''' Summary of energies (in hartree) '''

{| border="1" cellspacing="1" cellpadding="10"
|-
| ''' '''
| width="125" align="center" | '''HF/3-21G'''
| width="125" align="center" | '''B3LYP/6-31G*'''
| width="125" align="center" | '''B3LYP/6-31G*'''
| width="125" align="center" | '''B3LYP/6-31G*'''
|-
| ''' '''
| width="125" align="center" | '''Electronic energy'''
| width="125" align="center" | '''Electronic energy'''
| width="125" align="center" | '''Sum of electronic and zero-point energies'''
| width="125" align="center" | '''Sum of electronic and thermal energies'''
|-
| ''' '''
| ''' '''
| ''' '''
| width="125" align="center" | '''at 0 K'''
| width="125" align="center" | '''at 298.15 K'''
|-
| '''Reactant (''anti2'')'''
| align="center" | -231.6925
| align="center" | -233.2099
| align="center" | -233.0700
| align="center" | -233.1017
|}

== Diels-Alder Cycloaddition ==

[[Image:butmech.jpg]]

HOMO-[[Image:butlumo.jpg]]

The molecular orbital is antisymmetric respect to the plane and the axis.

LUMO[[Image:buthomo.jpg]]

The molecular orbital is antisymmetric respect to the plane nut symmetric respect to the axis.

When the cisbutadiene reacts with the alkene the symmetry properties of the orbitals that are overlapping need to be the same therefore the LUMO of ethene needs to antisymmetric to the plane and symmetric to the axis. this will keep the the stereochemistry of substituents.

[[Image:tsbevib.jpg]]

The transtion state frequency is at -818.548cm-1. The value suggests it a certain concerted pericyclic cycloadiition reaction. The next frequency is 166.607cm-1 this corresponds to the the rocking of the ethene fragment.

The fragments were set to be 2.2 angstroms for eachother.

Normal values for C-C bond lengths:

Double bond=1.34Å and single bond=1.54Å

My values have the double bonds at 1.37Å and the single bonds at 1.40Å throught the transition state.

HOMO of the transition state:
[[Image:tsbehomo.jpg]]

=== The Regioselectivity of the Diels Alder Reaction ===

[[Image:malmech.jpg]]

'''Endo'''

optimised energy= -609.403a.u.

LUMO-[[Image:mendolumo.jpg]]

HOMO-[[Image:mendohomo.jpg]]

'''Exo'''

optimised energy= -609.363a.u.

LUMO-[[Image:mexolumo.jpg]]

HOMO-[[Image:mexohomo.jpg]]

When looking the HOMO orbitals of the two products they are very different. If looking at the -C=O-CO-C=O- fragment compared to the rest of the molecule, the electron density moves depending on the product. Most of the electron density seems to sit on the part of the -C=O-CO-C=O- fragment closest to the CH=CH fragment of the ring in the exo product. This seems to be a favourable interaction as the phases of the orbitals are the same. But the endo product the orbitals has an unfavourable interaction with the CH2-CH2 fragment.

== References ==

1. http://www.science.uwaterloo.ca/~cchieh/cact/c120/bondel.html

Rep:Mod:jotp1357

2009-01-11T21:50:40Z

Jo206: /* The Regioselectivity of the Diels Alder Reaction */

== Cope Rearrangement ==

'''anti-hexadiene'''

anti2
HF/3-21G
energy= -231.69253506

point group= Ci with sub group C1

<jmol>
<jmolApplet>
<title>Pentahelicene</title>
<color>blue</color>
<size>300</size>
<script>zoom 80; cpk -25;frame 1; move 10 -20 10 0 0 0 0 0 3; delay 1;</script>
<uploadedFileContents>Anti2mol.mol</uploadedFileContents>
</jmolApplet>
<jmolMenu>
<item><text>Put a script here</text><script>spin on</script></item>
<item><text>Put another script here</text><script>spin off</script></item>
<menuHeight>-1</menuHeight>
</jmolMenu>
<jmolAppletButton>
<color>cyan</color>
<uploadedFileContents>Anti2mol1.mol</uploadedFileContents>
</jmolAppletButton>
</jmol>

'''gauche-hexadiene'''

energy= - 231.69266120
point group= C1 with subgroup C1 aswell.

reoptimised antihexadiene

[[Image:IRspect.jpg]]

experimental values
Sum of electronic and zero-point Energies= -233.070012
Sum of electronic and thermal Energies= -233.062608
Sum of electronic and thermal Enthalpies= -233.061664
Sum of electronic and thermal Free Energies= -233.101686

After reoptimising the anti2 linkage of hexadiene the energy lowered using the B3LYP/6-31G*.
The geometry only changed very slightly, as the bond angles changed from 111.36 to 112.41 for C-C-C and from 124.80 to 124.91 for C=C-C.

=== Chair and Boat Transition Structures ===

'''Chair'''

[[Image:allylvib.jpg]]

the vibration corresponding to the cope rearrangement was at -817.952cm-1 with an intensity of 5.9611.

bond forming= 1.5501
bond breaking= 4.74518

I found if the fragments were positioned more than 2.2 apart eachother then i had problems with running the calcualtion for the transition state. Once i had the bond lengths just lower than 2.2 then the calculation ran smoothly.

After doing the calculation by freezing coordinates method at the fixed bond lengths of 2.2 the chair transition state looked the same as above. Once the bonds were not fixed, the transition state looked changed, looking like the vibration that occurs in the bond breaking/forming. The transition state is showned below.

[[Image:chairmod2.jpg]]

'''Boat'''

Initially the job failed when doing the TS (QST2) until the bond angles and dihedral angles of the reactant and product when changed as the image below shows.

[[Image:REACTPROD.jpg]]

the transition state:

[[Image:boat.jpg]]

the transition state frequency at -839.497cm-1 at 1.607 intensity

[[Image:realboatvib.jpg]]

'''Results Table'''

<br />

''' Summary of energies (in hartree) '''

{| border="1" cellspacing="1" cellpadding="10"
|-
| ''' '''
| width="125" align="center" | '''HF/3-21G'''
| width="125" align="center" | '''HF/3-21G'''
| width="125" align="center" | '''HF/3-21G'''
| width="125" align="center" | '''B3LYP/6-31G*'''
| width="125" align="center" | '''B3LYP/6-31G*'''
| width="125" align="center" | '''B3LYP/6-31G*'''
|-
| ''' '''
| width="125" align="center" | '''Electronic energy'''
| width="125" align="center" | '''Sum of electronic and zero-point energies'''
| width="125" align="center" | '''Sum of electronic and thermal energies'''
| width="125" align="center" | '''Electronic energy'''
| width="125" align="center" | '''Sum of electronic and zero-point energies'''
| width="125" align="center" | '''Sum of electronic and thermal energies'''
|-
| ''' '''
| ''' '''
| width="125" align="center" | '''at 0 K'''
| width="125" align="center" | '''at 298.15 K'''
| ''' '''
| width="125" align="center" | '''at 0 K'''
| width="125" align="center" | '''at 298.15 K'''
|-
| '''Chair TS'''
| align="center" |
| align="center" |
| align="center" |
| align="center" |
| align="center" |
| align="center" |
|-
| '''Boat TS'''
| align="center" |
| align="center" |
| align="center" |
| align="center" |
| align="center" |
| align="center" |
|-
| '''Reactant (''anti2'')'''
| align="center" | -231.6925
| align="center" |
| align="center" |
| align="center" | -233.2099
| align="center" | -233.0700
| align="center" | -233.1017
|}

<br /> *1 hartree = 627.509 kcal/mol <br /><br />

''' Summary of activation energies (in kcal/mol) '''

{| border="1" cellspacing="1" cellpadding="10"
|-
| ''' '''
| width="125" align="center" | '''HF/3-21G'''
| width="125" align="center" | '''HF/3-21G'''
| width="125" align="center" | '''B3LYP/6-31G*'''
| width="125" align="center" | '''B3LYP/6-31G*'''
| width="125" align="center" | '''Expt.'''
|-
| ''' '''
| width="125" align="center" | '''at 0 K '''
| width="125" align="center" | '''at 298.15 K'''
| width="125" align="center" | '''at 0 K'''
| width="125" align="center" | '''at 298.15 K'''
| width="125" align="center" | '''at 0 K'''
|-
| '''ΔE (Chair)'''
| align="center" |
| align="center" |
| align="center" |
| align="center" |
| align="center" |
|-
| '''ΔE (Boat)'''
| align="center" |
| align="center" |
| align="center" |
| align="center" |
| align="center" |
|}

<br />

== Diels-Alder Cycloaddition ==

[[Image:butmech.jpg]]

HOMO-[[Image:butlumo.jpg]]

The molecular orbital is antisymmetric respect to the plane and the axis.

LUMO[[Image:buthomo.jpg]]

The molecular orbital is antisymmetric respect to the plane nut symmetric respect to the axis.

When the cisbutadiene reacts with the alkene the symmetry properties of the orbitals that are overlapping need to be the same therefore the LUMO of ethene needs to antisymmetric to the plane and symmetric to the axis. this will keep the the stereochemistry of substituents.

[[Image:tsbevib.jpg]]

The transtion state frequency is at -818.548cm-1. The value suggests it a certain concerted pericyclic cycloadiition reaction. The next frequency is 166.607cm-1 this corresponds to the the rocking of the ethene fragment.

The fragments were set to be 2.2 angstroms for eachother.

Normal values for C-C bond lengths:

Double bond=1.34Å and single bond=1.54Å

My values have the double bonds at 1.37Å and the single bonds at 1.40Å throught the transition state.

HOMO of the transition state:
[[Image:tsbehomo.jpg]]

=== The Regioselectivity of the Diels Alder Reaction ===

[[Image:malmech.jpg]]

'''Endo'''

optimised energy= -609.403a.u.

LUMO-[[Image:mendolumo.jpg]]

HOMO-[[Image:mendohomo.jpg]]

'''Exo'''

optimised energy= -609.363a.u.

LUMO-[[Image:mexolumo.jpg]]

HOMO-[[Image:mexohomo.jpg]]

When looking the HOMO orbitals of the two products they are very different. If looking at the -C=O-CO-C=O- fragment compared to the rest of the molecule, the electron density moves depending on the product. Most of the electron density seems to sit on the part of the -C=O-CO-C=O- fragment closest to the CH=CH fragment of the ring in the exo product. This seems to be a favourable interaction as the phases of the orbitals are the same. But the endo product the orbitals has an unfavourable interaction with the CH2-CH2 fragment.

== References ==

1. http://www.science.uwaterloo.ca/~cchieh/cact/c120/bondel.html

Rep:Mod:jotp1357

2009-01-11T21:40:50Z

Jo206: /* The Regioselectivity of the Diels Alder Reaction */

== Cope Rearrangement ==

'''anti-hexadiene'''

anti2
HF/3-21G
energy= -231.69253506

point group= Ci with sub group C1

<jmol>
<jmolApplet>
<title>Pentahelicene</title>
<color>blue</color>
<size>300</size>
<script>zoom 80; cpk -25;frame 1; move 10 -20 10 0 0 0 0 0 3; delay 1;</script>
<uploadedFileContents>Anti2mol.mol</uploadedFileContents>
</jmolApplet>
<jmolMenu>
<item><text>Put a script here</text><script>spin on</script></item>
<item><text>Put another script here</text><script>spin off</script></item>
<menuHeight>-1</menuHeight>
</jmolMenu>
<jmolAppletButton>
<color>cyan</color>
<uploadedFileContents>Anti2mol1.mol</uploadedFileContents>
</jmolAppletButton>
</jmol>

'''gauche-hexadiene'''

energy= - 231.69266120
point group= C1 with subgroup C1 aswell.

reoptimised antihexadiene

[[Image:IRspect.jpg]]

experimental values
Sum of electronic and zero-point Energies= -233.070012
Sum of electronic and thermal Energies= -233.062608
Sum of electronic and thermal Enthalpies= -233.061664
Sum of electronic and thermal Free Energies= -233.101686

After reoptimising the anti2 linkage of hexadiene the energy lowered using the B3LYP/6-31G*.
The geometry only changed very slightly, as the bond angles changed from 111.36 to 112.41 for C-C-C and from 124.80 to 124.91 for C=C-C.

=== Chair and Boat Transition Structures ===

'''Chair'''

[[Image:allylvib.jpg]]

the vibration corresponding to the cope rearrangement was at -817.952cm-1 with an intensity of 5.9611.

bond forming= 1.5501
bond breaking= 4.74518

I found if the fragments were positioned more than 2.2 apart eachother then i had problems with running the calcualtion for the transition state. Once i had the bond lengths just lower than 2.2 then the calculation ran smoothly.

After doing the calculation by freezing coordinates method at the fixed bond lengths of 2.2 the chair transition state looked the same as above. Once the bonds were not fixed, the transition state looked changed, looking like the vibration that occurs in the bond breaking/forming. The transition state is showned below.

[[Image:chairmod2.jpg]]

'''Boat'''

Initially the job failed when doing the TS (QST2) until the bond angles and dihedral angles of the reactant and product when changed as the image below shows.

[[Image:REACTPROD.jpg]]

the transition state:

[[Image:boat.jpg]]

the transition state frequency at -839.497cm-1 at 1.607 intensity

[[Image:realboatvib.jpg]]

'''Results Table'''

<br />

''' Summary of energies (in hartree) '''

{| border="1" cellspacing="1" cellpadding="10"
|-
| ''' '''
| width="125" align="center" | '''HF/3-21G'''
| width="125" align="center" | '''HF/3-21G'''
| width="125" align="center" | '''HF/3-21G'''
| width="125" align="center" | '''B3LYP/6-31G*'''
| width="125" align="center" | '''B3LYP/6-31G*'''
| width="125" align="center" | '''B3LYP/6-31G*'''
|-
| ''' '''
| width="125" align="center" | '''Electronic energy'''
| width="125" align="center" | '''Sum of electronic and zero-point energies'''
| width="125" align="center" | '''Sum of electronic and thermal energies'''
| width="125" align="center" | '''Electronic energy'''
| width="125" align="center" | '''Sum of electronic and zero-point energies'''
| width="125" align="center" | '''Sum of electronic and thermal energies'''
|-
| ''' '''
| ''' '''
| width="125" align="center" | '''at 0 K'''
| width="125" align="center" | '''at 298.15 K'''
| ''' '''
| width="125" align="center" | '''at 0 K'''
| width="125" align="center" | '''at 298.15 K'''
|-
| '''Chair TS'''
| align="center" |
| align="center" |
| align="center" |
| align="center" |
| align="center" |
| align="center" |
|-
| '''Boat TS'''
| align="center" |
| align="center" |
| align="center" |
| align="center" |
| align="center" |
| align="center" |
|-
| '''Reactant (''anti2'')'''
| align="center" | -231.6925
| align="center" |
| align="center" |
| align="center" | -233.2099
| align="center" | -233.0700
| align="center" | -233.1017
|}

<br /> *1 hartree = 627.509 kcal/mol <br /><br />

''' Summary of activation energies (in kcal/mol) '''

{| border="1" cellspacing="1" cellpadding="10"
|-
| ''' '''
| width="125" align="center" | '''HF/3-21G'''
| width="125" align="center" | '''HF/3-21G'''
| width="125" align="center" | '''B3LYP/6-31G*'''
| width="125" align="center" | '''B3LYP/6-31G*'''
| width="125" align="center" | '''Expt.'''
|-
| ''' '''
| width="125" align="center" | '''at 0 K '''
| width="125" align="center" | '''at 298.15 K'''
| width="125" align="center" | '''at 0 K'''
| width="125" align="center" | '''at 298.15 K'''
| width="125" align="center" | '''at 0 K'''
|-
| '''ΔE (Chair)'''
| align="center" |
| align="center" |
| align="center" |
| align="center" |
| align="center" |
|-
| '''ΔE (Boat)'''
| align="center" |
| align="center" |
| align="center" |
| align="center" |
| align="center" |
|}

<br />

== Diels-Alder Cycloaddition ==

[[Image:butmech.jpg]]

HOMO-[[Image:butlumo.jpg]]

The molecular orbital is antisymmetric respect to the plane and the axis.

LUMO[[Image:buthomo.jpg]]

The molecular orbital is antisymmetric respect to the plane nut symmetric respect to the axis.

When the cisbutadiene reacts with the alkene the symmetry properties of the orbitals that are overlapping need to be the same therefore the LUMO of ethene needs to antisymmetric to the plane and symmetric to the axis. this will keep the the stereochemistry of substituents.

[[Image:tsbevib.jpg]]

The transtion state frequency is at -818.548cm-1. The value suggests it a certain concerted pericyclic cycloadiition reaction. The next frequency is 166.607cm-1 this corresponds to the the rocking of the ethene fragment.

The fragments were set to be 2.2 angstroms for eachother.

Normal values for C-C bond lengths:

Double bond=1.34Å and single bond=1.54Å

My values have the double bonds at 1.37Å and the single bonds at 1.40Å throught the transition state.

HOMO of the transition state:
[[Image:tsbehomo.jpg]]

=== The Regioselectivity of the Diels Alder Reaction ===

[[Image:malmech.jpg]]

'''Endo'''

optimised energy= -609.403a.u.

LUMO-[[Image:mendolumo.jpg]]

HOMO-[[Image:mendohomo.jpg]]

'''Exo'''

optimised energy= -609.363a.u.

LUMO-[[Image:mexolumo.jpg]]

HOMO-[[Image:mexohomo.jpg]]

== References ==

1. http://www.science.uwaterloo.ca/~cchieh/cact/c120/bondel.html

File:Mexohomo.jpg

2009-01-11T21:34:18Z

Jo206:

Rep:Mod:jotp1357

2009-01-11T21:34:03Z

Jo206: /* Diels-Alder Cycloaddition */

== Cope Rearrangement ==

'''anti-hexadiene'''

anti2
HF/3-21G
energy= -231.69253506

point group= Ci with sub group C1

<jmol>
<jmolApplet>
<title>Pentahelicene</title>
<color>blue</color>
<size>300</size>
<script>zoom 80; cpk -25;frame 1; move 10 -20 10 0 0 0 0 0 3; delay 1;</script>
<uploadedFileContents>Anti2mol.mol</uploadedFileContents>
</jmolApplet>
<jmolMenu>
<item><text>Put a script here</text><script>spin on</script></item>
<item><text>Put another script here</text><script>spin off</script></item>
<menuHeight>-1</menuHeight>
</jmolMenu>
<jmolAppletButton>
<color>cyan</color>
<uploadedFileContents>Anti2mol1.mol</uploadedFileContents>
</jmolAppletButton>
</jmol>

'''gauche-hexadiene'''

energy= - 231.69266120
point group= C1 with subgroup C1 aswell.

reoptimised antihexadiene

[[Image:IRspect.jpg]]

experimental values
Sum of electronic and zero-point Energies= -233.070012
Sum of electronic and thermal Energies= -233.062608
Sum of electronic and thermal Enthalpies= -233.061664
Sum of electronic and thermal Free Energies= -233.101686

After reoptimising the anti2 linkage of hexadiene the energy lowered using the B3LYP/6-31G*.
The geometry only changed very slightly, as the bond angles changed from 111.36 to 112.41 for C-C-C and from 124.80 to 124.91 for C=C-C.

=== Chair and Boat Transition Structures ===

'''Chair'''

[[Image:allylvib.jpg]]

the vibration corresponding to the cope rearrangement was at -817.952cm-1 with an intensity of 5.9611.

bond forming= 1.5501
bond breaking= 4.74518

I found if the fragments were positioned more than 2.2 apart eachother then i had problems with running the calcualtion for the transition state. Once i had the bond lengths just lower than 2.2 then the calculation ran smoothly.

After doing the calculation by freezing coordinates method at the fixed bond lengths of 2.2 the chair transition state looked the same as above. Once the bonds were not fixed, the transition state looked changed, looking like the vibration that occurs in the bond breaking/forming. The transition state is showned below.

[[Image:chairmod2.jpg]]

'''Boat'''

Initially the job failed when doing the TS (QST2) until the bond angles and dihedral angles of the reactant and product when changed as the image below shows.

[[Image:REACTPROD.jpg]]

the transition state:

[[Image:boat.jpg]]

the transition state frequency at -839.497cm-1 at 1.607 intensity

[[Image:realboatvib.jpg]]

'''Results Table'''

<br />

''' Summary of energies (in hartree) '''

{| border="1" cellspacing="1" cellpadding="10"
|-
| ''' '''
| width="125" align="center" | '''HF/3-21G'''
| width="125" align="center" | '''HF/3-21G'''
| width="125" align="center" | '''HF/3-21G'''
| width="125" align="center" | '''B3LYP/6-31G*'''
| width="125" align="center" | '''B3LYP/6-31G*'''
| width="125" align="center" | '''B3LYP/6-31G*'''
|-
| ''' '''
| width="125" align="center" | '''Electronic energy'''
| width="125" align="center" | '''Sum of electronic and zero-point energies'''
| width="125" align="center" | '''Sum of electronic and thermal energies'''
| width="125" align="center" | '''Electronic energy'''
| width="125" align="center" | '''Sum of electronic and zero-point energies'''
| width="125" align="center" | '''Sum of electronic and thermal energies'''
|-
| ''' '''
| ''' '''
| width="125" align="center" | '''at 0 K'''
| width="125" align="center" | '''at 298.15 K'''
| ''' '''
| width="125" align="center" | '''at 0 K'''
| width="125" align="center" | '''at 298.15 K'''
|-
| '''Chair TS'''
| align="center" |
| align="center" |
| align="center" |
| align="center" |
| align="center" |
| align="center" |
|-
| '''Boat TS'''
| align="center" |
| align="center" |
| align="center" |
| align="center" |
| align="center" |
| align="center" |
|-
| '''Reactant (''anti2'')'''
| align="center" | -231.6925
| align="center" |
| align="center" |
| align="center" | -233.2099
| align="center" | -233.0700
| align="center" | -233.1017
|}

<br /> *1 hartree = 627.509 kcal/mol <br /><br />

''' Summary of activation energies (in kcal/mol) '''

{| border="1" cellspacing="1" cellpadding="10"
|-
| ''' '''
| width="125" align="center" | '''HF/3-21G'''
| width="125" align="center" | '''HF/3-21G'''
| width="125" align="center" | '''B3LYP/6-31G*'''
| width="125" align="center" | '''B3LYP/6-31G*'''
| width="125" align="center" | '''Expt.'''
|-
| ''' '''
| width="125" align="center" | '''at 0 K '''
| width="125" align="center" | '''at 298.15 K'''
| width="125" align="center" | '''at 0 K'''
| width="125" align="center" | '''at 298.15 K'''
| width="125" align="center" | '''at 0 K'''
|-
| '''ΔE (Chair)'''
| align="center" |
| align="center" |
| align="center" |
| align="center" |
| align="center" |
|-
| '''ΔE (Boat)'''
| align="center" |
| align="center" |
| align="center" |
| align="center" |
| align="center" |
|}

<br />

== Diels-Alder Cycloaddition ==

[[Image:butmech.jpg]]

HOMO-[[Image:butlumo.jpg]]

The molecular orbital is antisymmetric respect to the plane and the axis.

LUMO[[Image:buthomo.jpg]]

The molecular orbital is antisymmetric respect to the plane nut symmetric respect to the axis.

When the cisbutadiene reacts with the alkene the symmetry properties of the orbitals that are overlapping need to be the same therefore the LUMO of ethene needs to antisymmetric to the plane and symmetric to the axis. this will keep the the stereochemistry of substituents.

[[Image:tsbevib.jpg]]

The transtion state frequency is at -818.548cm-1. The value suggests it a certain concerted pericyclic cycloadiition reaction. The next frequency is 166.607cm-1 this corresponds to the the rocking of the ethene fragment.

The fragments were set to be 2.2 angstroms for eachother.

Normal values for C-C bond lengths:

Double bond=1.34Å and single bond=1.54Å

My values have the double bonds at 1.37Å and the single bonds at 1.40Å throught the transition state.

HOMO of the transition state:
[[Image:tsbehomo.jpg]]

=== The Regioselectivity of the Diels Alder Reaction ===

[[Image:malmech.jpg]]

'''Endo'''

LUMO-[[Image:mendolumo.jpg]]

HOMO-[[Image:mendohomo.jpg]]

'''Exo'''

LUMO-[[Image:mexolumo.jpg]]

HOMO-[[Image:mexohomo.jpg]]

== References ==

1. http://www.science.uwaterloo.ca/~cchieh/cact/c120/bondel.html

File:Mexolumo.jpg

2009-01-11T21:33:03Z

Jo206:

2009-01-11T20:49:53Z

Jo206:

File:Butmech.jpg

2009-01-11T20:49:04Z

Jo206:

Rep:Mod:jotp1357

2009-01-11T20:48:44Z

Jo206: /* Diels-Alder Cycloaddition */

== Cope Rearrangement ==

'''anti-hexadiene'''

anti2
HF/3-21G
energy= -231.69253506

point group= Ci with sub group C1

<jmol>
<jmolApplet>
<title>Pentahelicene</title>
<color>blue</color>
<size>300</size>
<script>zoom 80; cpk -25;frame 1; move 10 -20 10 0 0 0 0 0 3; delay 1;</script>
<uploadedFileContents>Anti2mol.mol</uploadedFileContents>
</jmolApplet>
<jmolMenu>
<item><text>Put a script here</text><script>spin on</script></item>
<item><text>Put another script here</text><script>spin off</script></item>
<menuHeight>-1</menuHeight>
</jmolMenu>
<jmolAppletButton>
<color>cyan</color>
<uploadedFileContents>Anti2mol1.mol</uploadedFileContents>
</jmolAppletButton>
</jmol>

'''gauche-hexadiene'''

energy= - 231.69266120
point group= C1 with subgroup C1 aswell.

reoptimised antihexadiene

[[Image:IRspect.jpg]]

experimental values
Sum of electronic and zero-point Energies= -233.070012
Sum of electronic and thermal Energies= -233.062608
Sum of electronic and thermal Enthalpies= -233.061664
Sum of electronic and thermal Free Energies= -233.101686

After reoptimising the anti2 linkage of hexadiene the energy lowered using the B3LYP/6-31G*.
The geometry only changed very slightly, as the bond angles changed from 111.36 to 112.41 for C-C-C and from 124.80 to 124.91 for C=C-C.

=== Chair and Boat Transition Structures ===

'''Chair'''

[[Image:allylvib.jpg]]

the vibration corresponding to the cope rearrangement was at -817.952cm-1 with an intensity of 5.9611.

bond forming= 1.5501
bond breaking= 4.74518

I found if the fragments were positioned more than 2.2 apart eachother then i had problems with running the calcualtion for the transition state. Once i had the bond lengths just lower than 2.2 then the calculation ran smoothly.

After doing the calculation by freezing coordinates method at the fixed bond lengths of 2.2 the chair transition state looked the same as above. Once the bonds were not fixed, the transition state looked changed, looking like the vibration that occurs in the bond breaking/forming. The transition state is showned below.

[[Image:chairmod2.jpg]]

'''Boat'''

Initially the job failed when doing the TS (QST2) until the bond angles and dihedral angles of the reactant and product when changed as the image below shows.

[[Image:REACTPROD.jpg]]

the transition state:

[[Image:boat.jpg]]

the transition state frequency at -839.497cm-1 at 1.607 intensity

[[Image:realboatvib.jpg]]

'''Results Table'''

<br />

''' Summary of energies (in hartree) '''

{| border="1" cellspacing="1" cellpadding="10"
|-
| ''' '''
| width="125" align="center" | '''HF/3-21G'''
| width="125" align="center" | '''HF/3-21G'''
| width="125" align="center" | '''HF/3-21G'''
| width="125" align="center" | '''B3LYP/6-31G*'''
| width="125" align="center" | '''B3LYP/6-31G*'''
| width="125" align="center" | '''B3LYP/6-31G*'''
|-
| ''' '''
| width="125" align="center" | '''Electronic energy'''
| width="125" align="center" | '''Sum of electronic and zero-point energies'''
| width="125" align="center" | '''Sum of electronic and thermal energies'''
| width="125" align="center" | '''Electronic energy'''
| width="125" align="center" | '''Sum of electronic and zero-point energies'''
| width="125" align="center" | '''Sum of electronic and thermal energies'''
|-
| ''' '''
| ''' '''
| width="125" align="center" | '''at 0 K'''
| width="125" align="center" | '''at 298.15 K'''
| ''' '''
| width="125" align="center" | '''at 0 K'''
| width="125" align="center" | '''at 298.15 K'''
|-
| '''Chair TS'''
| align="center" |
| align="center" |
| align="center" |
| align="center" |
| align="center" |
| align="center" |
|-
| '''Boat TS'''
| align="center" |
| align="center" |
| align="center" |
| align="center" |
| align="center" |
| align="center" |
|-
| '''Reactant (''anti2'')'''
| align="center" | -231.6925
| align="center" |
| align="center" |
| align="center" | -233.2099
| align="center" | -233.0700
| align="center" | -233.1017
|}

<br /> *1 hartree = 627.509 kcal/mol <br /><br />

''' Summary of activation energies (in kcal/mol) '''

{| border="1" cellspacing="1" cellpadding="10"
|-
| ''' '''
| width="125" align="center" | '''HF/3-21G'''
| width="125" align="center" | '''HF/3-21G'''
| width="125" align="center" | '''B3LYP/6-31G*'''
| width="125" align="center" | '''B3LYP/6-31G*'''
| width="125" align="center" | '''Expt.'''
|-
| ''' '''
| width="125" align="center" | '''at 0 K '''
| width="125" align="center" | '''at 298.15 K'''
| width="125" align="center" | '''at 0 K'''
| width="125" align="center" | '''at 298.15 K'''
| width="125" align="center" | '''at 0 K'''
|-
| '''ΔE (Chair)'''
| align="center" |
| align="center" |
| align="center" |
| align="center" |
| align="center" |
|-
| '''ΔE (Boat)'''
| align="center" |
| align="center" |
| align="center" |
| align="center" |
| align="center" |
|}

<br />

== Diels-Alder Cycloaddition ==

[[Image:butmech.jpg]]

[[Image:butlumo.jpg]]

The molecular orbital is antisymmetric respect to the plane and the axis.

[[Image:buthomo.jpg]]

The molecular orbital is antisymmetric respect to the plane nut symmetric respect to the axis

Rep:Mod:jotp1357

2009-01-11T20:13:32Z

Jo206: /* Chair and Boat Transition Structures */

== Cope Rearrangement ==

'''anti-hexadiene'''

anti2
HF/3-21G
energy= -231.69253506

point group= Ci with sub group C1

<jmol>
<jmolApplet>
<title>Pentahelicene</title>
<color>blue</color>
<size>300</size>
<script>zoom 80; cpk -25;frame 1; move 10 -20 10 0 0 0 0 0 3; delay 1;</script>
<uploadedFileContents>Anti2mol.mol</uploadedFileContents>
</jmolApplet>
<jmolMenu>
<item><text>Put a script here</text><script>spin on</script></item>
<item><text>Put another script here</text><script>spin off</script></item>
<menuHeight>-1</menuHeight>
</jmolMenu>
<jmolAppletButton>
<color>cyan</color>
<uploadedFileContents>Anti2mol1.mol</uploadedFileContents>
</jmolAppletButton>
</jmol>

'''gauche-hexadiene'''

energy= - 231.69266120
point group= C1 with subgroup C1 aswell.

reoptimised antihexadiene

[[Image:IRspect.jpg]]

experimental values
Sum of electronic and zero-point Energies= -233.070012
Sum of electronic and thermal Energies= -233.062608
Sum of electronic and thermal Enthalpies= -233.061664
Sum of electronic and thermal Free Energies= -233.101686

After reoptimising the anti2 linkage of hexadiene the energy lowered using the B3LYP/6-31G*.
The geometry only changed very slightly, as the bond angles changed from 111.36 to 112.41 for C-C-C and from 124.80 to 124.91 for C=C-C.

=== Chair and Boat Transition Structures ===

'''Chair'''

[[Image:allylvib.jpg]]

the vibration corresponding to the cope rearrangement was at -817.952cm-1 with an intensity of 5.9611.

bond forming= 1.5501
bond breaking= 4.74518

I found if the fragments were positioned more than 2.2 apart eachother then i had problems with running the calcualtion for the transition state. Once i had the bond lengths just lower than 2.2 then the calculation ran smoothly.

After doing the calculation by freezing coordinates method at the fixed bond lengths of 2.2 the chair transition state looked the same as above. Once the bonds were not fixed, the transition state looked changed, looking like the vibration that occurs in the bond breaking/forming. The transition state is showned below.

[[Image:chairmod2.jpg]]

'''Boat'''

Initially the job failed when doing the TS (QST2) until the bond angles and dihedral angles of the reactant and product when changed as the image below shows.

[[Image:REACTPROD.jpg]]

the transition state:

[[Image:boat.jpg]]

the transition state frequency at -839.497cm-1 at 1.607 intensity

[[Image:realboatvib.jpg]]

'''Results Table'''

<br />

''' Summary of energies (in hartree) '''

{| border="1" cellspacing="1" cellpadding="10"
|-
| ''' '''
| width="125" align="center" | '''HF/3-21G'''
| width="125" align="center" | '''HF/3-21G'''
| width="125" align="center" | '''HF/3-21G'''
| width="125" align="center" | '''B3LYP/6-31G*'''
| width="125" align="center" | '''B3LYP/6-31G*'''
| width="125" align="center" | '''B3LYP/6-31G*'''
|-
| ''' '''
| width="125" align="center" | '''Electronic energy'''
| width="125" align="center" | '''Sum of electronic and zero-point energies'''
| width="125" align="center" | '''Sum of electronic and thermal energies'''
| width="125" align="center" | '''Electronic energy'''
| width="125" align="center" | '''Sum of electronic and zero-point energies'''
| width="125" align="center" | '''Sum of electronic and thermal energies'''
|-
| ''' '''
| ''' '''
| width="125" align="center" | '''at 0 K'''
| width="125" align="center" | '''at 298.15 K'''
| ''' '''
| width="125" align="center" | '''at 0 K'''
| width="125" align="center" | '''at 298.15 K'''
|-
| '''Chair TS'''
| align="center" |
| align="center" |
| align="center" |
| align="center" |
| align="center" |
| align="center" |
|-
| '''Boat TS'''
| align="center" |
| align="center" |
| align="center" |
| align="center" |
| align="center" |
| align="center" |
|-
| '''Reactant (''anti2'')'''
| align="center" | -231.6925
| align="center" |
| align="center" |
| align="center" | -233.2099
| align="center" | -233.0700
| align="center" | -233.1017
|}

<br /> *1 hartree = 627.509 kcal/mol <br /><br />

''' Summary of activation energies (in kcal/mol) '''

{| border="1" cellspacing="1" cellpadding="10"
|-
| ''' '''
| width="125" align="center" | '''HF/3-21G'''
| width="125" align="center" | '''HF/3-21G'''
| width="125" align="center" | '''B3LYP/6-31G*'''
| width="125" align="center" | '''B3LYP/6-31G*'''
| width="125" align="center" | '''Expt.'''
|-
| ''' '''
| width="125" align="center" | '''at 0 K '''
| width="125" align="center" | '''at 298.15 K'''
| width="125" align="center" | '''at 0 K'''
| width="125" align="center" | '''at 298.15 K'''
| width="125" align="center" | '''at 0 K'''
|-
| '''ΔE (Chair)'''
| align="center" |
| align="center" |
| align="center" |
| align="center" |
| align="center" |
|-
| '''ΔE (Boat)'''
| align="center" |
| align="center" |
| align="center" |
| align="center" |
| align="center" |
|}

<br />

== Diels-Alder Cycloaddition ==

Rep:Mod:jotp1357

2009-01-11T20:04:42Z

Jo206: /* Chair and Boat Transition Structures */

== Cope Rearrangement ==

'''anti-hexadiene'''

anti2
HF/3-21G
energy= -231.69253506

point group= Ci with sub group C1

<jmol>
<jmolApplet>
<title>Pentahelicene</title>
<color>blue</color>
<size>300</size>
<script>zoom 80; cpk -25;frame 1; move 10 -20 10 0 0 0 0 0 3; delay 1;</script>
<uploadedFileContents>Anti2mol.mol</uploadedFileContents>
</jmolApplet>
<jmolMenu>
<item><text>Put a script here</text><script>spin on</script></item>
<item><text>Put another script here</text><script>spin off</script></item>
<menuHeight>-1</menuHeight>
</jmolMenu>
<jmolAppletButton>
<color>cyan</color>
<uploadedFileContents>Anti2mol1.mol</uploadedFileContents>
</jmolAppletButton>
</jmol>

'''gauche-hexadiene'''

energy= - 231.69266120
point group= C1 with subgroup C1 aswell.

reoptimised antihexadiene

[[Image:IRspect.jpg]]

experimental values
Sum of electronic and zero-point Energies= -233.070012
Sum of electronic and thermal Energies= -233.062608
Sum of electronic and thermal Enthalpies= -233.061664
Sum of electronic and thermal Free Energies= -233.101686

After reoptimising the anti2 linkage of hexadiene the energy lowered using the B3LYP/6-31G*.
The geometry only changed very slightly, as the bond angles changed from 111.36 to 112.41 for C-C-C and from 124.80 to 124.91 for C=C-C.

== Chair and Boat Transition Structures ==

'''Chair'''

[[Image:allylvib.jpg]]

the vibration corresponding to the cope rearrangement was at -817.952cm-1 with an intensity of 5.9611.

bond forming= 1.5501
bond breaking= 4.74518

I found if the fragments were positioned more than 2.2 apart eachother then i had problems with running the calcualtion for the transition state. Once i had the bond lengths just lower than 2.2 then the calculation ran smoothly.

After doing the calculation by freezing coordinates method at the fixed bond lengths of 2.2 the chair transition state looked the same as above. Once the bonds were not fixed, the transition state looked changed, looking like the vibration that occurs in the bond breaking/forming. The transition state is showned below.

[[Image:chairmod2.jpg]]

'''Boat'''

Initially the job failed when doing the TS (QST2) until the bond angles and dihedral angles of the reactant and product when changed as the image below shows.

[[Image:REACTPROD.jpg]]

the transition state:

[[Image:boat.jpg]]

the transition state frequency at -839.497cm-1 at 1.607 intensity

[[Image:realboatvib.jpg]]

=== Results Table ===

<br />

''' Summary of energies (in hartree) '''

{| border="1" cellspacing="1" cellpadding="10"
|-
| ''' '''
| width="125" align="center" | '''HF/3-21G'''
| width="125" align="center" | '''HF/3-21G'''
| width="125" align="center" | '''HF/3-21G'''
| width="125" align="center" | '''B3LYP/6-31G*'''
| width="125" align="center" | '''B3LYP/6-31G*'''
| width="125" align="center" | '''B3LYP/6-31G*'''
|-
| ''' '''
| width="125" align="center" | '''Electronic energy'''
| width="125" align="center" | '''Sum of electronic and zero-point energies'''
| width="125" align="center" | '''Sum of electronic and thermal energies'''
| width="125" align="center" | '''Electronic energy'''
| width="125" align="center" | '''Sum of electronic and zero-point energies'''
| width="125" align="center" | '''Sum of electronic and thermal energies'''
|-
| ''' '''
| ''' '''
| width="125" align="center" | '''at 0 K'''
| width="125" align="center" | '''at 298.15 K'''
| ''' '''
| width="125" align="center" | '''at 0 K'''
| width="125" align="center" | '''at 298.15 K'''
|-
| '''Chair TS'''
| align="center" |
| align="center" |
| align="center" |
| align="center" |
| align="center" |
| align="center" |
|-
| '''Boat TS'''
| align="center" |
| align="center" |
| align="center" |
| align="center" |
| align="center" |
| align="center" |
|-
| '''Reactant (''anti2'')'''
| align="center" | -231.6925
| align="center" |
| align="center" |
| align="center" | -233.2099
| align="center" | -233.0700
| align="center" | -233.1017
|}

<br /> *1 hartree = 627.509 kcal/mol <br /><br />

''' Summary of activation energies (in kcal/mol) '''

{| border="1" cellspacing="1" cellpadding="10"
|-
| ''' '''
| width="125" align="center" | '''HF/3-21G'''
| width="125" align="center" | '''HF/3-21G'''
| width="125" align="center" | '''B3LYP/6-31G*'''
| width="125" align="center" | '''B3LYP/6-31G*'''
| width="125" align="center" | '''Expt.'''
|-
| ''' '''
| width="125" align="center" | '''at 0 K '''
| width="125" align="center" | '''at 298.15 K'''
| width="125" align="center" | '''at 0 K'''
| width="125" align="center" | '''at 298.15 K'''
| width="125" align="center" | '''at 0 K'''
|-
| '''ΔE (Chair)'''
| align="center" |
| align="center" |
| align="center" |
| align="center" |
| align="center" |
|-
| '''ΔE (Boat)'''
| align="center" |
| align="center" |
| align="center" |
| align="center" |
| align="center" |
|}

<br />

File:REACTPROD.jpg

2009-01-11T20:02:08Z

Jo206:

Rep:Mod:jotp1357

2009-01-11T20:01:25Z

File:Anti2mol.mol

2009-01-08T20:24:21Z

Jo206:

Rep:Mod:jotp1357

2009-01-08T20:23:38Z

Jo206: /* Cope Rearrangement */

== Cope Rearrangement ==

'''antihexadiene'''

HF/3-21G
energy= -231.69253506

point group= Ci with sub group C1

<jmol>
<jmolApplet>
<title>Pentahelicene</title>
<color>blue</color>
<size>300</size>
<script>zoom 80; cpk -25;frame 1; move 10 -20 10 0 0 0 0 0 3; delay 1;</script>
<uploadedFileContents>anti2mol.mol</uploadedFileContents>
</jmolApplet>
<jmolMenu>
<item><text>Put a script here</text><script>spin on</script></item>
<item><text>Put another script here</text><script>spin off</script></item>
<menuHeight>-1</menuHeight>
</jmolMenu>
<jmolAppletButton>
<color>cyan</color>
<uploadedFileContents>anti2mol1.mol</uploadedFileContents>
</jmolAppletButton>
</jmol>

'''gauche hexadiene'''

energy= - 231.69266120
point group= C1 with subgroup C1 aswell.

reoptimised antihexadiene

[[Image:IRspect.jpg]]

experimental values
Sum of electronic and zero-point Energies= -233.070012
Sum of electronic and thermal Energies= -233.062608
Sum of electronic and thermal Enthalpies= -233.061664
Sum of electronic and thermal Free Energies= -233.101686

== Optimizing the "Chair" and "Boat" Transition Structures ==

allyl fragment

'''Chair'''

[[Image:allylvib.jpg]]

the vibration corresponding to the cope rearrangement was at -817.952 with an intensity of 5.9611.

bond forming= 1.5501
bond breaking= 4.74518

'''boat'''

[[Image:boat.jpg]]

has a chair conformation

after the geometry of the bonds

[[Image:realboat.jpg]]

the transition state frequency at -839.497 at 1.607 intensity

[[Image:realboatvib.jpg]]

=== Results Table ===

<br />

''' Summary of energies (in hartree) '''

{| border="1" cellspacing="1" cellpadding="10"
|-
| ''' '''
| width="125" align="center" | '''HF/3-21G'''
| width="125" align="center" | '''HF/3-21G'''
| width="125" align="center" | '''HF/3-21G'''
| width="125" align="center" | '''B3LYP/6-31G*'''
| width="125" align="center" | '''B3LYP/6-31G*'''
| width="125" align="center" | '''B3LYP/6-31G*'''
|-
| ''' '''
| width="125" align="center" | '''Electronic energy'''
| width="125" align="center" | '''Sum of electronic and zero-point energies'''
| width="125" align="center" | '''Sum of electronic and thermal energies'''
| width="125" align="center" | '''Electronic energy'''
| width="125" align="center" | '''Sum of electronic and zero-point energies'''
| width="125" align="center" | '''Sum of electronic and thermal energies'''
|-
| ''' '''
| ''' '''
| width="125" align="center" | '''at 0 K'''
| width="125" align="center" | '''at 298.15 K'''
| ''' '''
| width="125" align="center" | '''at 0 K'''
| width="125" align="center" | '''at 298.15 K'''
|-
| '''Chair TS'''
| align="center" |
| align="center" |
| align="center" |
| align="center" |
| align="center" |
| align="center" |
|-
| '''Boat TS'''
| align="center" |
| align="center" |
| align="center" |
| align="center" |
| align="center" |
| align="center" |
|-
| '''Reactant (''anti2'')'''
| align="center" | -231.6925
| align="center" |
| align="center" |
| align="center" | -233.2099
| align="center" | -233.0700
| align="center" | -233.1017
|}

<br /> *1 hartree = 627.509 kcal/mol <br /><br />

''' Summary of activation energies (in kcal/mol) '''

{| border="1" cellspacing="1" cellpadding="10"
|-
| ''' '''
| width="125" align="center" | '''HF/3-21G'''
| width="125" align="center" | '''HF/3-21G'''
| width="125" align="center" | '''B3LYP/6-31G*'''
| width="125" align="center" | '''B3LYP/6-31G*'''
| width="125" align="center" | '''Expt.'''
|-
| ''' '''
| width="125" align="center" | '''at 0 K '''
| width="125" align="center" | '''at 298.15 K'''
| width="125" align="center" | '''at 0 K'''
| width="125" align="center" | '''at 298.15 K'''
| width="125" align="center" | '''at 0 K'''
|-
| '''ΔE (Chair)'''
| align="center" |
| align="center" |
| align="center" |
| align="center" |
| align="center" |
|-
| '''ΔE (Boat)'''
| align="center" |
| align="center" |
| align="center" |
| align="center" |
| align="center" |
|}

<br />

File:Anti2pic.jpg

2009-01-08T20:20:22Z

Jo206:

Rep:Mod:jotp1357

2009-01-08T20:20:11Z

Jo206: /* Cope Rearrangement */

== Cope Rearrangement ==

'''antihexadiene'''

HF/3-21G
energy= -231.69253506

point group= Ci with sub group C1

[[Image:anti2pic.jpg]]

'''gauche hexadiene'''

energy= - 231.69266120
point group= C1 with subgroup C1 aswell.

reoptimised antihexadiene

[[Image:IRspect.jpg]]

experimental values
Sum of electronic and zero-point Energies= -233.070012
Sum of electronic and thermal Energies= -233.062608
Sum of electronic and thermal Enthalpies= -233.061664
Sum of electronic and thermal Free Energies= -233.101686

== Optimizing the "Chair" and "Boat" Transition Structures ==

allyl fragment

'''Chair'''

[[Image:allylvib.jpg]]

the vibration corresponding to the cope rearrangement was at -817.952 with an intensity of 5.9611.

bond forming= 1.5501
bond breaking= 4.74518

'''boat'''

[[Image:boat.jpg]]

has a chair conformation

after the geometry of the bonds

[[Image:realboat.jpg]]

the transition state frequency at -839.497 at 1.607 intensity

[[Image:realboatvib.jpg]]

=== Results Table ===

<br />

''' Summary of energies (in hartree) '''

{| border="1" cellspacing="1" cellpadding="10"
|-
| ''' '''
| width="125" align="center" | '''HF/3-21G'''
| width="125" align="center" | '''HF/3-21G'''
| width="125" align="center" | '''HF/3-21G'''
| width="125" align="center" | '''B3LYP/6-31G*'''
| width="125" align="center" | '''B3LYP/6-31G*'''
| width="125" align="center" | '''B3LYP/6-31G*'''
|-
| ''' '''
| width="125" align="center" | '''Electronic energy'''
| width="125" align="center" | '''Sum of electronic and zero-point energies'''
| width="125" align="center" | '''Sum of electronic and thermal energies'''
| width="125" align="center" | '''Electronic energy'''
| width="125" align="center" | '''Sum of electronic and zero-point energies'''
| width="125" align="center" | '''Sum of electronic and thermal energies'''
|-
| ''' '''
| ''' '''
| width="125" align="center" | '''at 0 K'''
| width="125" align="center" | '''at 298.15 K'''
| ''' '''
| width="125" align="center" | '''at 0 K'''
| width="125" align="center" | '''at 298.15 K'''
|-
| '''Chair TS'''
| align="center" |
| align="center" |
| align="center" |
| align="center" |
| align="center" |
| align="center" |
|-
| '''Boat TS'''
| align="center" |
| align="center" |
| align="center" |
| align="center" |
| align="center" |
| align="center" |
|-
| '''Reactant (''anti2'')'''
| align="center" | -231.6925
| align="center" |
| align="center" |
| align="center" | -233.2099
| align="center" | -233.0700
| align="center" | -233.1017
|}

<br /> *1 hartree = 627.509 kcal/mol <br /><br />

''' Summary of activation energies (in kcal/mol) '''

{| border="1" cellspacing="1" cellpadding="10"
|-
| ''' '''
| width="125" align="center" | '''HF/3-21G'''
| width="125" align="center" | '''HF/3-21G'''
| width="125" align="center" | '''B3LYP/6-31G*'''
| width="125" align="center" | '''B3LYP/6-31G*'''
| width="125" align="center" | '''Expt.'''
|-
| ''' '''
| width="125" align="center" | '''at 0 K '''
| width="125" align="center" | '''at 298.15 K'''
| width="125" align="center" | '''at 0 K'''
| width="125" align="center" | '''at 298.15 K'''
| width="125" align="center" | '''at 0 K'''
|-
| '''ΔE (Chair)'''
| align="center" |
| align="center" |
| align="center" |
| align="center" |
| align="center" |
|-
| '''ΔE (Boat)'''
| align="center" |
| align="center" |
| align="center" |
| align="center" |
| align="center" |
|}

<br />

Rep:Mod:jotp1357

2009-01-08T20:19:43Z

Jo206: /* Cope Rearrangement */

== Cope Rearrangement ==

'''antihexadiene'''

HF/3-21G
energy= -231.69253506

point group= Ci with sub group C1

[[Image:anti2.jpg]]

'''gauche hexadiene'''

energy= - 231.69266120
point group= C1 with subgroup C1 aswell.

reoptimised antihexadiene

[[Image:IRspect.jpg]]

experimental values
Sum of electronic and zero-point Energies= -233.070012
Sum of electronic and thermal Energies= -233.062608
Sum of electronic and thermal Enthalpies= -233.061664
Sum of electronic and thermal Free Energies= -233.101686

== Optimizing the "Chair" and "Boat" Transition Structures ==

allyl fragment

'''Chair'''

[[Image:allylvib.jpg]]

the vibration corresponding to the cope rearrangement was at -817.952 with an intensity of 5.9611.

bond forming= 1.5501
bond breaking= 4.74518

'''boat'''

[[Image:boat.jpg]]

has a chair conformation

after the geometry of the bonds

[[Image:realboat.jpg]]

the transition state frequency at -839.497 at 1.607 intensity

[[Image:realboatvib.jpg]]

=== Results Table ===

<br />

''' Summary of energies (in hartree) '''

{| border="1" cellspacing="1" cellpadding="10"
|-
| ''' '''
| width="125" align="center" | '''HF/3-21G'''
| width="125" align="center" | '''HF/3-21G'''
| width="125" align="center" | '''HF/3-21G'''
| width="125" align="center" | '''B3LYP/6-31G*'''
| width="125" align="center" | '''B3LYP/6-31G*'''
| width="125" align="center" | '''B3LYP/6-31G*'''
|-
| ''' '''
| width="125" align="center" | '''Electronic energy'''
| width="125" align="center" | '''Sum of electronic and zero-point energies'''
| width="125" align="center" | '''Sum of electronic and thermal energies'''
| width="125" align="center" | '''Electronic energy'''
| width="125" align="center" | '''Sum of electronic and zero-point energies'''
| width="125" align="center" | '''Sum of electronic and thermal energies'''
|-
| ''' '''
| ''' '''
| width="125" align="center" | '''at 0 K'''
| width="125" align="center" | '''at 298.15 K'''
| ''' '''
| width="125" align="center" | '''at 0 K'''
| width="125" align="center" | '''at 298.15 K'''
|-
| '''Chair TS'''
| align="center" |
| align="center" |
| align="center" |
| align="center" |
| align="center" |
| align="center" |
|-
| '''Boat TS'''
| align="center" |
| align="center" |
| align="center" |
| align="center" |
| align="center" |
| align="center" |
|-
| '''Reactant (''anti2'')'''
| align="center" | -231.6925
| align="center" |
| align="center" |
| align="center" | -233.2099
| align="center" | -233.0700
| align="center" | -233.1017
|}

<br /> *1 hartree = 627.509 kcal/mol <br /><br />

''' Summary of activation energies (in kcal/mol) '''

{| border="1" cellspacing="1" cellpadding="10"
|-
| ''' '''
| width="125" align="center" | '''HF/3-21G'''
| width="125" align="center" | '''HF/3-21G'''
| width="125" align="center" | '''B3LYP/6-31G*'''
| width="125" align="center" | '''B3LYP/6-31G*'''
| width="125" align="center" | '''Expt.'''
|-
| ''' '''
| width="125" align="center" | '''at 0 K '''
| width="125" align="center" | '''at 298.15 K'''
| width="125" align="center" | '''at 0 K'''
| width="125" align="center" | '''at 298.15 K'''
| width="125" align="center" | '''at 0 K'''
|-
| '''ΔE (Chair)'''
| align="center" |
| align="center" |
| align="center" |
| align="center" |
| align="center" |
|-
| '''ΔE (Boat)'''
| align="center" |
| align="center" |
| align="center" |
| align="center" |
| align="center" |
|}

<br />

Rep:Mod:jotp1357

2009-01-08T20:07:17Z

Jo206: /* Cope Rearrangement */

== Cope Rearrangement ==

'''antihexadiene'''

HF/3-21G
energy= -231.69253506

point group= Ci with sub group C1

'''gauche hexadiene'''

energy= - 231.69266120
point group= C1 with subgroup C1 aswell.

reoptimised antihexadiene

[[Image:IRspect.jpg]]

experimental values
Sum of electronic and zero-point Energies= -233.070012
Sum of electronic and thermal Energies= -233.062608
Sum of electronic and thermal Enthalpies= -233.061664
Sum of electronic and thermal Free Energies= -233.101686

== Optimizing the "Chair" and "Boat" Transition Structures ==

allyl fragment

'''Chair'''

[[Image:allylvib.jpg]]

the vibration corresponding to the cope rearrangement was at -817.952 with an intensity of 5.9611.

bond forming= 1.5501
bond breaking= 4.74518

'''boat'''

[[Image:boat.jpg]]

has a chair conformation

after the geometry of the bonds

[[Image:realboat.jpg]]

the transition state frequency at -839.497 at 1.607 intensity

[[Image:realboatvib.jpg]]

=== Results Table ===

<br />

''' Summary of energies (in hartree) '''

{| border="1" cellspacing="1" cellpadding="10"
|-
| ''' '''
| width="125" align="center" | '''HF/3-21G'''
| width="125" align="center" | '''HF/3-21G'''
| width="125" align="center" | '''HF/3-21G'''
| width="125" align="center" | '''B3LYP/6-31G*'''
| width="125" align="center" | '''B3LYP/6-31G*'''
| width="125" align="center" | '''B3LYP/6-31G*'''
|-
| ''' '''
| width="125" align="center" | '''Electronic energy'''
| width="125" align="center" | '''Sum of electronic and zero-point energies'''
| width="125" align="center" | '''Sum of electronic and thermal energies'''
| width="125" align="center" | '''Electronic energy'''
| width="125" align="center" | '''Sum of electronic and zero-point energies'''
| width="125" align="center" | '''Sum of electronic and thermal energies'''
|-
| ''' '''
| ''' '''
| width="125" align="center" | '''at 0 K'''
| width="125" align="center" | '''at 298.15 K'''
| ''' '''
| width="125" align="center" | '''at 0 K'''
| width="125" align="center" | '''at 298.15 K'''
|-
| '''Chair TS'''
| align="center" |
| align="center" |
| align="center" |
| align="center" |
| align="center" |
| align="center" |
|-
| '''Boat TS'''
| align="center" |
| align="center" |
| align="center" |
| align="center" |
| align="center" |
| align="center" |
|-
| '''Reactant (''anti2'')'''
| align="center" | -231.6925
| align="center" |
| align="center" |
| align="center" | -233.2099
| align="center" | -233.0700
| align="center" | -233.1017
|}

<br /> *1 hartree = 627.509 kcal/mol <br /><br />

''' Summary of activation energies (in kcal/mol) '''

{| border="1" cellspacing="1" cellpadding="10"
|-
| ''' '''
| width="125" align="center" | '''HF/3-21G'''
| width="125" align="center" | '''HF/3-21G'''
| width="125" align="center" | '''B3LYP/6-31G*'''
| width="125" align="center" | '''B3LYP/6-31G*'''
| width="125" align="center" | '''Expt.'''
|-
| ''' '''
| width="125" align="center" | '''at 0 K '''
| width="125" align="center" | '''at 298.15 K'''
| width="125" align="center" | '''at 0 K'''
| width="125" align="center" | '''at 298.15 K'''
| width="125" align="center" | '''at 0 K'''
|-
| '''ΔE (Chair)'''
| align="center" |
| align="center" |
| align="center" |
| align="center" |
| align="center" |
|-
| '''ΔE (Boat)'''
| align="center" |
| align="center" |
| align="center" |
| align="center" |
| align="center" |
|}

<br />

Rep:Mod:jotp1357

2009-01-08T20:03:43Z

Jo206: /* Results Table */

== Cope Rearrangement ==

'''antihexadiene'''

HF/3-21G
energy= -231.69253506

point group= Ci with sub group C1

'''gauche hexadiene'''

energy= - 231.69266120
point group= C1 with subgroup C1 aswell.

reoptimised antihexadiene

[[Image:IRspect.jpg]]

== Optimizing the "Chair" and "Boat" Transition Structures ==

allyl fragment

'''Chair'''

[[Image:allylvib.jpg]]

the vibration corresponding to the cope rearrangement was at -817.952 with an intensity of 5.9611.

bond forming= 1.5501
bond breaking= 4.74518

'''boat'''

[[Image:boat.jpg]]

has a chair conformation

after the geometry of the bonds

[[Image:realboat.jpg]]

the transition state frequency at -839.497 at 1.607 intensity

[[Image:realboatvib.jpg]]

=== Results Table ===

<br />

''' Summary of energies (in hartree) '''

{| border="1" cellspacing="1" cellpadding="10"
|-
| ''' '''
| width="125" align="center" | '''HF/3-21G'''
| width="125" align="center" | '''HF/3-21G'''
| width="125" align="center" | '''HF/3-21G'''
| width="125" align="center" | '''B3LYP/6-31G*'''
| width="125" align="center" | '''B3LYP/6-31G*'''
| width="125" align="center" | '''B3LYP/6-31G*'''
|-
| ''' '''
| width="125" align="center" | '''Electronic energy'''
| width="125" align="center" | '''Sum of electronic and zero-point energies'''
| width="125" align="center" | '''Sum of electronic and thermal energies'''
| width="125" align="center" | '''Electronic energy'''
| width="125" align="center" | '''Sum of electronic and zero-point energies'''
| width="125" align="center" | '''Sum of electronic and thermal energies'''
|-
| ''' '''
| ''' '''
| width="125" align="center" | '''at 0 K'''
| width="125" align="center" | '''at 298.15 K'''
| ''' '''
| width="125" align="center" | '''at 0 K'''
| width="125" align="center" | '''at 298.15 K'''
|-
| '''Chair TS'''
| align="center" |
| align="center" |
| align="center" |
| align="center" |
| align="center" |
| align="center" |
|-
| '''Boat TS'''
| align="center" |
| align="center" |
| align="center" |
| align="center" |
| align="center" |
| align="center" |
|-
| '''Reactant (''anti2'')'''
| align="center" | -231.6925
| align="center" |
| align="center" |
| align="center" | -233.2099
| align="center" | -233.0700
| align="center" | -233.1017
|}

<br /> *1 hartree = 627.509 kcal/mol <br /><br />

''' Summary of activation energies (in kcal/mol) '''

{| border="1" cellspacing="1" cellpadding="10"
|-
| ''' '''
| width="125" align="center" | '''HF/3-21G'''
| width="125" align="center" | '''HF/3-21G'''
| width="125" align="center" | '''B3LYP/6-31G*'''
| width="125" align="center" | '''B3LYP/6-31G*'''
| width="125" align="center" | '''Expt.'''
|-
| ''' '''
| width="125" align="center" | '''at 0 K '''
| width="125" align="center" | '''at 298.15 K'''
| width="125" align="center" | '''at 0 K'''
| width="125" align="center" | '''at 298.15 K'''
| width="125" align="center" | '''at 0 K'''
|-
| '''ΔE (Chair)'''
| align="center" |
| align="center" |
| align="center" |
| align="center" |
| align="center" |
|-
| '''ΔE (Boat)'''
| align="center" |
| align="center" |
| align="center" |
| align="center" |
| align="center" |
|}

<br />

2009-01-05T14:14:29Z

Jo206: /* Optimizing the "Chair" and "Boat" Transition Structures */

== Cope Rearrangement ==

'''antihexadiene'''

HF/3-21G
energy= -231.69253506

point group= Ci with sub group C1

'''gauche hexadiene'''

energy= - 231.69266120
point group= C1 with subgroup C1 aswell.

== Optimizing the "Chair" and "Boat" Transition Structures ==

allyl fragment

'''Chair'''
[[Image:allylvib.jpg]]

the vibration corresponding to the cope rearrangement was at -817.952 with an intensity of 5.9611.

bond forming= 1.5501
bond breaking= 4.74518

Rep:Mod:jotp1357

2009-01-05T14:13:56Z

Jo206: /* Optimizing the "Chair" and "Boat" Transition Structures */

== Cope Rearrangement ==

'''antihexadiene'''

HF/3-21G
energy= -231.69253506

point group= Ci with sub group C1

'''gauche hexadiene'''

energy= - 231.69266120
point group= C1 with subgroup C1 aswell.

== Optimizing the "Chair" and "Boat" Transition Structures ==

allyl fragment

[[Image:allylvib.jpg]]

the vibration corresponding to the cope rearrangement was at -817.952 with an intensity of 5.9611.

bond forming= 1.5501
bond breaking= 4.74518

File:Allylvib.jpg

2009-01-05T13:22:05Z

Jo206: