Chapter 6

Studying Reaction Mechanisms

molecules
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EXAMPLE 6.1: DIELS-ALDER REGIOSELECTIVITY

1-methoxy-1,3-butadiene
acrylonitrile
MOs involved in a diehls-alder reaction

EXAMPLE 6.2: REACTIVITY OF Al5O4

Al5O4 anion
MOs of Al5O4

EXAMPLE 6.3: INDANE AND TETRALIN

indane
tetralin
GaussView atom list editor

EXAMPLE 6.4: ROTATIONAL ISOMERIZATION IN ALLYL CATION

allyl cation
allyl cation rotational isomerization TS

EXAMPLE 6.5: SCAN CALCULATIONS: ROTATIONAL ISOMERIZATIONN

n-methyl-(2-nitrovinyl) amine
PES scan of n-methyl-(2-nitrovinyl)amine

EXAMPLE 6.6: BOND DISSOCIATION IN METHANE

methane
HOMO for stretched methane: restricted vs. unrestricted

EXAMPLE 6.7: STUDYING THE H2CO POTENTIAL ENERGY SURFACE

carbon monoxide
formaldehyde
hydrogen molecule
hydroxycarbene

EXAMPLE 6.8: CO2 ENTHALPY OF FORMATION

carbon dioxide
methane

EXAMPLE 6.9: TESTING HESS’S LAW

ethane

EXERCISE 6.1: ELECTRON DENSITIES OF SUBSTITUTED BENZENES

chlorobenzene
nitrobenzene

EXERCISE 6.2: ROTATIONAL BARRIERS

acetophenone
frozen dihedral angles

EXERCISE 6.3: THE H2CO POTENTIAL ENERGY SURFACE

formaldehyde
hydroxycarbene

EXERCISE 6.4: THE SILICON CATION + SILANE POTENTIAL ENERGY SURFACE

silane
the silicon cation + silane PES
Si+ + Silane hydrogen elimination reaction

EXERCISE 6.5: ISODESMIC REACTIONS

acetone
acetyl chloride
acetyl fluoride

EXERCISE 6.6: HEAT OF FORMATION FOR TETRAFLUOROSILANEN

tetrafluorosilane

ADVANCED EXERCISE 6.7: ETHYL ACETATE HYDROLYSIS REVISITED

methyl acetate
QST3 optimization input: BAC2 mechanism
QST3 optimization input: BAL2 mechanism

ADVANCED EXAMPLE 6.10: THE O3 POTENTIAL ENERGY SURFACE

ozone

ADVANCED EXERCISE 6.8: STUDYING KETO-ENOL TAUTOMERISM

2-hydroxypyridine
2-pyridone
Keto-enol tautomerization of 2-pyridone and 2-hydroxypyridine

ADVANCED EXAMPLE 6.11: A SIMPLE SN2 REACTION

methyl chloride
methyl fluoride
An SN2 reaction
IRC from an SN2 reaction

ADVANCED EXERCISE 6.9: LEAVING GROUP EFFECTS IN ETHYL HALIDE SN2 REACTIONS

acetate anion
ethyl acetate
ethyl bromide
ethyl chloride