CHEMISTRY II

 

Theoretical Chemistry - Molecular Structure and Bonding

[CHEM 20150: 10 Credit points]

 

Structure and Bonding II

p Electrons in Conjugated Organic Molecules

 

Dr. Adrian Mulholland

 

6 Lectures

 

·        The variation theorem.

·        Derivation of Hückel theory. 

·        Secular equations and secular determinants. 

·        Ionic-Covalent crossings and the non-crossing rule.

·        Eigenvalues - orbital energies and eigenvectors - orbital coefficients. 

·        MO's in organic molecules - -orbitals in conjugated hydrocarbons. 

·        Qualitative rules for molecular orbitals in chains and rings - nodes. 

·        HOMOs and LUMOs - electronic spectroscopy (dyes). 

·        Benzene and cyclobutadiene.  Aromaticity. 

·        Pericyclic reactions:  frontier orbitals and orbital symmetry. 

·        Woodward-Hoffmann rules.

·        2 + 2 cycloaddition forbidden, 4 + 2 cycloaddition allowed (Diels-Alder reaction ).  Stereochemical consequences.  Conrotatory and disrotatory ring openings.

 

Mathematical background:    

 

                simultaneous equations, determinants and matrices.

 

 

Recommended Text:

 

P.W. Atkins                    ‘Physical Chemistry’      (6th edn.) (OUP)

                                        ISBN 0-19-850101-3              £26.95

 

Other useful books: 

 

J.N. Murrell, S.F. Kettle          ‘Valence Theory’                    (John Wiley )

and  J.M. Tedder                     ISBN 0-471-62688-0              £11.30

 

F.A. Carroll,  ‘Perspectives on Structure and Mechanism in Organic Chemistry’ 

(Brooks/Cole Co.),                  ISBN 0-534-24948-5

 

M.Jones                   ‘Organic Chemistry’                       (Norton & Co.)

                                ISBN 0-393-97079-5

 

I. Fleming                        ‘Pericyclic Reactions’     (Oxford Chemistry Primer)

                                ISBN 0-19-850307 5                      

 

Lecture 1