CHM 668

Physical Organic Chemistry

Fall 2004

 

Instructor:                     Prof. Paul Wenthold               Office:  B135B     pgw@purdue.edu

Course Supervisor:       Ian Krouse                              Office:  B125B     krousei@purdue.edu

COURSE SYLLABUS

 

HOMEWORK CRIBS

Assignment #1 (no answers)

Assignment #2     Assignment #2 Answer Key

Assignment #3     Assignment #3 Answer Key

Exam #1     Exam #1 Answers

Fun with Symmetry       Answers

Fun with Aromaticity    Answers

Term Paper Guidelines

SUGGESTED READINGS & USEFUL LINKS

RESERVED READING LIST

CHEMISTRY e-JOURNALS AT PURDUE

CLICK ON JOE SHMO FOR

Simple Hückel Calculators: www.chem.ucalgary.ca/SHMO/

or http://www.ch.ic.ac.uk/vgibson/ormsby/SHMo2/SHMo2.html

NIST WEB BOOK

GAS PHASE ACIDITY TABLES

 

 

Good Hückel Sources:

Borden                           Modern Molecular Orbital Theory for Organic Chemists

Streitwieser                     Molecular Orbital Theory for Organic Chemists

0.      Hammett Parameters                   08/23         08/25

            A.      Hammett s, r for a dot            

 

Wenthold                                 Int. J. Mass Spectrom. Ion Proc. (1998), 175, 215-224.

 

          B.      Carboxylic acids                       08/27         08/30

 

                   Siggel and Thomas                   J. Am. Chem. Soc. (1986), 108, 4360-4363

                   Wiberg                                     J. Am. Chem. Soc. (1996), 118, 8291-8299

                   Taft                                          J. Am. Chem. Soc. (1990), 112, 2047-2052

                   Rablen                                      J. Am. Chem. Soc. (2000), 122, 357-368

 

I.       Quantum Basics                            09/01         09/03         09/08         09/10          09/13

Supplemental reading on variational principle (Anslyn and Dougherty)

          A.      Ethylene                                   09/15

          B.      Electron Spin                            09/17

 

II.      Hückel Theory                               09/20

A.      Allylic Systems (Open-Shell Wave Functions)        09/22         09/24         09/27

                                                                                      09/29         10/01         10/03          10/06

 

          Schleyer                                   J. Am. Chem. Soc. (1979), 101, 6032-6040

          Sustmann                                 J. Am. Chem. Soc. (1981), 103, 4483-4489

          Wiberg                                     J. Am. Chem. Soc. (1990), 112, 61-72

          Jorgenson                                 J. Am. Chem. Soc. (1984), 106, 5104-5112

          Frenking                                   J. Am. Chem. Soc. (1994), 116, 9275-9286

 

B.                Cyclopropenyl – The Real Story         10/08         10/13

 

Merrill, Kass                             J. Am. Chem. Soc. (1997), 119, 12322-12337

Glukhovtsev                             J. Phys. Chem. (1996), 100, 17801-17806

Lardin, Nash and Wenthold       J. Am. Chem. Soc. (2002), 124, 12612-12618

 

 

III.    [4]Annulene:  Cyclobutadiene              10/13

 

Masamune                                J. Am. Chem. Soc. (1978), 100, 4889-4891

                                                Tetrahedron (1980), 36, 343-370

                                                          (also Tetrahedron (1980), 36, pages 1464 and 1900)

Peters                                       Science (1999), 286 (5442), 1119-1122

 

IV.    MO Shortcuts

A.      Frost Mneomics                       10/15

 

          Frost                                        J. Chem. Phys. (1953), 21, 572-573   

 

B.      Symmetry Adapted Orbitals      10/18         10/20         10/22         10/27          Fun with Symmetry

                                                                                                                                       Answers

 

          Carter                                       Molecular Symmetry and Group Theory (reserve)

 

V.      [6]Annulene:  Benzene and Aromaticity      

 

A.      How much is 2b?                      10/29        

 

Dewar                                      J. Am. Chem. Soc. (1969), 91, 789-795

Kistiakowsky                            J. Am. Chem. Soc. (1935), 57, 876-882

                                                                   J. Am. Chem. Soc. (1936), 58, 146-153

                   Wiberg                                     Physical Organic Chemistry (on reserve)

                   Vollhardt                                  J. Am. Chem. Soc. (1986), 108, 3150-3152

                                                                   Chem. Eur. J. (1999), 5, 3399-3412

                                                                   J. Am. Chem. Soc. (2000), 122, 7819-7820

 

B.      What is Aromaticity?                 11/01         11/03

 

Schleyer                                   Pure & Appl. Chem. (1996), 68, 209-218

                                                                   J. Org. Chem. (2002), 67, 1333-1338

 

C.               s- and p- Bond Separation in Aromatic Systems     11/05

 

Jug, Hiberty and Shaik              Chem. Rev. (2001), 101, 1477-1500

 

VI.    [10]Annulene:  Strain                   11/08         11/10         11/12

 

                   Origin of Strain                         NOTES       (These notes are a combination of the three days above)

 

VII.   Reactions                                        11/15         11/17         11/19

A.      Transition State Theory

B.      Potential Energy Surfaces          HANDOUT

 

VIII. Intermediates & Miscellaneous

A.      Biradicals                                 11/22         11/29        

B.      Cope Rearrangement                 12/01         12/03

C.      Pechukas Symmetry                  12/06

D.      Carbenes                                  12/08         12/10         CLASS NOTES

Last Updated 12/11/04 by IAN