CHEM 636 - SCHEDULE FOR LECTURES: (updated 3/21/2011) Lecture # Topic 1 W 1/19 Review of Fundamentals: Inorganic Reaction types; Reaction energetics; 2 F 1/21 Cont’d; worksheet __________________________________________________________________________ 3 M 1/24 Simple Associative Reactions: Lewis Acid/base adducts; Associative reactions as in Ligand Substitution in Square Planar complexes 4 W 1/26 Cont’d. Nucleophilicity Scales; Nucleophilic Discrimination Cont’d. Time Scale Student project. Techniques for Monitoring Reaction Rates. Water exchange in aqua complexes; Distinguishing features of A vs D, Ia and Id pathways. Simple to Complex Rate Expressions; Steady State approximation and Competition Ratios Activation Barriers: Arrhenius and Eyring Eqns Ligand Substitution in Oh Complexes; Solvent Exchange and Solvent/Medium Effects; Redox Reactions; The Taube Experiment Inner vs Outer Sphere Mechanisms for Electron Transfer. Radical Chain Reactions in Inorganic/Organomet. Chemistry Guest Lecturer- Francois Gabbai: Frustrated Lewis Pairs and Roles in Catalysis 5 6 7 F 1/28 M 1/31 W 2/2 8 F 2/4 9 10 M 2/7 W 2/9 11 12 13 14 F M W F 15 16 17 M 2/21 W 2/23 F 2/25 Organometallic Rxn Mech. Overview Ox. Add’n/Reductive Elimination: Classic Halpern Migratory Insertion: Classic Whitesides 18 19 20 M 2/28 W 3/2 F 3/4 Reactions at Metal Bound Ligands: Nucleophilic Attack at M-CO Electrophilic Attack; Pi Complexes MIDTERM EXAMINATION 21 M 3/7 22 23 W 3/9 F 3/11 Marcus Theory – Self Exchange Rates Guest Lecturer: D.J. Darensbourg Long Range Electron Transfer: D.J. Darensbourg Fluxional Organometallics M 3/14-18 SPRING BREAK 24 25 26 M 3/21 W 3/23 F 3/25 O.A./R.E.; Nuc. Displac; MCO Anions Nucleophilicity C-H Bond Activation—Sam project Insertion Mechanisms 27 28 29 M 3/28 W 3/30 F 4/1 Report for Classic Paper I (outside class) Report for Classic Paper II (outside class) Discussion in class. 2/11 2/14 2/16 2/18 CHEM 636 - SCHEDULE FOR LECTURES: (updated 3/21/2011) 30 M 4/4 31 32 33 34 35 W F M W F 4/6 4/8 4/11 4/13 4/15 Dawei – Kinetics and Mechanisms of Olefin insertion into M-H bonds JACS 1985, 107, 2670-2682. CO/Olefin Copolymerization Catalysis: Andy CO/Olefin Copolymerization Discussion Vitamin B-12 Mechanism: Wan-Chum Vitamin B-12 Discussion and other Bioinorganic Mechanisms Reading Assignment 36 37 38 39 M W F M W 4/18 4/20 4/22 4/25 4/27 Randara – Carbonic Anhydrase: Carbonic Anhydrase Discussion READING DAY – NO CLASS Nucleophilic attack on Metal-bound ligands Selected Topics 40 F 4/29 Selected Topics in Catalysis 41 M 5/2 Selected Topics 42 T 5/3 5/10 (redefined day=F) FINAL EXAM – 8:00 AM – 10:00 AM CHEM 636 – Inorg. React. Mech. Project Choices Dawei Feng – Asymmetric Hydrogenation (Halpern Science) Andrew Yeung – CO/Olefin Co-polymerization Catalysis Wan-Chun Chung – The Mechanisms of Vitamin B12 Randara Pulukkody – Carbonic Anhydrase Sam John Rajkumar – C-H Bond Activation