Principles of Transition Metal Chemistry (CHE 226)

Location Bainer 1132 Meeting Times Monday, Wednesday, Friday 12:10 pm – 1:00 pm Instructor Dr. Frank Osterloh Office: Chemistry 210; Laboratory: Chemistry Annex 2445/2468 Web: http://www-chem.ucdavis.edu/groups/osterloh/teaching.htm Contact: (530) 754-6242, Fax (530) 752-8995, [email protected] Teaching Assistant Khoi Nguyen, Room 211, [email protected]; office hours Mo 1-2 pm in Science Laboratory Teaching Building, room 1064 Prerequisite Course 124A or Equivalent (Symmetry, Molecular Geometry and Molecular Orbital Theory of Bonding in Transition Element Compounds) Lecture Materials posted at http://www-chem.ucdavis.edu/groups/osterloh/teaching.htm Software Gmelin Database (Beilstein Commander), Cambridge Crystal Structure Database (Conquest 1.4), Chemical Abstracts Database (SciFinder): Software and Files are available on computers in room Chem annex 3450.

Books (recommended) D. F. Shriver, P. Atkins, Inorganic Chemistry, 3rd Edition, W. H. Freeman and Company, New York, 1999. $109.65 Hardcover, ISBN 0716736241 S. F. A. Kettle, Physical Inorganic Chemistry: A Coordination Chemistry Approach, Oxford Univ. Press, 2000, $45 Paperback. ISBN 0198504047 R. H. Crabtree, The Organometallic Chemistry of the Transition Metals, Second Edition, John Wiley & Sons, New York, 1994. $74.95 Hardcover. ISBN 0471592404 C. E. Housecroft, A. G. Sharpe, Inorganic Chemistry, Prentice Hall, First Edition, 2001, Paperback, ISBN 0582-31080-6, $103 J. E. Huheey, E. A. Keiter, R. L. Keiter , Inorganic Chemistry: Principles of Structure and Reactivity (4th Edition), Benjamin Cummings; 1997, ISBN 006042995X, $134

Journals dealing with inorganic chemistry see webpage at http://www-chem.ucdavis.edu/groups/osterloh/teaching.htm

Examinations 7-10 Homework Assignments (due always at the beginning of Friday class), One Midterm (50 min), one Final Examination (2h). Midterm will be on Friday, October 28th during normal lecture hours. Final Examination (2h) will be on Friday, December 9th, 4:00 - 6:00 pm, in room 172 (chemistry).

Grades The homework counts 20%, the midterm counts 30%, the final exam counts 50% towards the final grade. Course Outline September Friday (30.) 1. week Chapter I. Introduction Periodic Table; d- and f- orbitals

October Monday (3., 10., 17., 24, 31.) Wednesday (5., 12., 19., 26.) Friday ( 7., 14., 21., 28.) 2. week Geometry of TM Complexes, Electron Configurations, Oxidation Chapter II. Bonding in TM Examples of ligands States, Isomerism. Complexes From Ligand Field Nomenclature Theory to Molecular Orbital Theory. 3. week MO Theory of Octahedral MO Theory of Tetrahedral π Donor/π Acceptor Ligands Complexes. Complexes.

4. week Chapter III. Electronic Properties Ionic Radii, Effects of Spin States Ligand Field Stabilization High and Low Spin Complexes, on Physiological Function: Example Energy, Planar Geometries, Diamagnetism, Paramagnetism, Hemoglobin. Jahn-Teller Theorem. Curie Law, Ferro-, Antiferro-, Ferrimagnetism. 5. week Stereochemically Non-Rigid Electronic Absorption, Midterm Molecules: Tautomerism, Spectroscopy/Excited States, Fluxionality and its Detection. Spectrochemical Series. 6. week Electronic Configurations/Terms, Excitation Rules

November Monday (7., 14., 21., 28.) Wednesday (2.,9.,16.,23., 30.) Friday (4., 11.,18.,25.) 6. week Chapter IV. Reactions of Ligand Substitution Reactions: Transition Metal Complexes Associative vs. Dissociative Labile and Inert Complexes, Mechanism, Trans Effect Thermodynamic Stability, Hard and Soft Ligands, Chelate Effect. 7. week Transition State Theory - Inner Chapter V. Sphere vs Outer Sphere Electron Metal Clusters Transfer, Markus Theory and its Metal Metal bonding, bond order, Veterans Day Applications. Redox Cluster Synthesis. Potential/Latimer Diagrams 8. week Cluster Shapes and Electron Chapter VI. Carbonyl-, Phosphine-, Olefin-, Counting Organometallic Chemistry Allyl-, Dienyl-, Aromatic-, Ligand Types, Nomenclature, Carbene- Complexes Synthesis, Historical Background, 18-Electron Rule. 9. week Alkylidene-Complexes, Hydrogen- Fundamental Reactions and and Hydride- Complexes. Mechanisms: Substitution, Thanksgiving Insertion, Oxidative Addition, Reductive Elimination. 10. week Homogeneous Catalysis: Fischer Monsanto Process, Tropsch Hydroformulation, Wacker Process, Olefin Hydrogenation.

December Monday (5.) Wednesday (7.) Friday (2., 9.) 10. week Asymmetric Catalysis: L-DOPA Synthesis. 11. week Chapter VII. Transition Metal Questions/Answers Final Examination Nanoparticles Synthesis, Structural and Chemical Properties.

Suggested Reading for CHE226 D. F. Shriver, P. Atkins, Inorganic Chemistry, 3rd Edition, W. H. Freeman and Company, New York, 1999. S. F. A. Kettle, Physical Inorganic Chemistry: A Coordination Chemistry Approach, Oxford Univ. Press, 2000. R. H. Crabtree, The Organometallic Chemistry of the Transition Metals, Second Edition, John Wiley & Sons, New York, 1994.

Introduction to Coordination Compounds, Electron Configurations, Oxidation Chapter II. Electronic Structure Molecular Symmetry (Symmetry States, Stereochemistry. Crystal Field-, Ligand Field-, Operations, Point Groups) Ch.7.1-7.3 Ch. 3 Ch. 2 Molecular Orbital Theory. Ch.1 and Ch.4 Ch. 1 and 2 Ch.1 Ch.7.4-7.6 Ch. 7 MO Theory of Bonding: LCAO for LCAO for Tetrahedral Complexes. π Donor/π Acceptor Ligands Octahedral Complexes. Ch. 3.7.-3.9; 7.4-7.6 Ch. 7 Ch.7.6 Ch. 3.7.-3.9; 7.4-7.6 Ch. 7 Chapter III. Electronic Properties: Ionic Radii, Effects of Spin States on Ligand Field Stabilization Energy, High and Low Spin Complexes Physiological function: Hemoglobin. Structure Preference Energies, Diamagnetism/Paramagnetism - Curie Ch.19.3 Ch. 13.2; 16.2 Planar Geometries, Law, Ferro-/Antiferro-/Ferrimagnetism. Jahn-Teller Theorem. Ch.7.4 Ch. 9 Ch.7.5 Ch. 7 Stereochemically Non-Rigid Molecules: Electronic Absorption, Electronic Configurations/Terms, Tautomerism, Fluxionality and its Spectroscopy/Excited States, Excitation Rules Detection. Spectrochemical Series. Ch.13.1-13.3 Ch. 8 Ch.7.1 Ch. 14.8 Pages 244-250 Ch.7.4; 13.1-13.3 Ch. 8

Chapter IV. Transition State Theory - Inner Sphere Redox Potential/Latimer Diagrams, Reactions of Transition Metal vs Outer Sphere Electron Transfer, Biological Electron Transfer: Complexes Markus Theory and its Applications. Ferredoxins, Plastocyanin. Labile and Inert Complexes, Ch.14.13 Ch. 14.2 Ch.6.8; 19.6-19.7 Thermodynamic Stability, Hard and Soft Ligands, Chelate Effect. Ch.7.6; 13.1-13.3 Ligand Substitution Reactions: Chapter V. Chapter VI. Associative vs. Dissociative Mechanism, Metal Clusters: Metal-Metal bonds, Organometallic Chemistry Trans Effect Cluster Synthesis, Cluster Shapes and Ligand Types, Nomenclature, Ch.14 Ch. 14 Ch.4.3,4.4 Electron Counting, Wade Rules, Synthesis, Historical Background, Polyhedral Skeletal Electron Pair 18-Electron Rule. Theory (PSEPT). Ch.16 Ch. 3,4,5 Ch.16.10 Ch. 15 Ch. 13 Carbonyl-, Phosphine-, Olefin-, Allyl-, Alkylidene-Complexes, Hydrogen- and Fundamental Reactions and Dienyl-, Aromatic-, Carbene- Hydride- Complexes. Mechanisms: Substitution, Insertion, Complexes. Ch.16 Ch. 3,4,5 Oxidative Addition, Reductive Ch.16 Ch. 3,4,5; Ch.17 Ch.10.9 Elimination. Ch.14 Ch.6 ,7,8 Homogeneous Catalysis: Fischer Monsanto Process, Hydroformulation, Asymmetric Catalysis: L-DOPA Tropsch. Ch.17 Ch.9 Wacker Olefin Hydroformulation. Synthesis. Ch.17 Ch.9 Ch.17 Ch.9.2