Chemistry 652 - - - ORGANOMETALLIC CHEMISTRY - - - Spring 2011

Instructor:

Prof. Klaus H. Theopold, 214 Lammot du Pont Lab (Saturdays) or 102C Brown Lab

e-mail: theopold@udel.edu

Class Schedule:

Tuesdays & Thursdays 11:00 AM - 12:15 PM in BRL 207

Textbook: John Hartwig, Organotransition Metal Chemistry - From Bonding to Catalysis , University Science Books, 2010 (ISBN 978-1-891389-53-5)

The following books provide more information and/or different viewpoints and may be found in the Library.

1. R. H. Crabtree, The Organometallic Chemistry of the Transition Metals, 4^rd edition.

2. Collman, Hegedus, Norton, Finke; Principles and Applications of Organotransition Metal Chemistry, 2^nd edition.

3. Elschenbroich; Salzer; Organometallics, 2^nd or 3^rd edition.

4. Kochi; Organometallic Mechanisms and Catalysis.

5. Parshall, Ittel; Homogeneous Catalysis, 2^nd edition.

6. Atwood; Inorganic and Organometallic Reaction Mechanisms, 2^nd edition.

7. Huheey; Keiter, and Keiter; Inorganic Chemistry, 4^th edition

8. Cotton, Wilkinson; Advanced Inorganic Chemistry, 6^th edition.

Examinations/Homework:

Midterm (in class, on Thursday, April 7).

A paper - in the form of a research proposal - see below for details (due on April 28).

Reviews of 4 proposals (due on next to last day of class, i.e. May 12).

Comprehensive final (3 hours - to be scheduled).

Grading:

Midterm 30 %

Proposal/Reviews 30 %

Final 40 %

Total: 100 %

The year is 2017! After completing your Ph.D. at the University of Delaware and a year of postdoctoral research with the famous Prof. Noitall at Ivy U, you have just accepted an assistant professorship at Utopia State University. The chairperson of your department encourages you to secure external funding for your budding research effort. Now what?

Write a short proposal - e.g., to the Petroleum Research Fund of the American Chemical Society, an organization which gives out small "starter grants" - outlining a research project in organometallic chemistry. In no more than 5 single-spaced pages (or the equivalent), this should contain:

- a title and your name

- an abstract (no more than 100 words - a self-contained summary of your proposal)

- an introduction (background, prior work, significance of your project)

- a description of the research (details of representative experiments to be performed, methods of analysis, expected results etc.)

- a bibliography (references to prior work, see J. Am. Chem. Soc. for style).

Your proposal must be submitted electronically (preferably as a pdf file entitled 'yourname.pdf') to: theopold@udel.edu.

Review: Shortly after having submitted your proposal, your prayers to the gods of funding and your teaching schedule are rudely interrupted by the receipt (via e-mail) of several research proposals written by your peers at other institutions of higher learning all across the nation. ACS-PRF is seeking your (anonymous) evaluation of these proposals (by scientific merit, significance, chance of success, technical quality of proposal, etc.). Your comments and ratings will aid the program director in deciding which proposals will be funded this year. Unfortunately, there is not enough money available to fund all proposal (surprise!). Past experience has shown that only ca 30 % of all requests for funding can be accommodated.

Write short critical reviews of several of your colleague's proposals and rank them in order of your preference for funding (i.e. assign ranks 1, 2, 3 and 4). Your reviews must justify your rank order, and in the best of all worlds, they should also be helpful to the authors in rewriting their proposal for next year's competition.

Approximate Syllabus:

1 - Introduction: History, 18-electron rule, ligands

2 - Ligands cont’d, characterization & fluxionality

3 - Reductive Elimination/Oxidative Addition

4 - Migratory Insertion/Elimination

5 - Nucleophilic/Electrophilic attack on coordinated ligands

6 - Metal-carbon Multiple Bonds, Olefin Metathesis, ROMP

7 - CO-chemistry, hydroformylation, Fischer-Tropsch process, etc.

8 - Olefin-chemistry, isomerization, hydrogenation, polymerization

9 - oxidation, high-oxidation state organometallics, O₂-activation.

10 - C-H activation

11 - Main group organometallics.

12 - Applications in organic synthesis