Chemistry 652 - - - ORGANOMETALLIC CHEMISTRY - - - Spring 2021

Instructor:

Prof. Klaus H. Theopold, 214 Lammot duPont Lab

e-mail: theopold@udel.edu

Class Schedule:

Tuesdays & Thursdays 2:00 PM - 3:15 PM via Zoom, for now.

Textbook: R. H. Crabtree, The Organometallic Chemistry of the Transition Metals, 7^th edition, 2019. (ISBN 978-1-118-13807-6)

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

1. John Hartwig, Organotransition Metal Chemistry - From Bonding to Catalysis , University Science Books, 2010

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

3. G. A. Spessard & G. L. Miessler; Organometallic Chemistry, 2^nd edition, 2010.

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

5. Kochi; Organometallic Mechanisms and Catalysis.

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

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

8. R. B. Jordan; Reaction Mechanisms of Inorganic and Organometallic Systems, 2^nd edition, 1998.

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

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

Examinations/Homework:

Midterm (during class, on Thursday, April 1).

A paper - in the form of a research proposal - see below for details (due on April 29).

Reviews of 4 proposals (due on next to last day of class, i.e. May 14).

Comprehensive final (on May 27, 1-3 pm, via Zoom).

Grading:

Midterm 30 %

Proposal/Reviews 30 %

Problem Sets 10 %

Final 30 %

Total: 100 %

The year is 2028! After completing your Ph.D. at the University of Delaware and a couple of years 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 - i.e., 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, anticipated results etc.)

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

Your proposal must be submitted electronically by the deadline (as a pdf file entitled 'yourlastname.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) peer-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.

Assignment: Write short (~ 200 words) critical reviews of your colleague's proposals and rank them in order of your preference for funding (i.e. assign rankings 1, 2, 3 and 4 - no ties allowed!). 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. I will forward your reviews - verbatim - to the proposal authors.

Approximate Class 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 - Other small molecule activation (N₂, CO₂, ...).

12 - Applications in organic synthesis (maybe? guest lectures??)