Chemistry 652 - - - ORGANOMETALLIC CHEMISTRY - - - Spring 2014

Instructor:

Prof. Klaus H. Theopold, 214 Lammot duPont Lab

e-mail: theopold@udel.edu

Class Schedule:

Tuesdays & Thursdays 11:00 AM - 12:15 PM in QDH 004 :-(

Books

Textbook: R. H. Crabtree, The Organometallic Chemistry of the Transition Metals, 5th edition, 2009. (ISBN 978-0-470-25762-3)

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, 2nd edition.

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

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

5. Kochi; Organometallic Mechanisms and Catalysis.

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

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

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

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

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

Examinations/Homework:

Midterm (in class, on Tuesday, April 15).

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 13).

Comprehensive final (to be scheduled).

Grading:

Midterm 30 %

Proposal/Reviews 30 %

Problem Sets 30 %

Final 10 %

Total: 100 %

Research Proposal

The year is 2020! 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 by the deadline (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.

Assignment: 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 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 - Main group organometallics.

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

 

Overheads shown in class:

Historic Landmarks in Organotransition Metal Chemistry

The 16 and 18 Electron Rule in Organometallic Chemistry and Homogeneous Catalysis

1H- and 13C-NMR shifts of typical organometallic compounds

Physical properties of selected homoleptic metal carbonyls

The effect of symmetry on the IR spectra of metal carbonyl complexes

Fluxionality of Trofimenko's complex as observed by variable temperature NMR - a coalescence phenomenon

Rotation of ethylene in CpRh(C2H4)2 as observed by variable temperature NMR

MO scheme of metallocenes (Cp2M)

Other resources:

download Problem Set #1

download key to Problem Set #1

download Problem Set #2

download key to Problem Set #2

download a copy of the CHEM 652 midterm from 2011

download a solution key for the CHEM 652 midterm from 2011

download a solution key for this year's CHEM 652 midterm

read a discussion of recent trends in organometallic chemistry

 

Theopold Group Home Page
* Chemistry Home Page * University of Delaware Home Page.