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45765-SE
Radical Metal Complex Chemistry, at the ACS National Meeeting, September 2006, San Francisco, CA

Klaus H. Theopold, University of Delaware

This grant provided partial support for a symposium entitled "Radical Metal Complex Chemistry", organized by Profs. Klaus H. Theopold (University of Delaware, USA), Vernon Gibson (Imperial College, London, UK) and Rinaldo Poli (Toulouse, France), and held at the 232nd National ACS Meeting in San Francisco, CA on September 10-14, 2006.

The subject of the symposium was the role that open shell metal complexes and ane-electron processes ('radical reactions') play in variuos metal mediated reactions. Thus, most reactivity studies of transition metal complexes involve elementary steps where the metal undergoes two-electron processes (ligand coordination, insertion, elimination, oxidative addition, …). This is so whether the metal complex is used in metal-assisted organic synthesis, in organometallic catalysis, in coordination polymerization, or the bioinorganic area. Although one-electron changes have been explored since the pioneering work of Halpern, Kochi, and Meyerstein, a more detailed investigation and application of this reactivity has witnessed a rapid growth only recently. Biochemists are increasingly finding radical centers in a variety of metalloproteins. Carbon, sulfur, and oxygen radicals all appear to play central roles in catalysis by various enzymes. A variety of technologically important process involve metals and radicals, involving both heterogeneous and homogeneous catalysis. Selective organic syntheses involving the use of one-electron transformations (e.g. the Nozaki-Hiyama-Kishi reaction) are increasingly used. Finally, controlled radical polymerizations where a transition metal complex exerts its regulating function via one-electron transformations are revolutionizing the polymer industry.

The program was as follows:

Sunday, September 10, AM

Radical Metal Complex Chemistry

8:25 – 8:30

Introductory remarks

8:30 – 9:00

Rinaldo Poli (CNRS-LCC, Toulouse)

Interplay of various one-electron processes in metal-mediated controlled radical polymerization: Contribution of coordination chemistry

9:00 – 9:30

Krzysztof Matyjaszewski (Carnegie Mellon U., Pittsburgh)

Rational selection of catalysts for atom transfer radical polymerization (ATRP) for various monomers and reaction media

9:30 – 10:00

Vernon C. Gibson (Imperial College, London),

One-electron Chemistry in Iron Imine Systems and the Influence of Metal Spin State on Catalytic Reactivity

Intermission

10:15 – 10:45

Paul J. Chirik (Cornell U., Ithaca)

Iron-catalyzed bond forming reactions: The importance of ligand-centered radicals

10:45 – 11:15

Karl Wieghardt (Max Planck Institute, Mόlheim)

Electronic structure of (pyridinediimine) iron complexes

11:15 – 11:45

Sandro Gambarotta (U. of Ottawa),

Metal to ethylene electron transfer during the oligomerization process: the fundamental problem of how to control activity and selectivity

Monday, September 11, AM

Radical Metal Complex Chemistry II

8:30 – 9:00

Bradford B. Wayland (U. of Pennsylvania, Philadelphia)

Group Nine Metal-Centered Radical and Organo-Metal Pathways for Controlled Radical Polymerization of Olefins

9:00 – 9:30

Jack R. Norton (Columbia U., New York)

Applications of hydrogen atom transfer from transition metal hydrides

9:30 – 10:00

James M. Mayer (U. of Washington, Seattle)

Hydrogen atom transfer reactions of coordination complexes

Intermission

10:15 – 10:45

Klaus H. Theopold (U. of Delaware, Newark)

Proton Coupled Electron Transfer in Metal-Mediated C-H Activations

10:45 – 11:15

Robert M. Waymouth (Stanford U.)

Persistent effect in organometallic chemistry: Homolysis of weak M-X bonds derived from stable radicals

11:15 – 11:45

Odile Eisenstein (CNRS-LSDSMS, Montpellier)

C-H/C-M bond energy relationships from DFT calculations: reliable information on relative homolytic bond dissociation energies

Monday, September 11, PM

Radical Metal Complex Chemistry III

2:00 – 2:30

Kenneth G. Caulton (Indiana U., Bloomington)

Effect of single-electron increments: Impact on reactivity around the transition series

2:30 – 3:00

Daniel J. Mindiola (Indiana, U., Bloomington)

Terminal Titanium Alkylidene and Alkylidyne Functionalities Generated Indirectly Through a One-Electron Oxidation Step

3:00 – 3:30

Henry S. Rzepa (Imperial College, London),

Computational studies on Iron diimine complexes: understanding the role of metal spin state in catalytic polymerization

Intermission

3:45 – 4:15

Sason Shaik (Hebrew U. of Jerusalem),

Multi-state reactivity patterns of cytochrome P450 and nonheme oxidation catalysts

4:15 – 4:45

Andrew S. Borovik (U. of Kansas)

Reactivity of metal-oxo complexes generated from dioxygen activation

4:45 – 5:15

William B. Tolman (U. of Minnesota, Minneapolis)

Synthetic modeling of mono- and multicopper protein active Sites: Dioxygen activation and Cu-S chemistry

Tuesday, September 12, AM

Radical Metal Complex Chemistry IV

9:00 – 9:30

Lawrence Que (U. of Minnesota, Minneapolis),

Reactions of high-valent nonheme oxoiron complexes with hydrocarbons

9:30 – 10:00

Wonwoo Nam (Ewha Womans Univ, Seoul),

High-valent iron-oxo complexes of nonheme and heme ligands in oxidation reactions

10:00 – 10:30

George J. P. Britovsek (Imperial College, London)

Non-heme iron catalysts for the oxidation of alkanes

Intermission

10:45 – 11:15

Pier Giorgio Cozzi (U. of Bologna),

Catalytic enantioselective Reformatsky reactions promoted by M(Salen) metal complexes

11:15 – 11:45

Kazuhiko Takai (Okayama University, Japan)

Organic reactions initiated by one-electron transfer from chromium(II)"

11:45 – 12:15

Kevin M. Smith (U. of Prince Edward Island)

Evaluating Ligand Effects in the Reactivity of CpCr(LX) Complexes

Attendance was excellent and ranged between 50 and 250 people in the audience, depending on the session and time of day.

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