Chemistry of Catalytic Systems I

- Advanced Organometallic Chemistry -

Prof. Dr. D. Vogt Dr. H.C.L. Abbenhuis Dr. C. Mller

Course setup
1 Indtroduction, test, freshing up previous knowledge Tutorial: main group organometallics Tutorial: main group organometallics Paper presentations Tutorial: transition metal organometallics 6 Tutorial: transition metal organometallics Tutorial: transition metal organometallics Tutorial: transition metal organometallics Paper presentations Recapitulation & exam preparation

4 5

9 10

Course setup Advanced Organometallic Chemistry

1 2 General introduction, test History and trends in Organometallic Chemistry Polarity and reactivity of M-C bonds Preparation of Organometallic Compounds Handling of Organometallic Compounds Organometallic compounds in Nature Organometallic compounds in water Organolithium and Organomagnesium compounds 3 Organometallic chemistry of B, Al and Si Synthesis and structure Hydroboration, Hydrosilylation, MAO, MOCVD, Silicones, Silylenes versus Carbenes 4 Paper presentation

Course setup Advanced Organometallic Chemistry

5 Organotransition metal chemistry Bonding, e- - counting Thermodynamics of M-C bonds Ancillary ligands P-ligands O-ligands 6 Metal-hydrides Carbon monoxide, M-CO complexes Synthesis, characterization, bonding, reactivity 7

-Organyls
Alkyls, Aryls, Alkenyls, Acyls, synthesis, bonding, reactivity Metal-carbenes Metal-carbynes Synthesis, structure, reactivity

Course setup Advanced Organometallic Chemistry

8 C-C -coordination Polyenes Synthesis, reactivity, Cp-compounds, arenes 9 Paper presentation

10

Recapitulation

Information: http://edu.chem.tue.nl/6KM07/ http://edu.chem.tue.nl/6KM07/extra.htm

Recommended books for the course Chemistry of Catalytic Systems I Advanced Organometallic Chemistry

Ch. Elschenbroich, A. Salzer, Organometallics, A Concise Introduction, VCH-Weinheim (Euro 55,-). A.F. Hill, Organotransition Metal Chemistry, RSC

Chemistry of Catalytic Systems I

Organometallic Chemistry is the molecular basis of Homogeneous Catalysis.

This course deals with fundamentals of Organometallic Chemistry.

Polyolefins

Polymerization of Ethylene

Ethylene
C Zr Cl

Organometallic Catalyst
C Al

Polyethylene

Zirconocenedichloride

Methylaluminoxan (MAO)

The System Cp2ZrCl2 / MAO: a Homogeneous Catalyst for the polymerization of alkenes
Both transition-metal and main-group organometallic compounds are important for the generation of the active species!

C Zr Cl

C Al

Zirconocenedichloride

Methylaluminoxan (MAO)

Generation of the active species

1. Cl / CH3-exchange
C Cl Zr Al

Cl Al Zr C O

Generation of the active species

2. CH3- -abstraction

C Zr O

Al

+
Zr C

Al -

14 e- complex (cationic)

The active species at work

3. -coordination of ethylene to the electron deficient Zr-center

+
Zr

Al -

+
Al Zr

The active species at work

4. Insertion of ethylene into the Zr-carbon bond and chain growth

+
Zr

Al -

Zr

The active species at work

5. Chain termination, for example -H-elimination

+
Zr

+
Zr

The active species at work

catalyst activation

Zr

Cl Cl

Al

Al

Al

Al

Zr

CH3 + H3C MAO

Zirconocenedichloride

MAO

Polyethylene with Designer Catalysts

N Ni Br Br N

N Ni Br

N Br

N Ni Br

N Br

Polymer with short chain branches => soft, films soft, films highly branched polymer => rubber, elastic elastic

highly linear polymer => hard, fibers

This example of transition metal mediated polymerization of ethylene already covers very important aspects of Organometallic Chemsitry:

Organotransition metal complexes Main group organometallic compounds Metal-carbon bonds (synthesis, reactivity) 16 e- / 14 e- transition metal complexes

- coordination
Insertion of fragments into metal-carbon bonds

-H elimination